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DOE OSTI2023

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Bench-Scale Evaluation of the Genifuel Hydrothermal Processing Technology for Wastewater Solids

Hydrothermal Liquefaction (HTL) and Catalytic Hydrothermal Gasification (CHG) proof-of-concept bench-scale tests were performed to assess the potential of the Genifuel hydrothermal process technology for handling municipal wastewater sludge. HTL tests were conducted at 300-350°C and 20 MPa on three different feeds: primary sludge (11.9 wt% solids), secondary sludge (9.7 wt% solids), and post-digester sludge (also referred to as digested solids) (16.0 wt% solids). Corresponding CHG tests were conducted at 350°C and 20 MPa on the HTL aqueous phase output using a ruthenium based catalyst. A comprehensive analysis of all feed and effluent phases was also performed. Total mass and carbon balances closed to within ± 15% in all but one case. Biocrude yields from HTL tests were 37%, 25%, and 34% for primary sludge, secondary sludge, and digested solids feeds, respectively. The biocrude yields accounted for 59%, 39%, and 49% of the carbon in the feed for primary sludge, secondary sludge, and digested solids feeds, respectively. Biocrude composition and quality were comparable to that seen with biocrudes generated from algae feeds. Subsequent hydrotreating (i.e., upgrading) of the biocrude produced from primary sludge and digested solids resulted in a product with comparable physical and chemical properties to petroleum crude oil. CHG product gas consisted primarily of methane, with methane yields (relative to CHG input) on a carbon basis of 47%, 61%, and 64% for aqueous feeds that were the output of HTL tests with primary sludge, secondary sludge, and digested solids, respectively. Siloxane concentrations in the CHG product gas were below the detection limit and well below fuel input composition limits set by several engine manufacturers. Relative to that of the sludge feeds, the HTL-CHG process resulted in a reduction in chemical oxygen demand (COD) of greater than 99.9% and a reduction in residual solids for disposal of 94-99%. The test results, as a whole, support further long term testing in a larger scale integrated system that is representative of what would be installed at a water resource recovery facility (WRRF) in order to fully assess the technical and economic viability of this technology for wastewater sludge treatment.

biocrude↗

DOE OSTI2013

Evaluating the biogas potential of the dry fraction from pretreatment of food waste from households

Highlights: ► A novel approach for biogas production from a waste fraction that today is incinerated. ► Biogas production is possible in spite of the impurities of the waste. ► Tracer studies are applied in a novel way. ► Structural material is needed to improve the flow pattern of the waste. ► We provide a solution to biological treatment for the complex waste fraction. - Abstract: At the waste handling company NSR, Helsingborg, Sweden, the food waste fraction of source separated municipal solid waste is pretreated to obtain a liquid fraction, which is used for biogas production, and a dry fraction, which is at present incinerated. This pretreatment and separation is performed to remove impurities, however also some of the organic material is removed. The possibility of realising the methane potential of the dry fraction through batch-wise dry anaerobic digestion was investigated. The anaerobic digestion technique used was a two-stage process consisting of a static leach bed reactor and a methane reactor. Treatment of the dry fraction alone and in a mixture with structural material was tested to investigate the effect on the porosity of the leach bed. A tracer experiment was carried out to investigate the liquid flow through the leach beds, and this method proved useful in demonstrating a more homogenous flow through the leach bed when structural material was added. Addition of structural material to the dry fraction was needed to achieve a functional digestion process. A methane yield of 98 m{sup 3}/ton was obtained from the dry fraction mixed with structural material after 76 days of digestion. This was in the same range as obtained in the laboratory scale biochemical methane potential test, showing that it was possible to extract the organic content in the dry fraction in this type of dry digestion system for the production of methane.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Seeking to enhance the bioenergy of municipal sludge: Effect of alkali pre-treatment and soluble organic matter supplementation

Highlights: • Bioenergy of municipal waste has been studied. •Glycerine addition (GA) improved the methane production (MP). • GA not affected the pH sludge and organic matter content of the effluent. • GA not affected the stability of the reactor: ratio volatile fatty acid/Alkalinity was <0.4. • Alkali pre-treatment improved the sludge biodegradability. - Abstract: The aim of this research is to enhance the mesophilic anaerobic digestion of municipal sludge from Cadiz-San Fernando (Spain) wastewater treatment plant at 20 days hydraulic retention time (HRT). Two different strategies were tested to improve the process: co-digestion with the addition of soluble organic matter (1% v/v); and alkali sludge pre-treatment (NaOH) prior to co-digestion with glycerine (1% v/v). Methane production (MP) was substantially enhanced (from 0.36 ± 0.09 L CH{sub 4} l/d to 0.85 ± 0.16 L CH{sub 4} l/d), as was specific methane production (SMP) (from 0.20 ± 0.05 L CH{sub 4}/g VS to 0.49 ± 0.09 L CH{sub 4}/g VS) when glycerine was added. The addition of glycerine does not seem to affect sludge stability, the quality of the effluent in terms of pH and organic matter content, i.e. volatile fatty acids (VFA), soluble organic matter and total volatile solid, or process stability (VFA/Alkalinity ratio < 0.4). Alkali pre-treatment prior to co-digestion resulted in a high increase in soluble organic loading rates (more than 20%) and acidification yield (more than 50%). At 20 days HRT, however, it led to overload of the system and total destabilization of the mesophilic anaerobic co-digestion of sewage sludge and glycerine.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Enhancing the Quantification of Critical Elements in WTE and Coal Ash via Alkaline Fusion: Superiority of Lithium Metaborate (LiBO 2 )

Ashes generated from coal combustion, as well as waste incineration, can be a potential source of critical elements necessary for the ongoing transition towards electrification and greener energy technologies. For the quantification of critical elements, traditional methods such as acid digestion are time-intensive and can fail to dissolve critical elements in refractory minerals. One potential solution is to adopt alkaline fusion for faster, total digestion. However, the role of flux choice and the subsequent digestion efficiency (DE) is unknown. Here, we report a systematic investigation on the feasibility of alkaline fusion with Lithium Metaborate (LiBO 2 ) and Lithium Tetraborate (Li 2 B 4 O 7 ) as fluxes for the digestion of two standard reference materials (BCR 176R and SRM 1633c). Our findings suggest that LiBO 2 yields higher DE values than Li 2 B 4 O 7 for several critical REEs and volatiles, such as Pb and Cd. Specifically, for REEs in SRM 1633c, the DE values with LiBO 2 are, on average, ~16 percent higher than those with Li 2 B 4 O 7 . Similarly, for Pb and Cd in BCR 176R, the DE values with LiBO 2 are ~20 percent higher than with Li 2 B 4 O 7 . These results suggest that LiBO 2 is a superior flux for rapid ash digestion.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2012

Tank 40 Final SB7b Chemical Characterization Results

A sample of Sludge Batch 7b (SB7b) was taken from Tank 40 in order to obtain radionuclide inventory analyses necessary for compliance with the Waste Acceptance Product Specifications (WAPS). The SB7b WAPS sample was also analyzed for chemical composition including noble metals and fissile constituents, and these results are reported here. These analyses along with the WAPS radionuclide analyses will help define the composition of the sludge in Tank 40 that is currently being fed to the Defense Waste Processing Facility (DWPF) as SB7b. At the Savannah River National Laboratory (SRNL) the 3-L Tank 40 SB7b sample was transferred from the shipping container into a 4-L high density polyethylene bottle and solids were allowed to settle over the weekend. Supernate was then siphoned off and circulated through the shipping container to complete the transfer of the sample. Following thorough mixing of the 3-L sample, a 558 g sub-sample was removed. This sub-sample was then utilized for all subsequent analytical samples. Eight separate aliquots of the slurry were digested, four with HNO 3 /HCl (aqua regia) in sealed Teflon® vessels and four with NaOH/Na 2 O 2 (alkali or peroxide fusion) using Zr crucibles. Two Analytical Reference Glass - 1 (ARG-1) standards were digested along with a blank for each preparation. Each aqua regia digestion and blank was diluted to 1:100 mL with deionized water and submitted to Analytical Development (AD) for inductively coupled plasma - atomic emission spectroscopy (ICP-AES) analysis, inductively coupled plasma - mass spectrometry (ICP-MS) analysis, atomic absorption spectroscopy (AA) for As and Se, and cold vapor atomic absorption spectroscopy (CV-AA) for Hg. Equivalent dilutions of the alkali fusion digestions and blank were submitted to AD for ICP-AES analysis. Tank 40 SB7b supernate was collected from a mixed slurry sample in the SRNL Shielded Cells and submitted to AD for ICP-AES, ion chromatography (IC), total base/free OH - /other base, total inorganic carbon/total organic carbon (TIC/TOC) analyses, and Cs-137 gamma scan. Weighted dilutions of slurry were submitted for IC, TIC/TOC, and total base/free OH - /other base analyses. Activities for U-233, U-235, and Pu-239 were determined from the ICP-MS data for the aqua regia digestions of the Tank 40 WAPS slurry using the specific activity of each isotope. The Pu-241 value was determined from a Pu-238/-241 method developed by SRNL AD and previously described. The following conclusions were drawn from the analytical results reported here: (1) The ratios of the major elements for the SB7b WAPS sample are different from those measured for the SB7a WAPS sample. There is less Al and Mn relative to Fe than the previous sludge batch. (2) The elemental composition of this sample and the analyses conducted here are reasonable and consistent with DWPF batch data measurements in light of DWPF pre-sample concentration and SRAT product heel contributions to the DWPF SRAT receipt analyses. The element ratios for Al/Fe, Ca/Fe, Mn/Fe, and U/Fe agree within 10% between this work and the DWPF Sludge Receipt and Adjustment Tank (SRAT) receipt analyses. (3) Sulfur in the SB7b WAPS sample is 82% soluble, slightly less than results reported for SB3, SB4, and SB6 samples but unlike the 50% insoluble sulfur observed in the SB5 WAPS sample. In addition, 23% of the soluble sulfur is not present as sulfate in SB7b. (4) The average activities of the fissile isotopes of interest in the SB7b WAPS sample are (in μCi/g of total dried solids): 4.22E-02 U-233, 6.12E-04 U-235, 1.08E+01 Pu-239, and 5.09E+01 Pu-241. The full radionuclide composition will be reported in a future document. (5) The fission product noble metal and Ag concentrations appear to have largely peaked in previous DWPF sludge batches, with the exception of Ru, which still shows a slight increase in SB7b.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Comparison of autohydrolysis and ionic liquid 1-butyl-3-methylimidazolium acetate pretreatment to enhance enzymatic hydrolysis of sugarcane bagasse

The aim of this work was to evaluate the efficiency of an ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) pretreatment (110 C for 30 min) in comparison to high severity autohydrolysis pretreatment in terms of delignification, cellulose crystallinity and enzymatic digestibility. The increase in severity of autohydrolysis pretreatment had positive effect on glucan digestibility, but was limited by the crystallinity of cellulose. [C4mim][OAc] pretreated sugarcane bagasse exhibited a substantial decrease in lignin content, reduced cellulose crystallinity, and enhanced glucan and xylan digestibility. Glucan and xylan digestibility was determined as 97.4% and 98.6% from [C4mim][OAc] pretreated bagasse, and 62.1% and 57.5% from the bagasse autohydrolyzed at 205 C for 6 min, respectively. The results indicated the improved digestibility and hydrolysis rates after [C4mim][OAc] pretreatment when compared against a comparable autohydrolyzed biomass.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Ammonia pretreatment of corn stover enables facile lignin extraction

Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion—an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 °C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight ( M w ) of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA-pretreated/NaOH-extracted corn stover were higher by ~80% and ~60%, respectively, compared to untreated corn stover at 1% solids loadings. For digestions at 20% solids, a benefit of NaOH extraction is realized in achieving ~150 g/L of total monomeric sugars (glucose, xylose, and arabinose) in the enzymatic hydrolysates from AA-pretreated/NaOH-extracted corn stover. Altogether, this process enables facile lignin extraction in tandem with a leading thermochemical pretreatment approach, demonstrating excellent retention of highly digestible polysaccharides in the solid phase and a highly depolymerized, soluble lignin-rich stream.

09 BIOMASS FUELS↗

DOE OSTI2024

Soil application of high-lignin fermentation byproduct to increase the sustainability of liquid biofuel production from crop residues

When digestates from anaerobic digestion of crop residues are added to soil, a considerable body of information indicates that soil organic carbon (SOC) levels are comparable to those when crop residues are left in the field. This occurs although the amount of digestate added to soil is diminished by digestion and implies that digestion increases the proportion of carbon inputs stabilized as SOC. Here we examine the likelihood and implications of these features being manifested for soil application of high lignin-fermentation byproduct (HLFB) from liquid biofuel production. We show that steady-state SOC levels are much less sensitive to crop residue removal with HLFB return than without it, and provide an example supporting the feasibility of foregoing process energy and coproduct revenue when HLFB is returned to the soil. Informed by this review and analysis, we expect with moderate confidence that long-term SOC levels for soils amended with HLFB from some liquid cellulosic biofuel processes will not be substantially lower than those occurring when crop residues are left in the field. We have high confidence that the economically optimum rate of fertilizer nitrogen (N) application and N 2 O emissions will be lower at most sites for HLFB return to the soil than if crop residues were left in the field. We estimate that the per hectare N demand for processing crop residues to liquid biofuels is about a third of the per hectare demand for crop production, giving rise to an opportunity to use N twice and thereby realize cost savings and environmental benefits. These observations support but do not prove the hypothesis that a ‘win-win’ is possible wherein large amounts of liquid biofuel feedstock can be obtained from crop residues while improving the economics and sustainability of food and feed production. A research agenda aimed at exploring and testing this hypothesis is offered.

09 BIOMASS FUELS↗

DOE OSTI2017

Impact of Dietary Resistant Starch on the Human Gut Microbiome, Metaproteome, and Metabolome

ABSTRACT Diet can influence the composition of the human microbiome, and yet relatively few dietary ingredients have been systematically investigated with respect to their impact on the functional potential of the microbiome. Dietary resistant starch (RS) has been shown to have health benefits, but we lack a mechanistic understanding of the metabolic processes that occur in the gut during digestion of RS. Here, we collected samples during a dietary crossover study with diets containing large or small amounts of RS. We determined the impact of RS on the gut microbiome and metabolic pathways in the gut, using a combination of “omics” approaches, including 16S rRNA gene sequencing, metaproteomics, and metabolomics. This multiomics approach captured changes in the abundance of specific bacterial species, proteins, and metabolites after a diet high in resistant starch (HRS), providing key insights into the influence of dietary interventions on the gut microbiome. The combined data showed that a high-RS diet caused an increase in the ratio of Firmicutes to Bacteroidetes , including increases in relative abundances of some specific members of the Firmicutes and concurrent increases in enzymatic pathways and metabolites involved in lipid metabolism in the gut. IMPORTANCE This work was undertaken to obtain a mechanistic understanding of the complex interplay between diet and the microorganisms residing in the intestine. Although it is known that gut microbes play a key role in digestion of the food that we consume, the specific contributions of different microorganisms are not well understood. In addition, the metabolic pathways and resultant products of metabolism during digestion are highly complex. To address these knowledge gaps, we used a combination of molecular approaches to determine the identities of the microorganisms in the gut during digestion of dietary starch as well as the metabolic pathways that they carry out. Together, these data provide a more complete picture of the function of the gut microbiome in digestion, including links between an RS diet and lipid metabolism and novel linkages between specific gut microbes and their metabolites and proteins produced in the gut.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2017

Tank 40 final sludge batch 9 chemical and fissile radionuclide characterization results

A sample of Sludge Batch (SB) 9 was pulled from Tank 40 in order to obtain radionuclide inventory analyses necessary for compliance with the Waste Acceptance Product Specifications (WAPS)i. The SB9 WAPS sample was also analyzed for chemical composition, including noble metals, and fissile constituents, and these results are reported here. These analyses along with the WAPS radionuclide analyses will help define the composition of the sludge in Tank 40 that is fed to the Defense Waste Processing Facility (DWPF) as SB9. At the Savannah River National Laboratory (SRNL), the 3-L Tank 40 SB9 sample was transferred from the shipping container into a 4-L high density polyethylene bottle and solids were allowed to settle. Supernate was then siphoned off and circulated through the shipping container to complete the transfer of the sample. Following thorough mixing of the 3-L sample, a 547 g sub-sample was removed. This sub-sample was then utilized for all subsequent slurry sample preparations. Eight separate aliquots of the slurry were digested, four with HNO3/HCl (aqua regiaii) in sealed Teflon® vessels and four with NaOH/Na2O2 (alkali or peroxide fusioniii) using Zr crucibles. Three Analytical Reference Glass – 1iv (ARG-1) standards were digested along with a blank for each preparation. Each aqua regia digestion and blank was diluted to 1:100 with deionized water and submitted to Analytical Development (AD) for inductively coupled plasma – atomic emission spectroscopy (ICP-AES) analysis, inductively coupled plasma – mass spectrometry (ICP-MS) analysis, atomic absorption spectroscopy (AA) for As and Se, and cold vapor atomic absorption spectroscopy (CV-AA) for Hg. Equivalent dilutions of the alkali fusion digestions and blank were submitted to AD for ICP-AES analysis. Tank 40 SB9 supernate was collected from a mixed slurry sample in the SRNL Shielded Cells and submitted to AD for ICP-AES, ion chromatography (IC), total base/free OH-/other base, total inorganic carbon/total organic carbon (TIC/TOC) analyses. Weighted dilutions of slurry were submitted for IC, TIC/TOC, and total base/free OH-/other base analyses. Activities for U-233, U-235, and Pu-239 were determined from the ICP-MS data for the aqua regia digestions of the SB9 WAPS slurry using the specific activity of each isotope. The Pu-241 value was determined from a Pu-238/-241 method developed by SRNL AD and previously described.v

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

CEM MARS 6 Microwave Incident

A fire occurred in a CEM MARS 6 analytical microwave during microwave-assisted, acid digestion of a soil sample in a Research and Development (R&D) laboratory. The soil sample had been pretreated at 550°C for approximately 4 hours in a furnace prior to digesting in the microwave. Less than 1-gram aliquots of the pretreated soil sample were placed into separate microwave reaction vessels along with an acid mixture used for digestion. The microwave was used to facilitate digestion of the samples. Microwave reaction vessels were loaded with acid and soil samples, sealed in cassettes, and the cassettes placed onto a microwave carousel. A temperature probe that senses the reaction temperature during the run was inserted into the Reference Cell thermowell. The contents of the Reference Cell were identical to the contents of the other reaction cells. The researcher initiated the run and then left the laboratory to perform other work. Upon returning to check the digestion run, flames and smoke were observed originating from the microwave. The researcher exited the lab, immediate emergency actions were taken, and the local fire department responded and extinguished the fire. No personnel were injured, and no facility structural damage occurred. The affected microwave is a total loss. The fire investigation revealed the most credible cause of the fire is an incompatible temperature probe that did not accurately measure temperature of the liquid phase of the Reference sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13 C 18 O 16 O 2 in carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47 –temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47 –temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO 2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ 47 is a subject that warrants further investigation.

58 GEOSCIENCES↗

DOE OSTI2015

How chip size impacts steam pretreatment effectiveness for biological conversion of poplar wood into fermentable sugars

We report that woody biomass is highly recalcitrant to enzymatic sugar release and often requires significant size reduction and severe pretreatments to achieve economically viable sugar yields in biological production of sustainable fuels and chemicals. However, because mechanical size reduction of woody biomass can consume significant amounts of energy, it is desirable to minimize size reduction and instead pretreat larger wood chips prior to biological conversion. To date, however, most laboratory research has been performed on materials that are significantly smaller than applicable in a commercial setting. As a result, there is a limited understanding of the effects that larger biomass particle size has on the effectiveness of steam explosion pretreatment and subsequent enzymatic hydrolysis of wood chips. To address these concerns, novel downscaled analysis and high throughput pretreatment and hydrolysis (HTPH) were applied to examine whether differences exist in the composition and digestibility within a single pretreated wood chip due to heterogeneous pretreatment across its thickness. Heat transfer modeling, Simons’ stain testing, magnetic resonance imaging (MRI), and scanning electron microscopy (SEM) were applied to probe the effects of pretreatment within and between pretreated wood samples to shed light on potential causes of variation, pointing to enzyme accessibility (i.e., pore size) distribution being a key factor dictating enzyme digestibility in these samples. Application of these techniques demonstrated that the effectiveness of pretreatment of Populus tremuloides can vary substantially over the chip thickness at short pretreatment times, resulting in spatial digestibility effects and overall lower sugar yields in subsequent enzymatic hydrolysis. Finally, these results indicate that rapid decompression pretreatments (e.g., steam explosion) that specifically alter accessibility at lower temperature conditions are well suited for larger wood chips due to the non-uniformity in temperature and digestibility profiles that can result from high temperature and short pretreatment times. Furthermore, this study also demonstrated that wood chips were hydrated primarily through the natural pore structure during pretreatment, suggesting that preserving the natural grain and transport systems in wood during storage and chipping processes could likely promote pretreatment efficacy and uniformity.

09 BIOMASS FUELS↗

DOE OSTI2013

The influence of slaughterhouse waste on fermentative H{sub 2} production from food waste: Preliminary results

Highlights: • Co-digestion process finalized to bio-H{sub 2} production was tested in batch tests. • Slaughterhouse waste (SHW) and food waste (FW) were co-digested in different proportions. • The presence of SHW affected the H{sub 2} production from FW. • When SHW ranging between 50% and 70% the H{sub 2} production is improved. • SHW percentages above 70%, led to a depletion in H{sub 2} production. - Abstract: The aim of this study was to evaluate the influence of slaughterhouse waste (SHW; essentially the skin, fats, and meat waste of pork, poultry, and beef) in a fermentative co-digestion process for H{sub 2} production from pre-selected organic waste taken from a refectory (food waste [FW]). Batch tests under mesophilic conditions were conducted in stirred reactors filled with different proportions of FW and SHW. The addition of 60% and 70% SHW to a mixture of SHW and FW improved H{sub 2} production compared to that in FW only, reaching H{sub 2}-production yields of 145 and 109 ml gVS{sub 0}{sup -1}, respectively, which are 1.5–2 times higher than that obtained with FW alone. Although the SHW ensured a more stable fermentative process due to its high buffering capacity, a depletion of H{sub 2} production occurred when SHW fraction was higher than 70%. Above this percentage, the formation of foam and aggregated material created non-homogenous conditions of digestion. Additionally, the increasing amount of SHW in the reactors may lead to an accumulation of long chain fatty acids (LCFAs), which are potentially toxic for anaerobic microorganisms and may inhibit the normal evolution of the fermentative process.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2023

Herbivorous Fish Microbiome Adaptations to Sulfated Dietary Polysaccharides

Marine herbivorous fish that feed primarily on macroalgae, such as those from the genus Kyphosus, are essential for maintaining coral health and abundance on tropical reefs. Here, deep metagenomic sequencing and assembly of gut compartment-specific samples from three sympatric, macroalgivorous Hawaiian kyphosid species have been used to connect host gut microbial taxa with predicted protein functional capacities likely to contribute to efficient macroalgal digestion. Bacterial community compositions, algal dietary sources, and predicted enzyme functionalities were analyzed in parallel for 16 metagenomes spanning the mid- and hindgut digestive regions of wild-caught fishes. Gene colocalization patterns of expanded carbohydrate (CAZy) and sulfatase (SulfAtlas) digestive enzyme families on assembled contigs were used to identify likely polysaccharide utilization locus associations and to visualize potential cooperative networks of extracellularly exported proteins targeting complex sulfated polysaccharides. These insights into the gut microbiota of herbivorous marine fish and their functional capabilities improve our understanding of the enzymes and microorganisms involved in digesting complex macroalgal sulfated polysaccharides.

09 BIOMASS FUELS↗

DOE OSTI2025

Reinventing wastewater treatment plants: energy neutral treatment and enhanced fertilizer production through a novel resource recovery center

Wastewater treatment plants (WWTPs) are typically energy intensive, mainly due to the secondary treatment processes such as activated sludge (AS) for treatment of organics as well as nutrients like nitrogen. Nitrogen removal presents a big problem for WWTPs. The main form of nitrogen in wastewater is ammonium, and an AS process uses oxygen to convert ammonium into nitrite and nitrate which is then converted to nitrogen through denitrification process. During anaerobic digestion (AD), organic nitrogen gets degraded, resulting in an effluent stream (centrate) with a high nitrogen content, mostly in the form of ammonium. This contributes 15-30% of total nitrogen to the wastewater influent which further increases energy consumption for aeration. The project aims to transform this conventional municipal WWTPs into energy-neutral, resource-recovering facilities by integrating three core technologies: • Cloth Media Filtration (CMF) to replace conventional primary sedimentation (CPS) and increase the diversion of organics from the energy intensive secondary treatment to AD. This results in reduced energy demand for aeration in the secondary process while simultaneously increasing the biogas production in the anaerobic digesters. • Anerobic Digester to increase biogas and ammonia production. • Membrane Evaporation (ME) to recover ammonia from AD centrate and produce marketable fertilizer. The benefits of proposed WWTP process modifications were evaluated using techno economic analysis (TEA) and life cycle assessment (LCA). For CMF portion of the research a statistical analysis was employed to develop data-driven tools that could be used to enhance and optimize its performance in terms of energy savings and effluent quality. The main objective of this project is to reduce the energy demand for secondary treatment at municipal WWTPs by at least 50%, increase anaerobic digester (AD) biogas and ammonia production by 100% and 120%, respectively, and recover 90% of ammonia from the AD. Integrated CMF, AD, and ME was shown to work synergistically toward achieving these decarbonization targets through energy-positive treatment and fertilizer recovery techniques.

42 ENGINEERING↗

DOE OSTI2016

Cell wall composition and biomass recalcitrance differences within a genotypically diverse set of Brachypodium distachyon inbred lines

Brachypodium distachyon ( Brachypodium ) has emerged as a useful model system for studying traits unique to graminaceous species including bioenergy crop grasses owing to its amenability to laboratory experimentation and the availability of extensive genetic and germplasm resources. Considerable natural variation has been uncovered for a variety of traits including flowering time, vernalization responsiveness, and above-ground growth characteristics. However, cell wall composition differences remain underexplored. Therefore, we assessed cell wall-related traits relevant to biomass conversion to biofuels in seven Brachypodium inbred lines that were chosen based on their high level of genotypic diversity as well as available genome sequences and recombinant inbred line (RIL) populations. Senesced stems plus leaf sheaths from these lines exhibited significant differences in acetyl bromide soluble lignin (ABSL), cell wall polysaccharide-derived sugars, hydroxycinnamates content, and syringyl:guaiacyl:p-hydroxyphenyl (S:G:H) lignin ratios. Free glucose, sucrose, and starch content also differed significantly in senesced stems, as did the amounts of sugars released from cell wall polysaccharides (digestibility) upon exposure to a panel of thermochemical pretreatments followed by hydrolytic enzymatic digestion. Correlations were identified between inbred line lignin compositions and plant growth characteristics such as biomass accumulation and heading date (HD), and between amounts of cell wall polysaccharides and biomass digestibility. Finally, stem cell wall p-coumarate and ferulate contents and free-sugars content changed significantly with increased duration of vernalization for some inbred lines. Taken together, these results show that Brachypodium displays substantial phenotypic variation with respect to cell wall composition and biomass digestibility, with some compositional differences correlating with growth characteristics. Moreover, besides influencing HD and biomass accumulation, vernalization was found to affect cell wall composition and free sugars accumulation in some Brachypodium inbred lines, suggesting genetic differences in how vernalization affects carbon flux to polysaccharides. Lastly, the availability of related RIL populations will allow for the genetic and molecular dissection of this natural variation, the knowledge of which may inform ways to genetically improve bioenergy crop grasses.

09 BIOMASS FUELS↗