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At least 163 records · Page 9

Microbial Pathways for Cost-Effective Low-Carbon Renewable Indigoidine

Indigoidine is a bioadvantaged platform molecule with diverse applications, including use as a textile dye, biotransistor, biosolar cell, biosensor, and food coloring. There are multiple microbial hosts and carbon sources that can be used and optimized for its production, yet there is limited guidance for which options have the greatest commercial potential. Here, we consider five different host microbes and combine genome-scale metabolic models with techno-economic and lifecycle assessment models. Pseudomonas putida currently outperforms synthetic indigo production and other indigoidine-producing hosts, using glucose, xylose, and lignin-derived aromatics to produce indigoidine at a minimum selling price of $2.9/kg and a greenhouse gas (GHG) footprint of 3.5 kgCO 2e /kg. Optimizing pathways-achieving 90% of the theoretical indigoidine yield from sugars and aromatics-can reduce costs 6-7-fold and GHG emissions 3-10-fold. From a cost perspective, microbes that co-utilize aromatics are advantageous, while selecting hosts that coproduce other value-added molecules can reduce GHG emissions. System-wide improvements and the use of a low-cost, low-carbon nitrogen source are crucial for commercial viability in all cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Paired electrocatalysis in 5-hydroxymethylfurfural valorization

5-Hydroxymethylfurfural (HMF) has aroused considerable interest over the past years as an important biomass-derived platform molecule, yielding various value-added products. The conventional HMF conversion requires noble metal catalysts and harsh operating conditions. On the other hand, the electrocatalytic conversion of HMF has been considered as an environmentally benign alternative. However, its practical application is limited by low overall energy efficiency and incomplete conversion. Paired electrolysis and highly efficient electrocatalysts are two viable strategies to address these limitations. Herein, an overview of coupled electrocatalytic HMF hydrogenation or hydrogen evolution reaction (HER) with HMF oxidation as well as the associated electrocatalysts are reviewed and discussed. In this mini-review, a brief introduction of electrocatalytic HMF upgrading is given, followed by the recent advances and challenges of paired electrolysis with an emphasis on the integration HMF electrohydrogenation with HMF electrooxidation. Finally, a perspective for a future sustainable biomass upgrading community based on electrocatalysis is proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recovery of p -Hydroxybenzoic Acid from Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment of Hybrid Poplar

p-Hydroxybenzoic acid (pHBA) is present in some hardwood biomass feedstocks as an ester attached to the polymeric lignin subunits. Here, we report the isolation and recovery of pHBA from alkaline liquor waste streams obtained from fractionation of hybrid poplar using the “Cu-AHP process”. This process features two stages: alkaline pre-extraction (AP) of the biomass and copper-catalyzed alkaline hydrogen peroxide pretreatment. On a biomass scale of 100 g, 0.5 g of pHBA with a purity of 96% was obtained after decolorization and crystallization. The scalability of the purification process was demonstrated by using liquor obtained from the first-stage AP with 900 g of poplar biomass to afford 3.5 g of crystalline pHBA with 97% purity. Altogether, these results show that pHBA may be isolated and purified from waste streams generated in the two-stage Cu-AHP process without any alteration of the process conditions or impact on carbohydrate and lignin fractionation.

09 BIOMASS FUELS↗

A Novel Process for Converting Coal to High-Value Polyurethane Products

Battelle has demonstrated a patented process for making high-value, polyurethane (PU) foam from coal, based on preparing liquefied coal via direct liquefaction, converting it to polyols as an intermediate via ozonation, and then making PU foams from these polyols. This process represents a breakthrough in innovative utilization of U.S. coals, and is applicable to bituminous as well as sub-bituminous coals. The resulting PU foam products are projected to have an extremely high value (i.e., over $\$5,000$ /ton), with nearly 100% of carbon utilization from coalderived liquid feedstock, and 31.5% to 43.5% of the carbon in the PU foam polyol product being bio-based. The targeted products represent an extremely large (i.e., over $80 billion/year), existing PU foam market, which could expand into making coatings and adhesives. The process can further help reduce petroleum imports, while improving the economics of PU foam production. This work was completed with funding from the National Energy Technology Laboratory (NETL), with cost share from the State of Ohio’s Ohio Development Services Agency (ODSA) and others, and has advanced the process to 10 kg/day continuous scale and thus to Technology Readiness Level (TRL) 5. A total of 48 coal-based polyols were prepared and evaluated. The initial 28 polyols focused on range finding for ideal conditions. The later 20 polyols were produced as part of process optimizations. These optimizations were targeted around a continuous ozonolysis process to evaluate extended time reactions and to create the necessary intermediate for production of 1-gallon samples of polyol. The most unique attribute of Battelle’s polyol is in the utilization of coal’s aromaticity to gain final foam rigidity. Typically, polyols depend on the isocyanate fraction and cross-linking to gain rigidity. By utilizing coal, we were able to maintain rigidity while reducing the overall hydroxyl value of the polyol. This is important as lower hydroxyl value leads to greater percent weight of the coal-based polyol because less isocyanate is required for foaming. This leads to greater foam cost savings. This report provides the details, process, and process cost models of the conversion of coal to polyols and further to PU foams. Battelle’s process begins with coal liquids. These liquids can be obtained by two processes: coal coking or pyrolysis to produce coal tar, and Battelle’s biobased coal-to-liquids (CTL) process to produce heavy syncrude after liquifying >85% coal. After liquification, Battelle utilizes ozonolysis to create functionalization on the polyaromatic coal structure. The functionalization is then converted to the final polyester polyol through transesterification, or to hydroxyamide polyol through amidification. Equivalent or better standard properties have been obtained for 2 lb/ft 3 density rigid, water and freon-alternative blown foams, including compressive strength, density, R-value, and dimensional stability. Target applications for these foams are insulation, packaging, and energy-absorbing foams. Some exploratory testing also showed promise for adhesives applications. A detailed economic analysis showed that Battelle’s polyol process is economical, at a 140 metric tons per day (MTD) polyol production scale. An attractive return on investment (ROI) at competitive pricing validates the process is ready for a pilot-plant demonstration. A scale-up plan is provided.

01 COAL, LIGNITE, AND PEAT↗

Importance of suberin biopolymer in plant function, contributions to soil organic carbon and in the production of bio-derived energy and materials

Abstract Suberin is a hydrophobic biopolymer of significance in the production of biomass-derived materials and in biogeochemical cycling in terrestrial ecosystems. Here, we describe suberin structure and biosynthesis, and its importance in biological (i.e., plant bark and roots), ecological (soil organic carbon) and economic (biomass conversion to bioproducts) contexts. Furthermore, we highlight the genomics and analytical approaches currently available and explore opportunities for future technologies to study suberin in quantitative and/or high-throughput platforms in bioenergy crops. A greater understanding of suberin structure and production in lignocellulosic biomass can be leveraged to improve representation in life cycle analysis and techno-economic analysis models and enable performance improvements in plant biosystems as well as informed crop system management to achieve economic and environmental co-benefits.

09 BIOMASS FUELS↗

Identification of Critical Process Parameters for Knife Milling and Alternative Communication Strategies

An assessment of knife milling operations was performed to identify parameters that require consideration to model wear and degradation of knife blades. A quality-by-design (QbD) paradigm was followed to identify material and feedstock attributes, and processing parameters that impact the quality attributes of the blades used in the comminution of biomass into forms compatible with downstream operations. Based on analytical and experimental observations of knife and tool wear, a QbD model is proposed that considers three wear mechanisms (erosion, abrasion, and gouging) to predict volumetric wear of knife blades and sharpness. These factors, if properly applied, provide a science-based approach to predict the mechanical efficiency of the mill as a function of feedstock properties, knife blade material properties, and processing parameters (feed rate, speed, and design parameters).

09 BIOMASS FUELS↗

Identification and Quantification of Photosynthetic Pigments in Algae (Laboratory Analytical Procedure (LAP))

The Laboratory Analytical Procedure (LAP) outlined here describes a method to quantitatively extract phytopigments from microalgae biomass, as well as to identify and quantify individual pigments based on separation and detection with a High-Performance Liquid Chromatography (HPLC) system coupled to a Diode Array Detector (DAD). Pigments were extracted with greater than 95 % extraction efficiency. Chromatographic conditions allowed for isomeric resolution between pigments and identification based on UV/Vis spectra and comparison to analytical standards.

09 BIOMASS FUELS↗

Overview and technology opportunities for thermochemically-produced bio-blendstocks

Global demand for transportation fuels is projected to increase 40% by 2040, and biomass-derived fuels (biofuels) play a crucial role in substituting fossil fuels and mitigating greenhouse gas emissions. Currently, biofuels are mainly consumed as blendstocks combined with petroleum-based fuels, and effective conversion technologies can address the quality challenges for offering standalone biofuels. Thermochemical conversion process is one of the most promising pathways among existing technologies for biofuel production. However, the major barriers are unwanted characteristics (e.g., thermal instability) of intermediate products, such as bio-oil, and required upgrading treatments for producing compatible fuels. Here, this study highlights the merits and critical challenges of thermochemical conversion and physicochemical upgrading technologies for bio-blendstock production from lignocellulosic biomass. The novelty of this study lies in potential directions for future research through both critical and systematic literature reviews, and the proposed intensified process for lignocellulosic-based fuel blendstocks production. It is concluded that recovery and fractionation strategies (e.g., quenching and stripping) can maximize process yields and add values in the efficient conversion pathways. Effective quenching can stop secondary free radical reactions and improve liquid yields over gas and solid yields. Stripping process can improve process yield, catalyst lifespan, and thermal stability. It is further concluded that physicochemical treatments are not as effective as thermochemical treatments, but have advantages of mild operating conditions and potential for integrated solutions in conjunction with other treatments.

09 BIOMASS FUELS↗

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗

DOE Energy Frontier Research Centers Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)

New capabilities to predict, design and control the chemistries of carbon could answer a global imperative to transition from fossil-based to sustainable transportation fuels. While the use of inexpensive hydrocarbons has been an unparalleled achievement and enabler of economic prosperity for many nations, singular dependence upon crude oil has given rise to systemic vulnerabilities in climate, energy, economic, and national security. Lignocellulosic biomass, a renewable and carbon-neutral resource, has the potential to displace an estimated annual equivalent of three billion barrels of oil in the U.S. alone (National Research Council 2009, U. S. Department of Energy, 2011). However, biomass has only one-third the energy density of crude oil (Agrawal and Singh 2009, Richard 2010) and lacks petroleum’s versatility as a feedstock for fuels and chemicals. These limitations keep biomass conversion below the efficiency level needed for strategic impact while the scientific challenge of routing carbon from one molecular context to another remains unmet. In 2009, the Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) recognized the potential of chemical catalysis and fast pyrolysis to overcome such limitations by transforming the main components of biomass (cellulose, xylan, and lignin) from grasses and trees directly to liquid hydrocarbons and aromatic co-products. Enabled by the EFRC high-risk, high-reward approach to grand challenge science, C3Bio researchers have been key national players in disrupting the conventional paradigm of the cellulosic biorefinery into a new future of “no carbon left behind”—the full utilization of carbon from plant cell walls in energy-dense fuels (Fig. 1). We identified catalytic and fast-pyrolytic pathways that utilize cellulose, xylan and, most significantly, lignin. We developed catalytic processes that deoxygenate and transform monomers and isolated polymers into useful products and tested their use with intact biomass. We gained control of lignin synthesis within plants and initiated tailoring biomass to its end-use through the tools of plant molecular biology and genetic engineering. C3Bio breakthroughs have increased the energy density of biomass-derived substrates via catalytic and pyrolytic conversions into products such as benzoquinones, furfural and hydroxymethylfurfural, levoglucosan and levulinic acid, methoxypropylphenols and propylbenzene. Such advances in biomass conversion would not have been possible without simultaneous advances in analytical instrumentation and methodologies, and imaging technologies and applications. The legacy science developed by C3Bio enables design and control strategies for achieving a targeted product portfolio of fuel and chemical feedstocks from a diverse range of native and tailored biomass. Our research provides the knowledge base required for a bio-economy with product streams as diverse in functionality as those of the petrochemical industry. Coupling targeted computational modeling with experimentation, we achieved: (1) fundamental understanding of biopolymers and cell wall architecture assembly, (2) discovery of new chemistries that allow the development of highly selective pathways to fuels and desirable chemicals, and (3) an integrated systems-level understanding to control catalytic and pyrolytic pathways.

09 BIOMASS FUELS↗

Mechanistic Insights into the Conversion of Biorenewable Levoglucosanol to Dideoxysugars

Here, a molecular understanding of the conversion of biorenewable threo- and erythro-levoglucosanol (LGOL) to 3,4-dideoxysugars in aqueous medium is provided based on first-principles simulations. The synthetic importance of this transformation is that these intermediates can be quantitatively hydrogenated to (S,S)/(S,R) hexane-1,2,5,6-tetrol (tetrol), whose stereochemistry depends on which dideoxy sugar intermediates are formed during LGOL conversion. The thermodynamic and kinetic feasibility of the acetal (R 2 C(OR) 2 ) hydrolysis in LGOL is investigated via computing the free energy profile. In aqueous medium, the rate-determining step of LGOL hydrolysis is the protonation of the anhydro-bridge oxygen atom of LGOL concurrent with ring opening, yielding the cyclic forms of 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG) from threo- and erythro-LGOL, respectively. The measured activation energies of LGOL hydrolysis are 20.5 and 23.6 kcal/mol for DDM and DDG formation, respectively. These values are in agreement with the computed protonation free energies of 17.1 and 18.2 kcal/mol, respectively. Based on the simulations, a Bronsted base-catalyzed isomerization from DDG or DDM to 3,4-dideoxy fructose (DDF) is preferred with lower apparent activation free energy barriers compared to the acid-catalyzed isomerization. In summary, this study provides mechanistic information about the conversion of the biomass-derived anhydro-sugar LGOL to 3,4-dideoxy sugars, which are precursors to renewable high-value chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BETO 2021 Peer Review - Analytical Development & Support WBS 2.5.1.101

The objective of the Analytical Development and Support (ADS) Project is to produce and maintain the critical analytical methods and tools that enable evaluation of emerging biofuels R&D at NREL and in the broader biofuels research community. Our project is divided into two tasks: one task to develop novel analytical techniques and improve existing methods and one task to maintain existing analytical capabilities at NREL and provide outreach to the wider community. The ADS Project is world-recognized for our Laboratory Analytical Procedures (LAPS) which provide detailed procedures for compositional analysis of biomass and have been adopted as the de facto standards within the biofuels community largely due to the transparency of the methods and the high reputation of NREL's research. Our dialog with stakeholders allows us to provide robust, precise, accurate, and publicly available analytical procedures for better valuation of scientific tools such as our recent accomplishment in developing a cellulose assay to support the EPA and industry in calculation of converted cellulose during starch ethanol production. We continue to develop analytical capabilities to support BETO's directives to research cost advantaged fuels such as animal wastes and novel bioproducts like 2,3-Butane-diol.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Extraction of Furfural and Furfural/5-Hydroxymethylfurfural from Mixed Lignocellulosic Biomass-Derived Feedstocks

We present a combined in silico and experimental study on the extraction of furfural and 5-hydroxymethylfurfural (HMF) in aqueous–organic biphasic systems. We predict the liquid–liquid equilibria and furfural/HMF partition coefficients of over 2200 water-organic biphasic systems using the multiscale COSMO-RS model and measure experimentally single-component (furfural) and mixture (furfural and HMF) partition coefficients at room and dehydration reaction-relevant temperatures in 28 solvents. We find the experimental data to be within a factor of 2 from the COSMO-RS predictions. Even though furfural and HMF have chemical similarity, the slight differences in molecular structure render the separation of furfural easier by the supply of more solvents of higher partition coefficient for extraction. We leverage this molecular difference and experimentally demonstrate that with an additional extraction step, using dichloromethane or toluene, we can selectively extract furfural from furfural-HMF mixtures, which can coexist in lignocellulosic biomass dehydration products, despite their partition coefficients being generally correlated. We complement solvent selection criteria for biphasic lignocellulosic biomass processes with a simple mass balance extraction model for determining volume ratios in multistage extraction. Lastly, the molecular nature of the preferential furfural extraction is rationalized using COSMO-RS σ-profile analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stochastic Techno Economic Model

The Stochastic Techno-Economic Model or STEM is an analytical tool that estimates the logistics cost of different biomass feedstocks by incorporating uncertainty into the modeling framework. The scope of the model covers multiple stages of the biomass life cycle spanning feedstock harvest, collection, transportation and handling, preprocessing, and storage. The model determines the total logistics cost per dry metric ton ($/DM ton) for biomass and breaks down the costs for important cost categories including ownership related costs such as interest and depreciation, insurance, housing, and taxes as well as operating costs like repairs and maintenance, labor costs, and fuel and lube costs.

Burli, PralhadH↗

Standard Analytical Methods for Pyrolysis Bio-Oils

There has been significant recent interest in the production of renewable fuels and chemicals from biomass and waste feedstocks. Pyrolysis pathways produce a liquid bio-oil product, which must be processed further, or upgraded, to yield fuel or chemical products. Bio-oils are very complex and often unstable samples, and research and development on upgrading processes needs reliable analytical information. In particular, chemical characterization techniques are needed to quantify both functional groups and individual compounds present in bio-oils. Reliable analytics are also needed to enable the bioenergy industry, as industrial facilities often have different analytical needs and capabilities than research facilities. In this presentation, we will discuss the development of a suite of standard analytical methods for pyrolysis bio-oils. Analytical methods to be discussed include: Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in bio-oils; Accelerated Aging of Fast Pyrolysis Bio-oil using Carbonyl Titration; Determination of Water Content in Bio-oils by Volumetric Karl Fischer Titration; Determination of Carbon Functional Groups; Elemental Analysis of Bio-oils by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) - Na, K, Mg, Ca, S, P, and Fe; Determination of Phenolic Groups in Bio-oils using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader; Corrosivity of Bio-oils: Screening Test using Metal Leaching; Determination of Biogenic Content by 14C Measurement using Liquid Scintillation Counter. These new analytical methods are publicly available as Laboratory Analytical Procedures (https://www.nrel.gov/bioenergy/bio-oil-analysis.html), along with previously developed standard methods: GC-MS, Acid Titration, Carbonyl Titration, and 31P NMR. Additionally, the development of diffusion ordered NMR for characterization of bio-oil molecular weight will be discussed. Collectively, this suite of analytical methods represents the most comprehensive set of standard methods available for pyrolysis bio-oils. These standard methods are commonly used by the bioenergy community, and provide reliable information that enables research, scaleup, and industrial processing of biomass to produce renewable fuels and chemicals.

analytical↗

Direct determination of cellulosic glucan content in starch-containing samples

A simple and highly selective analytical procedure is presented for the determination of cellulosic glucan content in samples that contain both cellulose and starch. This method eliminates the unacceptably large compounding errors of current two-measurement methods. If both starch and cellulose are present before analytical hydrolysis, both will be hydrolyzed to glucose causing bias and inaccuracy in the method. To prevent this interference, the removal of starch prior to cellulosic quantification is crucial. The method presented here is a concise in-series procedure with minimal measurements, eliminating large compounding errors. Sample preparation consists of a starch extraction employing enzymatic hydrolysis followed by a simple filtration and wash. The samples are then subjected to a two-stage acid hydrolysis. The concentration of glucose is determined by ion exchange high-performance liquid chromatography with a Pb 2+ column and a refractive index detector. The cellulosic glucan content is calculated based on the initial dry weight of the starting material. Data for the native biomass materials studied show excellent reproducibility, with coefficients of variance of 3.0% or less associated with the method. This selectivity for cellulosic glucan by the procedure was validated with several analytical techniques such as liquid chromatography coupled with mass spectrometry (LC–MS), Raman spectroscopy, and nuclear magnetic resonance.

09 BIOMASS FUELS↗

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13 C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. Furthermore, we demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extreme Molecular Complexity Resulting in a Continuum of Carbonaceous Species in Biomass Burning Tar Balls from Wildfire Smoke

Biomass burning emits a wide range of carbonaceous particles into the atmosphere and has negative impacts on human health and the Earth’s radiative balance. Nonvolatile spherical organic aerosol particles, commonly known as tar balls, represent one of the most abundant particles in aged biomass burning smoke. However, the detailed molecular-level composition of ambient tar balls is largely unknown but critical to access their environmental impacts. Ambient aerosol samples collected during a wildfire event, which were ~90% tar balls by number fraction, were analyzed using ultrahigh resolution Orbitrap Elite mass spectrometry with four complementary ionization modes. Our results show the molecular composition of tar balls to be complex, composed of over 10,000 molecular formulas. Model estimated saturation mass concentrations and relative humidity dependent glass transition temperatures were consistent with low volatility and solid morphology as expected for tar balls. Room-temperature evaporation kinetics showed that these particles were composed of ~90% non-volatile species. The molecular complexity detected here signifies a continuum of carbonaceous species, ranging from C3 to C45 with continuous ranges of oxygenation and hydrogen saturation for each Cn. Approximately 24% of molecular formulas were estimated the be highly aromatic, which could indicate chemical compounds with negative health effects, and which may contribute to visible light absorption. The carbon continuum observed here has significant implications for the molecular characterization of atmospheric organic matter. The level of complexity detected here should not be ignored in future studies and we demonstrate that multiple analytical methods may be required to suitably interpret this complexity on a molecular level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗