Garold L. Gresham

Understanding biomass feedstock variability

If the singular goal of biomass logistics and the design of biomass feedstock supply systems is to reduce the per-ton supply cost of biomass, these systems may very well develop with ultimate unintended consequences of highly variable and reduced quality biomass feedstocks. This paper demonstrates that, due to inherent species variabilities, production conditions and differing harvest, collection and storage practices, this is a very real scenario that biomass producers and suppliers as well as conversion developers should be aware of. Biomass feedstock attributes of ash, carbohydrates, moisture and particle morphology will be discussed. We will also discuss specifications for these attributes, inherent variability of these attributes in biomass feedstocks, and approaches and solutions for reducing variability for improving feedstock quality.

Effect of pelleting process variables on physical properties and sugar yields of ammonia fiber expansion pretreated corn stover

Pelletization process variables, including grind size (4, 6mm), die speed (40, 50, 60 Hz), and preheating (none, 70°C), were evaluated to understand their effect on pellet quality attributes and sugar yields of ammonia fiber expansion (AFEX) pretreated biomass. The bulk density of the pelletized AFEX corn stover was three to six times greater compared to untreated and AFEX-treated corn stover. Also, the durability of the pelletized AFEX corn stover was>97.5% for all pelletization conditions studied except for preheated pellets. Die speed had no effect on enzymatic hydrolysis sugar yields of pellets. Pellets produced with preheating or a larger grind size (6mm) had similar or lower sugar yields. Pellets generated with 4mm AFEX-treated corn stover, a 60Hz die speed, and no preheating resulted in pellets with similar or greater density, durability, and sugar yields compared to other pelletization conditions.

Infrared Spectroscopy of Dioxouranium(V) Complexes with Solvent Molecules: Effect of Reduction

UO(2) (+)-solvent complexes having the general formula [UO(2)(ROH)](+) (R=H, CH(3), C(2)H(5), and n-C(3)H(7)) are formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they are isolated by mass-to-charge ratio, and then photofragmented using a free-electron laser scanning through the 10 mum region of the infrared spectrum. Asymmetric O=U=O stretching frequencies (nu(3)) are measured over a very small range [from approximately 953 cm(-1) for H(2)O to approximately 944 cm(-1) for n-propanol (n-PrOH)] for all four complexes, indicating that the nature of the alkyl group does not greatly affect the metal centre. The nu(3) values generally decrease with increasing nucleophilicity of the solvent, except for the methanol (MeOH)-containing complex, which has a measured nu(3) value equal to that of the n-PrOH-containing complex. The nu(3) frequency values for these U(V) complexes are about 20 cm(-1) lower than those measured for isoelectronic U(VI) ion-pair species containing analogous alkoxides. nu(3) values for the U(V) complexes are comparable to those for the anionic [UO(2)(NO(3))(3)](-) complex, and 40-70 cm(-1) lower than previously reported values for ligated uranyl(VI) dication complexes. The lower frequency is attributed to weakening of the O=U=O bonds by repulsion related to reduction of the U metal centre, which increases electron density in the antibonding pi* orbitals of the uranyl moiety. Computational modelling of the nu(3) frequencies using the B3LYP and PBE functionals is in good agreement with the IRMPD measurements, in that the calculated values fall in a very small range and are within a few cm(-1) of measurements. The values generated using the LDA functional are slightly higher and substantially overestimate the trends. Subtleties in the trend in nu(3) frequencies for the H(2)O-MeOH-EtOH-n-PrOH series are not reproduced by the calculations, specifically for the MeOH complex, which has a lower than expected value.

Characterization of VX on concrete using ion trap secondary ionization mass spectrometry

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate) was analyzed on the surface of concrete samples using an ion trap secondary ion mass spectrometer (IT-SIMS). It was found that VX could be detected down to an absolute quantity of 5 ng on a concrete chip, or to a surface coverage of 0.0004 monolayers on crushed concrete. To achieve these levels of detection, the m/z 268 → 128 ion fragmentation was measured using MS2, where m/z 268 corresponds to [VX + H]+, and 128 corresponds to a diisopropylvinylam-monium isomer, that is formed by the elimination of the phosphonothiolate moiety. Detection at these levels was accomplished by analyzing samples that had been recently exposed to VX, i.e., within an hour. When the VX-exposed concrete samples were aged, the SIMS signature for intact VX had disappeared, which signaled the degradation of the compound on the concrete surface. The VX signature was replaced by ions which are interpreted in terms of VX degradation products, which appear to be somewhat long lived on the concrete surface. These compounds include ethylmethylphosphonic acid (EMPA), diisopropyl taurine (DIPT), diisopropylaminoethanethiol (DESH), bis(diisopropylaminoethane)disulfide [(DES)2], and a particularly tenacious compound that may correspond to diisopropylvinylamine (DIVA), or an isomer thereof. It was found that the thiolamine-derived degradation products DIPT, DESH, and (DES)2 were removed with isopropyl alcohol extraction. However, the DIVA-related degradation product was observed to strongly adhere to the concrete surface for longer than one week. Although quantitation was not possible in this set of experiments, the results clearly show the rapid degradation of VX on concrete, as well as the surface sensitivity of the IT-SIMS for intact VX and its adsorptive degradation products.

Elucidation of the collision induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation

Multiple-stage tandem mass spectrometry was used to characterize the dissociation pathways for complexes composed of (1) the uranyl ion, (2) nitrate or hydroxide, and (3) water or alcohol. The complex ions were derived from electrospray ionization (ESI) of solutions of uranyl nitrate in H2O or mixtures of H2O and alcohol. In general, collisional induced dissociation (CID) of the uranyl complexes resulted in elimination of coordinating water and alcohol ligands. For undercoordinated complexes containing nitrate and one or two coordinating alcohol molecules, the elimination of nitric acid was observed, leaving an ion pair composed of the uranyl cation and an alkoxide. For complexes with coordinating water molecules, MSn led to the generation of either [UO22+OH−] or [UO22+NO3−]. Subsequent CID of [UO22+OH−] produced UO2+. The base peak in the spectrum generated by the dissociation of [UO22+NO3−], however, was an H2O adduct to UO2+. The abundance of the species was greater than expected based on previous experimental measurements of the (slow) hydration rate for UO2+ when stored in the ion trap. To account for the production of the hydrated product, a reductive elimination reaction involving reactive collisions with water in the ion trap is proposed.

Static secondary ionization mass spectrometry and mass spectrometry/mass spectrometry (MS2) characterization of the chemical warfare agent HD on soil particle surfaces

Abstract Detection of the blister agent HD [bis(2-chloroethyl)sulfide] or distilled mustard directly on the surface of soil particles using ion trap secondary ion mass spectrometry in the static mode is demonstrated. HD by its very nature is adsorptive; this attribute makes detection of surface adsorbed HD by gas-phase approaches difficult, but renders the compound amenable to surface detection. Two different ion trap (IT) mass spectrometers, modified to perform secondary ionization mass spectrometry using a ReO 4 − primary ion beam, were employed in the present study. Sputtered ions were trapped in the gas phase in the IT, where they could be scanned out (MS 1 ), or isolated and fragmented (MS 2 ). The intact HD molecular ion was not observed, however an abundant ion corresponding to [HD − Cl] + was formed, as were lower mass fragment ions, and ions derived from the chemical background. Ab initio calculations were used to propose structures of the fragment ions. At 0.5 monolayers surface coverage, [HD − Cl] + and lower mass HD fragment ions were significantly more abundant than the background. At lower concentrations, however, the HD secondary ion signal became masked by the background. Sensitivity and selectivity were significantly improved in the MS 2 mode of operation. MS 2 of [HD − Cl] + resulted in production of analytically diagnostic C 2 H 4 SH + and other S- and Cl-bearing fragment ions. HD was detected at 0.07 monolayers using the MS 2 approach, which corresponds to 108 ppm on a mass/mass basis.

Identification of the nitrogen-based blister agents bis(2-chloroethyl)methylamine (HN-2) and tris(2-chloroethyl)amine (HN-3) and their hydrolysis products on soil using ion trap secondary ion mass spectrometry.

The nitrogen blister agents HN-2 (bis(2-chloroethyl)methylamine) and HN-3 (tris(2-chloroethyl)amine) were directly analyzed on the surface of soil samples using ion trap secondary ion mass spectrometry (SIMS). In the presence of water, HN-1 (bis(2-choroethyl)ethylamine), HN-2 and HN-3 undergo hydrolysis to form N-ethyldiethanolamine, N-methyldiethanolamine and triethanolamine (TEA), respectively; these compounds can be readily detected as adsorbed species on soil particles. When soil samples spiked with HN-3 in alcohol were analyzed, 2-alkoxyethylamine derivatives were observed on the sample surfaces. This result shows that nitrogen blister agents will undergo condensation reactions with nucleophilic compounds and emphasizes the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of ion trap SIMS to isolate and accumulate ions, and then perform tandem mass spectrometric analysis improves the detection of low-abundance surface contaminants and the selectivity of the technique. Utilizing these techniques, the limits of detection for HN-3 were studied as a function of surface coverage. It was found that HN-3 could be detected at a surface coverage of 0.01 monolayer, which corresponds to 20 ppm (mass/mass) for a soil having a surface area of 2.2 m(2) g(-1). TEA, the exhaustive hydrolysis product of HN-3, was detected at a surface coverage of 0.001 monolayer, which corresponds to 0.86 ppm.

Effect of pelleting on the recalcitrance and bioconversion of dilute-acid pretreated corn stover under low- and high-solids conditions

Background: Knowledge regarding the performance of densified biomass in biochemical processes is limited. The effects of densification on biochemical conversion are explored here. Results: Pelleted corn stover samples were generated from bales that were milled to 6.35 mm. Low-solids acid pretreatment and simultaneous saccharification and fermentation were performed for pelleted and ground stover (6.35 and 2 mm) formats. Monomeric xylose yields were significantly higher for pellets (∼60%) than for ground formats (∼38%). Pellets achieved approximately 84% of theoretical ethanol yield; ground stover formats had similar profiles, reaching approximately 68% theoretical ethanol yield. Pelleted and 6.35-mm ground stover were evaluated using a ZipperClave® reactor under high-solids, process-relevant conditions for multiple pretreatment severities (Ro); feedstock reactivity increased slightly following combined pretreatment and enzymatic hydrolysis for three of five severities tested. Conclusion: Pelleting did not render corn stover more recalcitrant to dilute-acid pretreatment under low- or high-solids conditions, and even enhanced ethanol yields.

Investigations of acidity and nucleophilicity of diphenyldithiophosphinate ligands using theory and gas-phase dissociation reactions

Diphenyldithiophosphinate (DTP) ligands modified with electron-withdrawing trifluoromethyl (TFM) substitutents are of high interest because they have demonstrated potential for exceptional separation of Am (3+) from lanthanide (3+) cations. Specifically, the bis( ortho-TFM) (L 1 (-)) and ( ortho-TFM)( meta-TFM) (L 2 (-)) derivatives have shown excellent separation selectivity, while the bis( meta-TFM) (L 3 (-)) and unmodified DTP (L u (-)) did not. Factors responsible for selective coordination have been investigated using density functional theory (DFT) calculations in concert with competitive dissociation reactions in the gas phase. To evaluate the role of (DTP + H) acidity, density functional calculations were used to predict p K a values of the free acids (HL n ), which followed the trend of HL 3 < HL 2 < HL 1 < HL u. The order of p K a for the TFM-modified (DTP+H) acids was opposite of what would be expected based on the e (-)-withdrawing effects of the TFM group, suggesting that secondary factors influence the p K a and nucleophilicity. The relative nucleophilicities of the DTP anions were evaluated by forming metal-mixed ligand complexes in a trapped ion mass spectrometer and then fragmenting them using competitive collision induced dissociation. On the basis of these experiments, the unmodified L u (-) anion was the strongest nucleophile. Comparing the TFM derivatives, the bis( ortho-TFM) derivative L 1 (-) was found to be the strongest nucleophile, while the bis( meta-TFM) L 3 (-) was the weakest, a trend consistent with the p K a calculations. DFT modeling of the Na (+) complexes suggested that the elevated cation affinity of the L 1 (-) and L 2 (-) anions was due to donation of electron density from fluorine atoms to the metal center, which was occurring in rotational conformers where the TFM moiety was proximate to the Na (+)-dithiophosphinate group. Competitive dissociation experiments were performed with the dithiophosphinate anions complexed with europium nitrate species; ionic dissociation of these complexes always generated the TFM-modified dithiophosphinate anions as the product ion, showing again that the unmodified L u (-) was the strongest nucleophile. The Eu(III) nitrate complexes also underwent redox elimination of radical ligands; the tendency of the ligands to undergo oxidation and be eliminated as neutral radicals followed the same trend as the nucleophilicities for Na (+), viz. L 3 (-) < L 2 (-) < L 1 (-) < L u (-).

Characterization of copper chloride cluster ions formed in secondary ion mass spectrometry

Abstract The surfaces of copper chloride salts were investigated using three different secondary ion mass spectrometry (SIMS) instruments: a quadrupole instrument equipped with an ReO4− primary ion, a time-of-flight (ToF) instrument equipped with a Ga+ primary ion, and an ion trap instrument equipped with ReO4−. The research was conducted to identify copper chloride species sputtered from the surface of the copper chloride salts and to attempt to relate these species to the composition of the salt. Rich anion spectra were recorded using all three instruments for CuCl2 and CuCl, which were dominated by CuCl3− and CuCl2−. Other copper chloride adduct ions were also observed at higher masses. An examination of these ions revealed Cu primarily in the +1 and +2 oxidation state, irrespective of the oxidation state of the original salt. The presence of the Cu(+1)-bearing ions originating from the Cu(+2) salt has been attributed to reduction processes occurring during the bombardment event. However, oxidation processes must also be occurring, because Cu(+2)-bearing ions are observed in the spectra of the Cu(+1) salt. In contrast to the anion spectra, the only Cu-bearing cations contained in the CuCl(1,2) spectrum were acquired using the quadrupole- and ToF-SIMS corresponded to Cu+ and low abundance Cu2Cl+ and Cu3Cl2+ [(all Cu(+1)]. CuCl(1,2) were further investigated using the ion trap SIMS instrument: in these analyses, abundant cation clusters could be observed in addition to Cu+. The ions have been grouped into one of four categories: highly oxidized, one e− oxidized, redox neutral, and reduced. The most abundant species were redox neutral [e.g. (CuCl2)2CuCl+)] and one e− oxidized (e.g. (CuCl2)3+). Keywords: SIMS; Cluster ions; MS/MS; Ion trap; Copper chloride