Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

We present results of a combined vacuum ultravioloet (VUV) and infrared (IR) photoabsorption study of amorphous benzene:water mixtures and layers to investigate the benzene-water interaction in the solid phase. UV spectra of 1:1, 1:10 and 1:100 benzene:water mixtures at 24 K reveal a concentration dependent shift in the energies of the 1B2u, 1B1u and 1E1u electronic states of benzene. All the electronic bands blueshift from pure amorphous benzene towards gas phase energies with increasing water concentration. IR results reveal a strong dOH-π benzene-water interaction via the dangling OH stretch of water with the delocalised π system of the benzene molecule. Although this interaction influences the electronic states of benzene with the benzenewater interaction causing a redshift in the electronic states from that of the free benzene molecule, the benzene-benzene interaction has a more significant effect on the electronic states of benzene. VUV spectra of benzene and water layers show evidence of non-wetting between benzene and water, characterised by Rayleigh scattering tails at wavelengths greater than 220 nm. Our results also show evidence of benzene-water interaction at the benzene-water interface affecting both the benzene and the water electronic states. Annealing the mixtures and layers of benzene and water show that benzene remains trapped within in/under water ice until water desorption near 160 K. These first systematic studies of binary amorphous mixtures in the VUV, supported with complementary IR studies, provide a deeper insight into the influence of intermolecular interactions on intramolecular electronic states with significant implications for our understanding of photochemical processes in more realistic astrochemical environments

Atmospheric benzene observations from oil and gas production in the Denver-Julesburg Basin in July and August 2014

High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA’s “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO

Health Effects of Indoor-Air Benzene in Anchorage Residences: A Study of Indoor-Air Quality in Houses with Attached Garages

Benzene is a known carcinogen. It affects white blood cells; it causes leukemia and aplastic anemia. It may also affect the immune system which is dependent on white blood cells.1 It has been removed from all household products, but it is still present in gasoline. Alaskan gasoline is particularly high in benzene (>5%). Gasoline refined in Alaska has high concentrations of benzene and other the aromatic compounds as much as 50% aromatics by volume. Leaving the aromatics in the gasoline helps cars start in the cold, but it also puts high concentrations of benzene in both the ambient and indoor air. We already knew from previous work done in Alaska by Bernard Goldstein in Valdez2 and the Anchorage Department of Health and Human Services in Anchorage3 that people were exposed to high ambient levels of benzene in the winter, and that there were high indoor benzene concentrations in homes with attached garages if the garage was used to store gasoline or gasoline powered engines. Benzene does not bioaccumulate in the body as dioxin or some pesticides do. But are its effects cumulative? Does a little dose of benzene everyday have the same effect as a large dose over less time? Benzene reduces CD4 cells in a dose-response manner at workplace concentrations less than 1 ppm (OSHA 8-hour exposure limit) in workers.4 People who live in homes with high benzene concentrations may be exposed 24 hours a day, seven days a week. There have been no studies of health effects of such environmental exposure to benzene. This study was done to determine three things: 1. What percentage of Anchorage homes with attached garages had high levels of indoor benzene? 2. Were the high levels of indoor benzene affecting the health of the residents? 3. Were residents more likely to develop asthma in homes with high levels of indoor benzene?Municipality of AnchorageIntroduction / Methods / Recruitment / Results / Laboratory Results / Smoking / Health Results / Demographics / Determining Risk Levels / Asthma Outcomes / Children / Work and Hobby Exposure / General Health / Conclusions / Bibliography / Appendice

Benzene C−H Bond Activation in Carboxylic Acids Catalyzed by O-Donor Iridium(III) Complexes: An Experimental and Density Functional Study

The mechanism of benzene C−H bond activation by [Ir(μ-acac-O,O,C^3)(acac-O,O)(OAc)]_2 (4) and [Ir(μ-acac-O,O,C^3)(acac-O,O)(TFA)]_2 (5) complexes (acac = acetylacetonato, OAc = acetate, and TFA = trifluoroacetate) was studied experimentally and theoretically. Hydrogen−deuterium (H/D) exchange between benzene and CD_(3)COOD solvent catalyzed by 4 (ΔH^‡ = 28.3 ± 1.1 kcal/mol, ΔS^‡ = 3.9 ± 3.0 cal K^(−1) mol^(−1)) results in a monotonic increase of all benzene isotopologues, suggesting that once benzene coordinates to the iridium center, there are multiple H/D exchange events prior to benzene dissociation. B3LYP density functional theory (DFT) calculations reveal that this benzene isotopologue pattern is due to a rate-determining step that involves acetate ligand dissociation and benzene coordination, which is then followed by heterolytic C−H bond cleavage to generate an iridium-phenyl intermediate. A synthesized iridium-phenyl intermediate was also shown to be competent for H/D exchange, giving similar rates to the proposed catalytic systems. This mechanism nicely explains why hydroarylation between benzene and alkenes is suppressed in the presence of acetic acid when catalyzed by [Ir(μ-acac-O,O,C^3)(acac-O,O)(acac-C^3)]_2 (3) (Matsumoto et al. J. Am. Chem. Soc. 2000, 122, 7414). Benzene H/D exchange in CF_(3)COOD solvent catalyzed by 5 (ΔH^‡ = 15.3 ± 3.5 kcal/mol, ΔS^‡ = −30.0 ± 5.1 cal K^(−1) mol^(−1)) results in significantly elevated H/D exchange rates and the formation of only a single benzene isotopologue, (C_(6)H_(5)D). DFT calculations show that this is due to a change in the rate-determining step. Now equilibrium between coordinated and uncoordinated benzene precedes a single rate-determining heterolytic C−H bond cleavage step

Sub-Doppler UV spectroscopy by resonance-enhanced two-photon ionization: the structure of the benzene20,22Ne cluster

In this work it is demonstrated that mass selected multiphoton ionization is a powerful technique for high resolution spectroscopy, isotope cluster separation and investigation of the structure of van der Waals clusters. The rotationally resolved UV spectra of the benzene-20Ne and benzene-22Ne clusters are selectively measured in a natural isotopic mixture of benzene and benzene-Ne clusters in a cooled supersonic jet. The analysis of these spectra yields accurate values for the rotational constants of both species. From this data it is found that the Ne atom is located on the C6 rotational axis of the benzene ring at an average distance of 3.46 Å with a slight difference for the two isotopes. This distance decreases by 40 mÅ when benzene is electronically excited. The influence of the large amplitude van der Waals vibrations on the average bond length is discussed

A New Pseudopolymorph of Hexakis-(4-cynaophenyl)benzene

The title compound (systematic name: benzene-4,4′,4′′,4′′′,-4′′′′,4′′′′′-hexaylhexabenzonitrile dichloromethane disolvate), C48H24N6•2CH2Cl2, crystallizes as an inclusion compound during the slow diffusion of methanol into a solution of hexakis(4-cyanophenyl)benzene in CH2Cl2. The hexakis(4- cyanophenyl)benzene molecule lies on an axis of twofold rotation in the space group Pbcn. Weak C—H•••N interactions between hexakis(4-cyanophenyl)benzene molecules define an open network with space for including guests. The resulting structure is a new pseudopolymorph of hexakis-(4-cyanophenyl)benzene. The eight known pseudopolymorphs have few shared architectural features, in part because none of the intermolecular interactions that are present plays a dominant role or forces neighboring molecules to assume particular relative orientations

Simulation of benzene transport and biodegradation during transient hydraulic conditions

Thesis (M.S.) University of Alaska Fairbanks, 2000MODFLOW and BIOMOC were used to simulate transport and biodegradation of benzene in the alluvial aquifer adjacent to the Chena River. MODFLOW was used to calculate ground water fluxes at the boundaries of the BIOMOC model, which was used to model transport and biodegradation of benzene. A benzene plume located 300 ft. southeast of the study site is superimposed onto the cross-sectional model of the study area. Only saturated zone processes were modeled. Anaerobic biodegradation was the only simulated biodegradation process. The simulation shows 0.003% of the theoretical benzene entering the saturated zone is biodegraded, 0.6% is adsorbed by solids, and 99.4% leaves the model boundaries. The simulation predicts theoretical concentrations of benzene are 2 to 8 ug/l when discharging into the river. Field data do not support this finding. Processes not simulated, such as aerobic degradation at the water table, may make significant contributions toward limiting benzene transport

Leukemia-related chromosomal loss detected in hematopoietic progenitor cells of benzene-exposed workers.

Benzene exposure causes acute myeloid leukemia and hematotoxicity, shown as suppression of mature blood and myeloid progenitor cell numbers. As the leukemia-related aneuploidies monosomy 7 and trisomy 8 previously had been detected in the mature peripheral blood cells of exposed workers, we hypothesized that benzene could cause leukemia through the induction of these aneuploidies in hematopoietic stem and progenitor cells. We measured loss and gain of chromosomes 7 and 8 by fluorescence in situ hybridization in interphase colony-forming unit-granulocyte-macrophage (CFU-GM) cells cultured from otherwise healthy benzene-exposed (n=28) and unexposed (n=14) workers. CFU-GM monosomy 7 and 8 levels (but not trisomy) were significantly increased in subjects exposed to benzene overall, compared with levels in the control subjects (P=0.0055 and P=0.0034, respectively). Levels of monosomy 7 and 8 were significantly increased in subjects exposed to <10 p.p.m. (20%, P=0.0419 and 28%, P=0.0056, respectively) and ≥ 10 p.p.m. (48%, P=0.0045 and 32%, 0.0354) benzene, compared with controls, and significant exposure-response trends were detected (P(trend)=0.0033 and 0.0057). These data show that monosomies 7 and 8 are produced in a dose-dependent manner in the blood progenitor cells of workers exposed to benzene, and may be mechanistically relevant biomarkers of early effect for benzene and other leukemogens

Isolation and characterization of Alicycliphilus denitrificans strain BC, which grows on benzene with chlorate as the electron acceptor

A bacterium, strain BC, was isolated from a benzene-degrading chlorate-reducing enrichment culture. Strain BC degrades benzene in conjunction with chlorate reduction. Cells of strain BC are short rods that are 0.6 microm wide and 1 to 2 microm long, are motile, and stain gram negative. Strain BC grows on benzene and some other aromatic compounds with oxygen or in the absence of oxygen with chlorate as the electron acceptor. Strain BC is a denitrifying bacterium, but it is not able to grow on benzene with nitrate. The closest cultured relative is Alicycliphilus denitrificans type strain K601, a cyclohexanol-degrading nitrate-reducing betaproteobacterium. Chlorate reductase (0.4 U/mg protein) and chlorite dismutase (5.7 U/mg protein) activities in cell extracts of strain BC were determined. Gene sequences encoding a known chlorite dismutase (cld) were not detected in strain BC by using the PCR primers described in previous studies. As physiological and biochemical data indicated that there was oxygenation of benzene during growth with chlorate, a strategy was developed to detect genes encoding monooxygenase and dioxygenase enzymes potentially involved in benzene degradation in strain BC. Using primer sets designed to amplify members of distinct evolutionary branches in the catabolic families involved in benzene biodegradation, two oxygenase genes putatively encoding the enzymes performing the initial successive monooxygenations (BC-BMOa) and the cleavage of catechol (BC-C23O) were detected. Our findings suggest that oxygen formed by dismutation of chlorite can be used to attack organic molecules by means of oxygenases, as exemplified with benzene. Thus, aerobic pathways can be employed under conditions in which no external oxygen is supplie