We show that resonant impulsive excitation of the Qy absorption band of bacteriochlorophyll a (BChl) launches a rapidly damped (gamma < 200 fs) ground-state coherent wave-packet motion that arises from intermolecular modes with clustered solvent molecules. Femtosecond pump-probe, dynamic-absorption signals were obtained at room temperature with BChl solutions in pyridine, acetone, and 1-propanol. The vibrational coherence observed in the 0-800-fs regime is modeled in the time domain by two (or three, in the case of 1-propanol) modulation components with asymmetric, inhomogeneously broadened line shapes and frequencies in the 100-200-cm(-1) range. The mean frequency of the vibrational coherence exhibits at least a quadratic dependence on the dipole moment of the solvent molecules and a y-intercept in the 100-cm(-1) regime. This trend is modeled by an expression for the natural frequency of a "6-12" potential composed of attractive terms from van der Waals forces and a repulsive term from the exchange (Pauli exclusion) force. The model suggests that comparable contributions to the potential are provided by the dipole-dipole and London dispersion interactions. These results support the hypothesis that the low-frequency vibrational modes in the 100-cm(-1) regime that are coupled to the light-driven charge-separation reactions in the reaction center from purple bacteria are derived from intermolecular vibrational modes between the chromophores and the surrounding protein medium.

Among radioactive contaminants, iodine-129 (129 I) is commonly either the top or among the top risk drivers, along with technetium-99 (99 Tc), at radiological waste disposal sites and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. Radioactive iodine (129 I) is of environmental concern due to its long half-life (1.6 × 10 7 years), toxicity, and mobility in the environment (Councell et al. 1997). However, there are currently very few approaches that effectively manage risks to human health and the environment. At the Hanford Site in Washington State, radioactive iodine (129 I), a fission product of plutonium, was discharged in 200 West Area disposal cribs. This discharge is responsible for the majority of 129 I contamination found in the groundwater (Zhang et al. 2013). The 200 West Area contains two separate plumes covering 1,500 acres where 129 I concentrations are ~3.5 pCi/L. The objective of this study was to evaluate the efficacy of commercial ion exchange resins and granular activated carbon (GAC) materials which will enable direct removal of all iodine species present in Hanford groundwater through treatment at the 200W pump and treat. Iodine sorption onto seven resins and six carbon materials was evaluated using water from well 299-W19-36 on the Hanford Site. These materials were tested using a range of solution-to-solid ratios. The test results are as follows:  The efficacy of the resin and granular activated carbon materials was less than predicted based on manufacturers' performance data. It is hypothesized that this is due to the differences in speciation previously determined for Hanford groundwater.  The sorption of iodine is affected by the iodine species in the source water. Iodine loading on resins using source water ranged from 1.47 to 1.70 µg/g with the corresponding K d values from 189.9 to 227.0 mL/g. The sorption values when the iodine is converted to iodide ranged from 2.75 to 5.90 µg/g with the corresponding K d values from 536.3 to 2979.6 mL/g. It is recommended that methods to convert iodine to iodide be investigated in fiscal year (FY) 2015.  The chemicals used to convert iodine to iodate adversely affected the sorption of iodine onto the carbon materials. Using as-received source water, loading and K d values ranged from 1.47 to 1.70 µg/g and 189.8 to 226.3 mL/g respectively. After treatment, loading and K d values could not be calculated because there was little change between the initial and final iodine concentration. It is recommended the cause of the decrease in iodine sorption be investigated in FY15.  In direct support of CH2M HILL Plateau Remediation Company, Pacific Northwest National Laboratory has evaluated samples from within the 200W pump and treat bioreactors. As part of this analysis, pictures taken within the bioreactor reveal a precipitate that, based on physical properties and known aqueous chemistry, is hypothesized to be iron pyrite or chalcopyrite, which could affect iodine adsorption. It is recommended these mater...

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The low-frequency vibrational coherence in the bacteriochlorophyll (BChl)-containing subunit proteins B777 and B820 from the LH1 light-harvesting complex isolated from Rhodospirillum rubrum G9 exhibits rapidly damped modulation components arising from intermolecular, formally nonbonding interactions between the BChl macrocycle and polar groups in the surrounding detergent or protein. The vibrational coherence observed in the monomeric B777 system resembles that observed previously with BChl in acetone because it contains a pair of broad overlapping line shapes with a mean frequency of 191 cm(-1), but the 10:1 intensity ratio of the librational and translational components is distinctive of the motions of the polar head groups in the nonionic detergent micelle that solvates the BChl macrocycle. In contrast, the vibrational coherence observed with the dimeric B820 complex is almost 20 times weaker in intensity and exhibits narrower line shapes and lower average frequencies than observed in B777. The structure of the B820 complex sterically protects the pair of BChl macrocycles from the surrounding solvent, so modulation components assigned to intrinsic interactions between the BChl and the protein and between the pair of BChl's are revealed. A relatively well-ordered interaction between the BChl macrocycle and a tryptophan residue in each alpha-helical polypeptide accounts for a 28 cm(-1) component with a narrow line shape, but most of the intensity arises from a broader 46 cm(-1) component that is assigned to the interaction between the paired BChl macrocycles. The breadth of the line shape for this component is a measure of the disorder in the ensemble of B820 subunits. The results support the hypothesis that the excited-state vibrational dynamics and the optical and/or Marcus charge-transfer reorganization energies of BChl in photosynthetic light-harvesting proteins and reaction centers are strongly controlled by van der Waals modes with neighboring molecules, with dominant contributions to the intermolecular potential arising from the London dispersion and dipole-dipole interactions.

Testing SummaryThe U.S. Department of Energy (DOE) Office of River Protection's Waste Treatment and Immobilization Plant (WTP) will process and treat radioactive waste stored in tanks at the Hanford Site. The waste treatment process in the pretreatment facility will mix both Newtonian and non-Newtonian slurries in large process tanks. Process vessels mixing non-Newtonian slurries will use pulse jet mixers (PJMs), air sparging, and recirculation pumps. An anti-foam agent (AFA) will be added to the process streams to prevent surface foaming but may also increase gas holdup and retention within the slurry.Some gas retention tests that were carried out in nonprototypic systems-bubble columns and impeller-mixed vessels-indicated trends that posed process and flammable-gas concerns . Both types of nonprototypic results indicated that the presence of AFA in a chemical simulant of Hanford Tank 241-AZ-101 high-level waste (HLW) might increase gas retention by a factor of 10 or more over that in clay without AFA, the simulant on which WTP design studies were based (see Section 1.2). In addition, the increase over clay holdup was greater at lower simulant yield stress, implying that the 30-Pa simulant results, which had been used for WTP design, might not bound gas retention.The work described in this report addresses gas retention and release in simulants with AFA through prototypic testing and analytical studies. This test program was established to determine whether the AFA has as strong an effect in a large-scale prototypic mixing system as it did in the small-scale nonprototypic tests. Gas holdup and release tests were conducted in a 1/4-scale replica of the lag storage vessel operated in the Pacific Northwest National Laboratory (PNNL) Applied Process Engineering Laboratory using a kaolin/bentonite clay and an AZ-101 chemical simulant with non-Newtonian rheological properties representative of actual waste slurries. Additional tests were performed in a smallscale mixing vessel in the PNNL Physical Sciences Building using liquids and slurries representing major components of typical WTP waste streams to address the fact that simulants delivered to the WTP will come from other tanks in addition to 241-AZ-101. Analytical studies were directed at discovering how the effect of AFA might depend on gas composition, and a model was developed for predicting the effect of AFA on gas retention and release in the WTP, including the effects of mass transfer to the sparge air.The prototypic gas retention and release tests performed in this test program indicate that gas holdup with AZ-101 simulant with AFA is higher than it is in clay, but not to the extent that initially raised WTP design concerns. In addition, the trend to a higher increase in holdup with decreasing simulant yield stress was not seen in the prototypic system. The work at PNNL was part of a larger program that included tests conducted at Savannah River National Laboratory (SRNL) that is being reported separately. SRNL conducted gas holdup tests in a small-scale m...