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1609848CHE - Environmental Chemical Science

PD 09-6882 11/02/15

141368361

SUNY College of Environmental Science and Forestry

0028514000

SUNY College of Environmental Science and ForestryPO Box 9Albany, NY. 122010009

SUNY College of Environmental Science and ForestrySUNY College of Environmental Science and Forestry SUNY College of Environmental Science and Forestry1 Forestry DriveSyracuse ,NY ,132101220 ,US.

Molecular Insights into the Oxidation of Atmospheric Mercury: The Next Frontier in Atmospheric Mercury Science

566,431 36 01/01/16

Chemistry Department

315-470-6856

1 Forestry Drive121 Jahn LaboratorySyracuse, NY 13210United States

Theodore S Dibble PhD 1992 315-470-6596 tsdibble@esf.edu

Chuji Wang PhD 1998 662-325-9455 cw175@msstate.edu

152606125

A collaborative proposal from one organization (GPG II.D.4.a)Research - other than RAPID or EAGER

11/02/2015 1 03090000 CHE 6882 08/30/2017 9:24am S

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AUTHORIZED ORGANIZATIONAL REPRESENTATIVE SIGNATURE DATE

NAME

TELEPHONE NUMBER EMAIL ADDRESS FAX NUMBER

fm1207rrs-07

Page 3 of 3

William J Nicholson Nov 2 2015 1:20PMElectronic Signature

315-470-6606 wjnichol@esf.edu 315-470-6779

B. PROJECT SUMMARY Overview Mercury is a well-known neurotoxin that severely affects human and environmental health. Mercury is emitted to the atmosphere primarily as atomic mercury (Hg(0)), which largely stays in the atmosphere until it is oxidized. Unfortunately, we lack the most basic molecular-level information about mercury oxidation reactions: for most reactions the rate constants and the identity of the reaction products are unknown! This huge scientific gap frustrates progress towards understanding global mercury cycling and determining the rate of mercury transfer to ecosystems. Oxidation of Hg(0) is dominated by reaction with atomic bromine (Br•), a reaction which forms •HgBr radical. To fill the void in our knowledge of the fate of •HgBr, we propose to combine cutting-edge tools of spectroscopy and computational chemistry to achieve three major goals:

1) Characterize a clean photolytic source of •HgBr radicals to ensure reliable kinetic studies 2) Determine rate constants for atmospherically significant •HgBr reactions: its reactions with O3,

volatile organic compounds (VOCs), and atmospherically abundant radicals 3) Identify •HgBr reaction products and enable their measurement in the field

Experiments will take advantage of the power of cavity ringdown spectroscopy (CRDS) to characterize the •HgBr source, determine •HgBr rate constants, and identify reaction products. Advanced theoretical methods will yield mechanisms and rate constants, and, in addition, determine the spectroscopic and mass spectrometric signatures of the unknown •HgBr reaction products. This first-of-its kind data will largely fill the present gaps in our knowledge of the mechanisms and kinetics of Br-initiated oxidation of Hg(0).

Intellectual Merit Kinetic studies of mercury oxidation have been bedeviled by interferences from wall reactions and secondary chemistry. The proposed approach (pulsed photolysis of HgBr2 in a flow cell) is a direct source of •HgBr; it is a clean source of •HgBr in that it avoids wall-catalyzed reactions. Determination of the quantum yields for HgBr2 photolysis will enable evaluation and suppression of side reactions that could otherwise confound experimental studies of kinetics and mechanism. CRDS experiments and computational chemistry will be used to determine, for the first time, the rate constants for reactions of •HgBr with ozone, VOCs, and atmospherically abundant radicals (•Y = NO, NO2, HOO, ClO, BrO, and IO). Rate constants will be determined as a function of temperature and pressure to span the full range of atmospheric conditions. The as-yet unknown •HgBr reaction products will be identified using CRDS in the UV-visible. Theoretical calculations will ensure the reliable interpretation of experimental spectra. This will represent the first-ever experimental detection of these species. Quantum calculations will provide the information needed to quantify these compounds in the field by mass spectrometry, even in the absence of authentic standards.

Broader Impacts The mechanisms and rate constants determined here will be seized upon by modelers to improve their descriptions of mercury chemistry at local to global scales. The experimental research tools generated in this research will be used to design new field experiments to validate these models. These synergistic interactions between scientists doing field studies, modeling, and laboratory work will greatly accelerate progress towards understanding global mercury cycling. The unique societal benefit of the proposed research lies, ultimately, in reducing the impact of mercury on human and environmental health. Two graduate students and several undergraduate students from varied disciplines will be trained in this project. Outreach will be carried out with diverse local communities and via the Internet.

TABLE OF CONTENTSFor font size and page formatting specifications, see PAPPG section II.B.2.

Total No. of Page No.*Pages (Optional)*

Cover Sheet for Proposal to the National Science Foundation

Project Summary (not to exceed 1 page)

Table of Contents

Project Description (Including Results from Prior

NSF Support) (not to exceed 15 pages) (Exceed only if allowed by aspecific program announcement/solicitation or if approved inadvance by the appropriate NSF Assistant Director or designee)

References Cited

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Current and Pending Support

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*Proposers may select any numbering mechanism for the proposal. The entire proposal however, must be paginated.Complete both columns only if the proposal is numbered consecutively.

1

1

15

11

4

12

2

2

2

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I. INTRODUCTION Mercury is a widespread neurotoxin that severely impacts human health and the health of ecosystems globally. Although mercury has been the subject of study for decades, fundamental and important questions about mercury still challenge scientists. The critical question we propose to address is: at what rate is mercury transferred from the atmosphere into ecosystems, subsequently affecting animal and human life? Mercury enters the atmosphere largely as elemental mercury (Hg(0)) and is transferred to ecosystems mainly after oxidation to Hg(II).1 As a result, this oxidation largely controls when and where mercury enters ecosystems. It is well accepted that uncertainties in the mechanism and kinetics of Hg(0) oxidation contribute some of the largest variability to predictions of mercury transfer from the atmosphere to ecosystems (see Fig. 1).2-5 Clearly, the lack of molecular-level insights into Hg(0) oxidation processes severely limits our understanding of the global transport and cycling of mercury.

Our ignorance of the mechanism and kinetics of Hg(0) oxidation has additional consequences. For example, comparisons of models and measurements are confounded by the vast uncertainties in mechanisms and rate constants assumed in models. Also, ignorance of the identity of Hg(II) species hinders field measurement of their concentrations, which further limits model-measurement comparisons. Atomic bromine (Br) is now believed to be the dominant oxidant of atmospheric mercury, globally. 6-8 The goal of this proposal is to transform our understanding of mercury oxidation by Br. We propose to determine the kinetics and mechanisms of the reactions of the •HgBr intermediate formed in the first step of Br-initiated oxidation of Hg(0). This research will combine modern techniques of spectroscopy and theoretical chemistry. This integrated program of experimental and computational research will, ultimately, transform our understanding of global mercury transport, deposition, and cycling. II. GOALS AND SIGNIFICANCE The specific goals of this proposal are motivated by the present state of knowledge of Br-initiated oxidation of mercury. Atomic bromine initiates oxidation of Hg(0) via the reaction:9-10 Br• (g) + Hg (g) •HgBr (g) (1) The atmospheric fate of •HgBr has yet to be determined by experiment. Instead, current models rely on a few studies using computational chemistry. Over a decade ago, calculations11-12 demonstrated that •HgBr radical can react with OH and Br to make stable compounds: •HgBr (g) + •OH (g) BrHgOH (g) (2) •HgBr (g) + •Br (g) HgBr2 (g) (3)

Reactions (2) and (3) are expected to possess high rate constants because two radicals simply add together to form a bond. It is known that rate constants for such radical + radical reactions usually depend rather little on the identity of the radicals. In light of this, we asked the question: does •HgBr form stable gas-phase compounds with radicals (•Y), such as NO, NO2, HOO, ClO, and BrO, that are much more abundant than •Br and •OH?

0

4000

2000

Base Model no OH + Hg reaction Higher k(O3 + Hg)

Figure 1. Dependence of total mercury wet deposition (ng m-2 month-1) on gas-phase oxidation mechanism and kinetics of Hg(0) (Ref. 4).

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The PI13-14 used quantum chemistry to demonstrate, that, in fact, •HgBr can form stable compounds (BrHgY) with most of these radicals via: •HgBr (g) + •Y (g) BrHgY (g) (4) These findings were quickly incorporated into other studies.7,

15-21 Modeling confirmed that the proposed reactions of •HgBr with abundant NO2 and HOO dominate the fate of •HgBr, both in the marine boundary layer15 and globally7 (see Fig. 2).

This work has three closely linked goals concerning •HgBr radicals:

1) Characterize a “Clean” and Direct Photolytic Source of •HgBr Radicals

Unwanted side reactions or formation of solid products (see Figure 3) have confounded efforts to determine rate constants and mechanisms for Hg(0) oxidation.22, 23 To avoid these problems we will use

laser photolysis of HgBr2 in the ultraviolet (UV) to produce •HgBr. HgBr2 photolysis is known to form readily detectable concentrations of •HgBr.24-25 Unfortunately, the quantum yield for •HgBr formation (versus other products) from HgBr2 photolysis is not known. This means that we are ignorant of the potential for unwanted side reactions following HgBr2 photolysis. The quantum yield for •HgBr formation will be determined using cavity ringdown spectroscopy (CRDS), a powerful method for absorption spectroscopy. This data will aid the design and analysis of future kinetic studies. Characterization of this clean and direct •HgBr

source will transform laboratory scientists’ ability to investigate •HgBr reactions.

2) Determine Rate Constants of Reactions of •HgBr with Abundant Radicals (•Y), VOCs, and Ozone Rate constants for reactions of •HgBr with •Y have not been measured, leaving modelers to guess at their values (as was done in the model that led to Figure 2). The reactions of •HgBr with ozone and Volatile Organic Compounds (VOCs) have not even been considered, but could be as significant for •HgBr (and Hg(0) oxidation) as they are for the fate of other atmospheric radicals. The proposed work represents the first experimental or computational study of the kinetics of •HgBr reactions with atmospherically abundant radicals and trace gases. Both experiment and theory will be used to obtain rate constants for these reactions. The experiments will use CRDS to monitor the concentration of •HgBr. Pseudo-first order conditions will be used to suppress side reactions. The experimental rate constants will also be used to validate results obtained from high levels of quantum chemistry and theoretical kinetics. This will enable theory to reliably compute rate constants for reactants (HOO, ClO, BrO, and IO) or conditions (pressures and temperatures) not amenable to experimental study. The results will enable modelers to realistically predict the fate of •HgBr under the full range of conditions relevant to the entire troposphere and stratosphere.

3) Identify •HgBr Reaction Products and Enable Their Quantification in the Field No experiment has attempted to detect the important •HgBr reaction products in the laboratory, let alone in field studies. The various BrHgY compounds potentially exist as multiple isomers (e.g. BrHgONO vs. BrHgNO2), whose atmospheric fates are likely different. Our ignorance of the actual products of •HgBr + •Y reactions represents a critical uncertainty in evaluating the influence of these reactions. CRDS experiments will be used to obtain UV-visible spectra of the products of •HgBr reactions. High-level theoretical studies will predict the spectroscopy of expected reaction products. These computed spectra will be used in experiments to select wavelength regions to study and to interpret

Figure 3. SEM image of products of Hg reaction with iodine.

HgBr+BrHgBr+OH

HgBr+HO2

HgBr+NO2

HgBr+BrOHgBr+ClOHg+Claqueous (O3, HOCl)

Figure 2. Global average fraction of atmospheric Hg(II) formation from various reactions (Ref. 7).

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observed spectra. Theory will also investigate whether electronic excitation leads to photolysis. From these investigations we will determine the potential for photolysis to control the fate of these Hg(II) compounds. This work will provide the first experimental identification of •HgBr reaction products, and be the first to assess their potential for photolysis.

Chemical ionization mass spectrometry (CI-MS),26-27 unlike UV-visible absorption spectroscopy, could be a viable tool for detecting and quantifying BrHgY compounds in the atmosphere. To enable CI-MS studies of these compounds, we will use theory to determine the rate constants and product ions for reactions of BrHgY with CI-MS reagents. This information will enable other scientists to quantify a variety of Hg(II) compounds using CI-MS, even in the absence of authentic standards.

The research tools developed in this project will be enormously valuable for further experimental studies in the laboratory and in field work. The rate constants and mechanisms generated from this research will transform our understanding of atmospheric mercury chemistry. The incorporation of these molecular-level insights into the research of scientists doing modeling and field work would resolve the most outstanding uncertainties in atmospheric mercury chemistry. This, in turn, would enable a better understanding of global mercury cycling and mercury transfer into ecosystems.

III. BACKGROUND Mercury is a widespread and dangerous neurotoxin, and very low-level exposure in utero can cause subtle problems in cognitive and motor skills.28 Six percent of U.S. women of childbearing-age have blood mercury levels at or above the level of concern.29 Mercury also harms fish and waterfowl.17 Ambient concentrations of Hg(0) are typically ~1 107 atoms cm-3 (< 1 pptv). Concentrations of Hg(II) are typically less than that of Hg(0), due to the slow rate of Hg(0) oxidation and the fast rate of Hg(II) transfer to ecosystems. Chemical speciation of Hg(II) compounds is not yet achievable in the field. While the summed concentrations of Hg(II) compounds can be measured, detection efficiencies usually depend on the identity of the Hg(II) compound, and species-dependent interferences from ozone may also occur.30-33 These challenges severely limit the ability of field work to advance atmospheric mercury science. Upon entering ecosystems Hg(II) transforms readily into organomercury compounds,34 which are the most toxic form of mercury.35 For most Americans, mercury exposure arises from eating fish, which bioaccumulate organomercury.28, 36 Since mercury is mostly emitted to the atmosphere as Hg(0), knowledge of the rate of Hg(0) oxidation to stable Hg(II) compounds is critical to predicting where mercury will enter ecosystems and impact ecological and human health.

III.A. Atmospheric Chemistry of Mercury and the Role of Atomic Bromine Prior to 2005, models of atmospheric mercury (like the one whose results are displayed in Figure 1) assumed that OH radical and O3 dominated oxidation of Hg(0).37-38 Since then, it has been shown that OH radical binds Hg(0) too weakly to be important under most atmospheric conditions.11, 39-40 The Hg + O3 reaction produces largely solids and no feasible gas-phase reaction product is known.23, 39-43 Together with the recognition of Br as a globally important oxidant for Hg(0), these facts have led many scientists to neglect OH and O3 as oxidants of Hg(0).2, 6-8, 15, 44 Atomic bromine is the key species initiating atmospheric mercury depletion events in polar coastal regions.45-46 Field work in marine surface air at low latitudes indicate that Br but not OH or ozone is able to account for daily cycles of Hg(II) production.15, 47 Modeling studies indicate that Br could account for most of the global oxidation of Hg(0) to Hg(II).2, 6 Other halogens are mostly unimportant due to low abundance or weak bonds to mercury.2, 11, 40 Therefore, many models of local, regional and global Hg(0) oxidation find that Br is nearly the sole oxidant.2, 6-8, 15, 44

III.B. Critical Gaps in Knowledge of Bromine-Initiated Mercury Oxidation in the Atmosphere

1) Rate constants, k(•HgBr + •Y), are not known. As a result, modelers typically assume that k(HgBr + •Y) equals k(•HgBr + •Br) for all •Y,6, 11 as in the model that led to Figure 2.7

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2) The products of •HgBr + •Y reactions are not known. As noted above, our preliminary studies show that •HgBr can form thermally stable BrHgY compounds. Notably, potential alternative reaction pathways have yet to be explored: see Table 1, below. Almost all of the alternative products listed in Table 1 appear thermodynamically feasible; moreover, these reactions have well-established analogues,12,

48-49 meaning that chemical intuition argues for their feasibility.

Table 1. Some Competing Reaction Pathways for BrHg• + •Y Reactionsa Y Radical-Radical Addition Disproportionation Reduction to Hg(0) •NO2 BrHgNO2 and BrHgONO BrHgO• + NO BrNO2 + Hg •OOH BrHgOOH BrHgH + O2 (3 ) BrOOH + Hg •OX (X= Cl, Br, I) BrHgOX and BrHgXO BrHgO• + •X BrOX + Hg a) Thermodynamic arguments allow all of these reactions, except formation of BrHgO• + NO

Modelers incorporating the reactions of •HgBr with •Y have only considered BrHgY formation, but not the alternative pathways included in Table 1. Some of the alternative reactions listed in Table 1 reduce the mercury in •HgBr back to Hg(0)!12 To the extent this occurs, •HgBr reaction with •Y does not lead to oxidation, and model predictions are misleading.

3) Concentrations of ozone and summed VOC concentrations greatly exceed those of radicals, so the oxidation of BrHg• might be controlled by reactions with ozone and VOCs. Unfortunately, reactions of •HgBr with ozone and VOCs have yet to be considered.

As a result of the uncertainties enumerated above, we conclude that our understanding of the bromine-initiated oxidation of Hg(0) is still in its infancy. This means that atmospheric lifetime of mercury remains highly uncertain, and the spatial distribution of mercury deposition and entry into ecosystems cannot be reliably modeled from the rudimentary kinetic and mechanistic information currently available.

III.C. Experimental Approach for Clean Production and Reliable Kinetic Studies of •HgBr Experiments to fill the critical gaps in our knowledge of the fate of •HgBr require a clean source of •HgBr, and some experiments will require knowledge of the yield of •HgBr (versus Br + Hg + Br). Use of HgBr2 photolysis as an •HgBr source avoids interference from wall-catalyzed oxidation of Hg(0) forming solids (see Figure 3, above). This method also avoids the slow rate of the Hg(0) + Br reaction9 and the potential for many side reactions that arise from using indirect methods of •HgBr production.24-25 The high sensitivity, universality, and high spectral resolution of cavity ringdown spectroscopy (CRDS) will be exploited in this research. CRDS will be used to monitor the temporal evolution of concentrations of •HgBr in the presence of excess co-reactant (that is, using pseudo-first order conditions). This will ensure that we obtain highly reliable rate constants. Although radical concentrations will be higher than atmospheric, the rate constants obtained will still be valid at atmospheric concentrations. CRDS will also be used to obtain UV-visible spectra of •HgBr reaction products, using guidance from quantum calculations. The co-PI has extensive experience with CRDS, including measurements of [Hg(0)] in reactive environments and 1 atmosphere of air.50-52

III.D. Computational Approach for Reliable Thermodynamics and Kinetics The equations of quantum mechanics and the algorithms used to solve those equations apply equally well to radicals, ions and transition states as to stable molecules. This enables quantum chemistry to provide quantitative insights into stability, spectra, and kinetics that may be hard to obtain from experiments. We will make use of NSF-supported High-Performance Computing Facilities (XSEDE) for these calculations. The analysis of quantum chemistry data with statistical theories of kinetics will allow us to compute rate constants, k(T) or k(P,T), for all reactions of interest here. We will use results from the literature and the proposed experiments to ensure the accuracy of our methods for both quantum chemistry and kinetics. The PI has extensive experience in using quantum chemistry and theoretical kinetics to improve our

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understanding of atmospheric chemistry. IV. METHODS IV.A. Experimental Methods IV.A.1 CRDS for measurements of concentration

CRDS53-58 is an absorption technique, so it can be used to detect absorbing species. It achieves high sensitivity because of the multi-pass nature of the optical absorption path. In CRDS, as illustrated in Fig. 4, a laser pulse is injected through one end-mirror of an optical cavity (absorption cell), where the injected light pulse remains trapped between the mirror surfaces. The intensity of the light in the cavity decays exponentially with time at a rate defined by the round-trip losses experienced by the laser pulse. These losses are due to the finite reflectivity of the cavity mirrors, optical absorption, and/or scattering. Absorption is determined from the measured difference in the decay time (ringdown time), , for light trapped in the optical cavity in the presence versus absence of an absorber (or ON versus OFF an absorption line). CRDS determines absolute absorbance, so it can accurately quantify concentrations without calibration.

In the simplest case, where there are no absorbing species present, the ringdown time, 0, is controlled by the speed of light, c, the mirror reflectivity, R, and the distance between the mirrors, d (see eqn. 5a). With an absorber, the ringdown time is described by equation 5b:

)1(0 Rcd , (5a) )1( ndRc

d (5b)

where is the absorption cross section (cm2 molecule-1) of the absorber and n is the number density (Absorbance= nd). When an absorber fills only a length l (l < d) of the ringdown cavity, the absorbance of the sample is nl. This will be the case for •HgBr and other species we produce by photolysis. The multipass nature of CRDS enables it to achieve sensitivities more than 10,000 times greater than single-pass absorbance measurements. In addition to its high sensitivity, a single ringdown event is brief enough to provide the temporal resolution needed for kinetic studies. CRDS can be coupled to high-resolution laser sources to spectroscopically resolve narrow absorption peaks of atomic and diatomic molecules, like Hg(0) and •HgBr. CRDS at 253.65 nm has been used by the co-PI50-52 and others59-62 to measure concentrations of Hg(0) in a variety of reactive environments. CRDS has not yet been implemented to study atmospheric Hg(0) oxidation or •HgBr reactions. The minimum detectable absorbance, (1-R) / , of the ringdown system is determined by the mirror reflectivity, R, and the overall ringdown baseline stability, / , where is the standard deviation of the ringdown time, . These two parameters determine the minimum detectable absorbance ( nl) of a ringdown system to be 3 × 10-7, given a mirror reflectivity of 99.99% and a ringdown stability of 0.3%, both of which are achievable with an optimized ringdown system. As demonstrated in Section IV.A.3, below, this leads to single-shot detection limits much lower than

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the anticipated species concentrations. The spectral and temporal resolution of CRDS enables quantification of multiple species in mere minutes.

IV.A.2 Generating Radicals •HgBr radicals will be generated using laser photolysis (LP) via the reaction:

HgBr2 + h •HgBr + •Br (6) Donahoue demonstrated that is approach is superior to others for generating •HgBr radicals.24 This approach avoids the problem (see Figure 3) of extensive Hg(0) oxidation on reactor walls because Hg in HgBr2 is already oxidized. Donahoue obtained excellent signal-to-noise ratios (S/N) with laser-induced fluorescence when using this method to generate •HgBr. She also showed that the •HgBr transitions are readily resolved from those of Hg(0). Laser photolysis will be carried out at 266 nm, where HgBr2 has an absorption cross-section of 10-18 cm2 molecule-1.63 The room temperature vapor pressure of HgBr2 is estimated using a Clausius-Clapeyron analysis of literature data64 as 3 × 1012 molecules cm-3. The extent of photolysis can be calculated from the laser pulse energy and beam size. For example, 350 mJ per pulse at 266 nm and a beam diameter of 1.0 cm would result in photolysis of 1 × 1012 molecules cm-3 of HgBr2 when the HgBr2 concentration is only 75% of the saturation vapor pressure at 298 K. Two atmospherically important and abundant radicals (NO and NO2) can be obtained from gas cylinders in high concentrations and readily quantified, so experimental studies of •HgBr + •Y reactions will focus on these radicals. Our preliminary modeling studies confirm that side reactions and unwanted photochemistry will not interfere with measurements of the desired rate constants. Studies of •HgBr reactions with other atmospherically important radicals, such as halogen oxides (ClO, BrO, and IO) and HOO, present challenges in producing radicals: (a) cleanly (without side reactions), (b) in a spatially uniform manner; and (c) in high concentration. As a result, this proposal includes computational but not experimental studies of •HgBr reactions with halogen oxides and HOO.

IV.A.3 Monitoring Concentrations of Radicals As an absorption technique, CRDS is universal. Table 2, below, lists the known absorption wavelengths and absorption cross-sections of the species to be measured using CRDS. This data is used to select laser wavelengths for both photolysis and CRDS measurements. Our ability to meet several experimental challenges is discussed here:

1) Near-simultaneous measurements of Hg(0) and •HgBr We take the advantage of the unique natural coincidence of the spectral wavelengths of the Hg(0) transition at 253.65 nm and the •HgBr (4-1) band at 254.28 nm to measure Hg(0) and •HgBr nearly simultaneously. These two wavelengths are close enough to be covered by one set of ringdown mirrors but also readily resolved in the proposed CRDS system.24, 65-

66 Switching the ringdown laser output between these two wavelengths can be done within 1 minute, ensuring measurements of [Hg] and [•HgBr] are carried out under identical conditions. The laser wavelength will be monitored by a Toptica-WSU30 wavemeter with an accuracy of 0.0001 nm.

2) Detection sensitivities As described in Section IV.A.1, the minimum detectable single-pass absorbance ( nl) is 3 × 10-7, so the limit of detection (LOD) is three times this: 1 × 10-6. The estimated LP path-length that is overlapped with ringdown (RD) beam is 2.7 cm (see Research Plan). The detection limit near 254 nm for changes in [HgBr2] in this path-length is 4 × 1011 molecules cm-3. The detection limit for Hg(0) (at 253.65 nm50-59) in this experiment is 1.5 × 107 atoms cm-3. Under the assumptions listed in IV.A.2, and with the •HgBr quantum yield at 266 nm conservatively assumed to be as low as 0.1,24 we will produce [•HgBr] of 1 × 1011 molecules cm-3. The detection limit for •HgBr will be 3 × 109 molecules cm-3, given an absorption cross-section of 10-15 cm2 molecule-1. The resulting high S/N of >1000, 30, and 2.5 for Hg(0), •HgBr, and HgBr2, respectively, means that changes in their concentrations can be readily monitored by CRDS.

3) Selectivity As described in point (1), immediately above, the sharp spectral lines of Hg(0) and •HgBr are readily distinguished. By contrast, the UV spectrum of HgBr2 has no vibrational structure, and its

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absorption cross-section is ~1000 times smaller than those of Hg(0) and •HgBr. Thus, the broad absorption of HgBr2 can be treated as a baseline of the CRDS system. Loss of HgBr2 due to photolysis will appear as a decrease in the baseline. Absorptions due to •HgBr reaction products will be readily distinguished from those of other species not only by wavelength (see below), but also by the kinetics of their appearance.

4) Spectra of •HgBr reaction products Preliminary calculations by the PI, shown in Table 2, indicate that BrHgY species absorb light in the same spectral region as HgBr2. Absorptions by products in this region can be distinguished from those of HgBr2 by the kinetics of their appearance. The PI’s preliminary calculations on BrHgONO suggest that it also absorbs at longer wavelengths (280-360 nm) of tropospheric relevance. Note that raising the reactor temperature to 100 °C would increase the potential HgBr2 concentration by a factor of about 1000,64 with the result that product spectra would have S/N ratios of ~25 (single shot) even if their absorption cross-sections are an order of magnitude lower than that of HgBr2. •HgBr is sufficiently thermally stable (lifetime of ~100 ms at 100 °C and 200 Torr)13 that such temperatures are readily useable in the proposed experiments.

Table 2. Absorption wavelengths and cross-sections for selected mercury species. Results for BrHgONO and BrHgNO2 are from preliminary computations.

Chemical species

Wavelength (nm) Cross-section, (cm2 atom-1)

or (cm2 molecule-1)Notes

experiment calculated

Hg(0) 253.65 -- 2.4 - 3.3 × 10-14 at 254 nm

CRDS of Hg(0) by the co-PI and others45-46

HgBr (D-X)

254.28 the (4-1) band 258 10-14 -10-15

This band in the D-X system is the one closest to the Hg(0) 254

nm line65-66

HgBr2 230 a 233 b 10-18 at 250-266 nmd

Concentration changes will be monitored near 250 nm.

BrHgONO -- 222-361 c Estimated as 10-17-10-19 from

calculation

The wavelengths re-calculated by the PI will be used to guide the search for their CRDS spectra.e BrHgNO2 -- 215-293 c

a) Peak of broad transitions; b) Vertical excitation energies from preliminary calculations using time-dependent density functional theory (TD-DFT) using the basis sets as in Ref. 13; c) As with (b), but multiple spin-allowed vertical excitations within the listed wavelength band. d) Reference 63. e) The proposed work would use EOM-CCSD in place of TD-DFT.

IV.B. Achieving Reliable Quantum Chemical Results and Verifying Reliability IV.B.1 Electron Correlation and Basis Sets The quality and reliability of quantum calculations largely depends on two factors:67 1) the level of treatment of electron correlation and 2) the flexibility of the atom-centered basis functions used to construct molecular orbitals. The “gold standard”68-70 for treating electron correlation is the coupled cluster singles and doubles (CCSD) with the inclusion of a perturbative estimate of the triples excitations (CCSD(T)).71-73 The PI used CCSD(T) in his previous work13, 14 and plans to use it here. Basis sets used for calculations on mercury, bromine, and iodine will account for scalar relativistic effects using effective core potentials (ECPs). The ECPs of the Stuttgart group74-76 together with the corresponding triple zeta basis sets for non-core electrons have demonstrated high accuracy for mercury chemistry when combined with CCSD or CCSD(T).12, 14, 42, 77-79 These are the basis sets we have used and plan to continue employing. We will also account for an additional relativistic effect: spin-orbit

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coupling.12, 79-81 For some systems we plan to study, the computational cost of CCSD(T) for obtaining molecular geometries and vibrational frequencies may be unreasonably high. Yet we still want the accuracy of CCSD(T) energies for reaction enthalpies, etc. One can approach the accuracy of CCSD(T) energies by computing them at the geometries calculated at a less demanding level of theory, such as CCSD. This common approach relies on two facts: 1) CCSD is still very successful at computing molecular geometries and frequencies; and 2) it requires much less cpu time to compute energies at a given geometry than to optimize a molecular geometry. We find this approach to be very efficient using the CFOUR program82 on NSF-supported High Performance Computing resources. In cases where electron correlation is not well-treated by CCSD(T), such as bond-breaking, we will exploit recent extensions of CCSD(T),83-84 or multireference methods.85-88 Various diagnostics will be used to establish when such approaches are needed.89-90 Excited states are very well described by the equation of motion (EOM) variant of CCSD theory.91-92 EOM-CCSD is coded very efficiently in CFOUR, and obtains an accuracy of better than 0.1 eV in excitation energies.93 EOM-CCSD will also be used to compute integrated peak intensities and the potential for photolysis of excited states.

IV.B.2 Theoretical Methods for Determining Rate Constants Data obtained from quantum calculations are used as input for theoretical calculations of rate constants. Transition state theory (TST)94 gives expressions for computing temperature-dependent rate constants, k(T), of elementary bimolecular reactions. Rate constants for barrierless association reactions of radicals and unimolecular dissociation reactions can be obtained from variational TST (VTST) in the high pressure limit,95 e.g., using the POLYRATE program.96 To use the most accurate VTST method (variable reaction coordinate VTST) requires repeating thousands of quantum chemistry calculations per reaction. To make this computational effort feasible, it will be necessary to take advantage of the efficiency and reliability of density functional theory (DFT). The DFT method to be used will be validated with CCSD(T) calculations. Rate constants for such reactions depend on the temperature (T) and total pressure (P). To obtain effective rate constants, k(P,T), for these reactions, we will carry out RRKM/Master Equation calculations97 using the MESMER program.98 Rate constants for ion-molecule reactions (for studies of chemical ionization MS) will be calculated using Langevin theory99 for non-polar molecules and the average dipole orientation theory100 for polar molecules.

V. PLAN OF RESEARCH The proposed experimental work will be carried out primarily by one graduate student under the supervision of the co-PI, with frequent consultation with the PI. The proposed computational studies will be carried out primarily by one graduate student working under the direction of the PI. The research effort breaks down into six tasks, detailed below, split between experimental and theoretical tasks.

Experimental Task 1. Construction of the Laser Photolysis-Cavity Ringdown Spectroscopy (LP-CRDS) System and Determination of •HgBr Quantum Yields from HgBr2 Photolysis A) Construction of a LP-CRDS reaction system

Figure 5 shows the proposed experimental system. The ringdown (RD) cavity consists of two RD mirrors with a reflectivity 99.99% and a mirror spacing of 50 cm. The RD laser source will be an optical parametric oscillator (OPO) system (Spectra-Physics, MOPO-HF

Figure 5. The proposed laser photolysis-cavity ringdown spectroscopy (LP-CRDS) system.

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PRO-270-10, linewidth <0.005 nm, spectral range of 227 nm – 4.3 m, pulse duration ~10 ns). The optical axis of the RD cavity crosses the axis of the LP arm at a small angle (~20 degrees). The LP beam will be reformed to have a beam diameter of 1.0 cm, so that the overlapped length (highlighted in green) of the LP beam and RD beam will be maximized (at ~2.7 cm). Gas will flow continuously through the cell. Two donut-shape plates will be placed as shown in the figure to minimize turbulent diffusion of the radicals in the flow cell.

The view port in the reactor has a quartz window installed to enable LIF detection (of •HgBr or other species) in future studies. The timing sequence between the LP and RD lasers will be controlled by a pulse generator (DG 535), whose 1 ns precision is more than precise enough for the proposed studies. The LP repetition rate and gas flow rate will be controlled to ensure photolysis products do not accumulate in the reactor and do not confound the interpretation of experiments.

B) Determination of quantum yields of in HgBr2 photolysis HgBr2 photolysis at 266 nm is known to produce •HgBr radicals, but photolysis also leads to Hg + 2 Br.24 Determining the quantum yields of products from HgBr2 photolysis will be invaluable for planning future kinetic and spectroscopic investigations of •HgBr reactions, e.g., with HOO and halogen oxides (XO). We will use the known absorption cross-sections50, 59, 63 of Hg(0) and HgBr2 to quantify their concentrations using CRDS near 254 nm immediately before and after photolysis at 266 nm. The quantum yields of Br and •HgBr formed in photolysis will then be determined by mass balance.

Characterization of a clean and direct •HgBr source will transform scientists’ ability to reliably investigate •HgBr reactions of atmospheric importance. Computational Task 1. Kinetics and Mechanism of •HgBr reacting with NOx, O3, and VOCs A) Reaction of •HgBr + NOx

This computational task will focus first on the rate constants for reaction •HgBr with NO2. Recall from Table 1 that there are at least three potential sets of products of this reaction: BrHgNO2 BrHgONO Hg + BrNO2 each with (potentially) different consequences for mercury oxidation. Formation of BrNO2 + Hg might appear unlikely, but this reaction is exactly analogous to the barrierless reaction:12 •HgBr + •Br Hg + Br2 (7) which possesses a higher rate constant than reaction (3):12

•HgBr + •Br HgBr2 (3) Formation of Hg + BrONO, like reaction (7), does not lead to Hg(0) oxidation. Given the expected importance of the BrHg• + NO2 reactions and the varied consequences of their formation, it is necessary to establish the relative importance of each set of products. Our calculations13 indicate that •HgBr binds only weakly with NO, but we will refine the bond energy and compute the rate constants for formation of BrHgNO. The rate constant, k(T), for formation of the alternative product, BrNO + Hg, will also be calculated. Rate constants will be computed as a function of temperature, and, where relevant, of pressure, to provide data for use in modeling •HgBr chemistry throughout the troposphere and stratosphere. Chemically activated processes will be considered, that is: •HgBr + •Y BrHgY* other products (where * denotes an energized intermediate).

B) Reaction of •HgBr with VOCs This will be the first study of the reaction of •HgBr with VOCs. Reactions of radicals with VOCs proceed via abstraction of hydrogen atoms: •HgBr + RH R• + BrHgH (8) or addition to sp2-hybridized carbon atoms: •HgBr + RCH=CHR’ RC•HCHR’HgBr (9)

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We will investigate the thermodynamics, mechanisms and kinetics of these processes using representative VOCs (small alkanes, alkenes, oxygenates, aromatic compounds, etc.). If any of these reactions are revealed to be important, the subsequent reactions of atmospheric relevance will be investigated. If hydrogen-abstraction reactions are feasible, rate constants for those reactions will be refined to account for effects of quantum-mechanical tunneling.101-102

C) Reaction of •HgBr with ozone This will be the first study of the reaction of •HgBr with ozone. We will survey a range of possible products, starting with the one that is most obvious to an atmospheric chemist: •HgBr + O3 BrHgO• + O2 (10) The thermodynamic stability of BrHgO• is known from theory,79 and reaction (10) is exothermic by ~34 kcal/mol. If BrHgO• formation is revealed to be important, we will investigate its likely reactions in the atmosphere. The kinetics of radical + O3 reactions are well described using CCSD,103 giving us confidence in the reliability of our theoretical approach. The rate constants determined in this task will provide wide-ranging insights into the fate of •HgBr in the atmosphere.

Experimental Task 2. Kinetics and Product Spectra of •HgBr Reactions with NO, NO2, and VOCs A) Rate constants of •HgBr with NOx and test of prediction of weak •HgBr bonding with NO

The PI predicted that •HgBr bonds strongly with NO2 but only weakly with NO, and these results were consistent between modest and high levels of theory.13-14 These experiments will measure variations in the loss rate of •HgBr versus [NO] or [NO2], separately, to enable determination of rate constants under pseudo-first order conditions. If theory is correct, we will probably see little evidence of reaction with NO. The use of pseudo-first order conditions means that rate constants can be reliably measured despite any uncertainties and inhomogeneities in the concentration of •HgBr. The radical concentrations created by photolysis of HgBr2 and NO2 are too low for side reactions to interfere with the fast reaction of •HgBr + NO2. We will use N2 as a bath gas to mimic atmospheric conditions, and correct for NO2 dimerization. The temperature and total pressure will be varied over a wide range to enable predictions of the rate constants at temperatures of 200-400 K and 10-760 Torr.

B) Rate constants of •HgBr with VOCs The likely reactions of •HgBr with VOCs are described by reactions (8) and (9) in Computational Task 1 (above). VOC will be added in excess to the reactor to establish conditions for pseudo-first order loss of •HgBr. This will suppress side reactions and ensure that the measured rate constants are reliable. VOC photochemistry at 266 nm is not a concern for alkanes, alkenes, alcohols, or ethers.104 The small yields of reactive products from by photolysis of carbonyl compounds (<1% at the 266 nm wavelength of the photolysis laser)105 should be a negligible problem. Aromatic hydrocarbons little propensity for photolysis upon 266 nm irradiation.106-108 Other secondary chemistry should also be minor, but kinetic modeling will be used to verify this expectation.

C) UV-visible spectra of •HgBr reaction products No experimental spectra have been reported for •HgBr reaction products, so the results from Computational Task 2 (below) will be used as a guide for initial spectral searches. The time scale of disappearance of •HgBr will be compared to that for appearance of product spectra to verify the assignment of new peaks as reaction products. Comparison of predicted and observed spectra will ensure the accurate determination of the molecular identity of reaction products.

The rate constants measured in this task are critical for understanding the rate of Hg(0) oxidation in the atmosphere and the subsequent entrance of Hg(II) into ecosystems. These experimental results would validate theoretical methods we plan to use to compute rate constants for reactions and conditions (pressure and temperature) not readily accessible to experiment.

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Computational Task 2. Help Experiments Identify and Quantify Products of •BrHg Reactions As listed in Table 1 and discussed above for •HgBr + •NO2, there are multiple products possible for •HgBr reactions, each with different consequences for mercury oxidation. Part of this Computational Task is to characterize the excited states of potential reaction products to support their identification by CRDS measurements of their UV-visible spectra. This effort will also assess the potential for the photolysis to control the fate of reaction products. A separate sub-task will determine how to identify and quantify reaction products using chemical ionization mass spectrometry (CI-MS).

A) UV visible spectra of reaction products The UV-visible spectra of the •HgBr reaction products have never been studied, so these computational investigations of their excited states will provide a valuable guide to searching for and interpreting new spectral features observed in Experimental Tasks 2 and 3. We have already obtained reliable geometries for BrHgY using CCSD with large basis sets,14 and will do so for the other •HgBr reaction products postulated here. The next step is to compute excitation energies for singlet and triplet excited states, and oscillator strengths (integrated intensities) for singlet-singlet transitions with the EOM-CCSD method. We will account for spin-orbit effects on transition energies, which may be large, as discussed by Wadt.109 Absorption intensities for singlet-triplet transitions, which are normally negligible, are enhanced by the presence of heavy atoms such as Hg, Br, and I. This relativistic effect will be captured using multireference wavefunctions. To determine the potential for photolysis of •HgBr reaction products, we will investigate the stability of the singlet and triplet excited states with respect to isomerization and dissociation. The spin-flip variants of EOM-CCSD are ideal for this task.110 The results will establish the potential for their photolysis of •HgBr reactions products under atmospheric conditions. Initial work will focus on the species potentially formed from •HgBr reactions with NO2, VOCs and ozone, as these will be the first we plan to study experimentally (in Experimental Task 2). In year 3 these efforts will be extended to products of •HgBr reactions with HOO and halogen oxides. The spectra determined in this task will help confirm the identity of •HgBr reaction products observed in the laboratory. This will be the first study to investigate the influence of gas-phase photolysis of Hg(II) compounds on the rate of Hg(0) oxidation.

B) Enabling Hg(II) detection with CI-MS in the laboratory and in the field Iodide and nitrate anions provide extraordinary sensitivity as reagents in chemical ionization-MS (CI-MS).26-27 As we did for H3O+ + BrHgY,111 we will compute the products and rate constants for the reactions of NO3¯ and I ¯ with •HgBr reaction products. The ion-molecule rate constants can be used to quantitate yields of products even in the absence of authentic standards.27, 112 To ensure reliable identification of the product ions, we will establish the mode of reactivity: charge transfer (11a) or complex formation (11b), for example: BrHgY + I ¯ BrHgY ¯ + I• (11a) BrHgY + I ¯ BrHgYI ¯ (11b) The binding energy of the ion-molecule complex and its stability with respect to fragmentation will be determined. This will enable prediction of which ion peaks will dominate the mass spectra. Commercially available Hg(II) compounds will also be studied, so that they can be used as calibration standards. Hg(II) concentrations in the atmosphere can often reach concentrations that are measureable by CI-MS.113-115

These studies of reactions of Hg(II) compounds with CI-MS reagents will provide an additional tool for laboratory studies of Hg(0) oxidation processes. They will also provide the first opportunity for field studies to identify and quantify individual Hg(II)compounds rather than total Hg(II). Experimental Task 3. Study of reactions of •HgBr with O3

A) Kinetics of •HgBr + O3 Product In much of the troposphere, ozone can be 1000 times more abundant than radicals, so even a modest rate constant for the •HgBr + O3 reaction could cause it to dominate the fate of •HgBr. As described

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below, this experiment presents issues not present in the other proposed studies, which is why we address it separately. We will use N2 as a bath gas to mimic atmospheric conditions. LP will be used to generate •HgBr as described above, and its concentration will be monitored by CRDS using its sharp absorption peaks. Ozone, created in a discharge in O2, will be added in excess to establish pseudo-first order conditions for loss of •HgBr. The nearly structureless absorption of O3 will lower the baseline of the ringdown system near 254 nm for •HgBr detection. However, a single-shot S/N of at least 30 can still be obtained for •HgBr near 254 nm, e.g., when [O3] is ~1014 molecules cm-3 and [•HgBr] is as low as 1011 molecules cm-3. Ozone will be monitored in the broad Hartley band, which is also centered at 254 nm. Atomic bromine formed from HgBr2 photolysis will, in the presence of ozone, lead to BrO formation. The modest [BrO] created may compete with O3 to determine the fate of •HgBr, a competition we can control by varying the cell temperature and pressure, as well as the initial [HgBr2] and [O3]. Our control of initial conditions, together with kinetic modeling and computational studies of side reactions, will be used to ensure that measured rate constants for •HgBr + O3 are reliable. One might worry that ozone photolysis would interfere with kinetic measurements, but this is not the case. It is true that at the photolysis pulse energies we expect to use, much of the ozone in the path of the photolysis laser will be photolyzed.105 Excited state atomic oxygen, O(1D), formed in the photolysis will be very quickly quenched to ground state O(3P). The presence of ample O2 will rapidly convert these O(3P) atoms back to ozone (e.g., 200 Torr O2 leads to 98% conversion in 200 s). The co-PI has previously demonstrated the ability to monitor Hg(0) against a background of 1 atm of air, so the presence of O2 will not impede the spectroscopic monitoring of Hg(0) or •HgBr.50

B. Spectroscopic characterization of products of •HgBr + O3 reactions If experiment provides evidence for the occurrence of significant •HgBr + O3 reaction, we will search for characteristic absorptions of reaction products using CRDS. While spectra can be scanned in a wide wavelength range (UV to visible), insights from the results of Computational Task 2 will be used to guide the search. Generation of ozone is usually carried out in a discharge in O2, so the potential influence of the •HgBr + O2 BrHgO2 reaction will be investigated. Fortunately, the equilibrium constant for BrHgO2 formation strongly favors reactants, so that this reaction will likely not interfere with kinetic measurements.11, 13 This task will determine if ozone, rather than radicals, can control the fate of •HgBr under atmospheric conditions. Computational Task 3. Reactivity and product spectra of •HgBr + HOO, BrO, ClO, and IO As described in section IV.A.2, experimental kinetic studies of reactions of •HgBr with radicals such as HOO and halogen oxides present several challenges that cannot be addressed in this proposal. However, theoretical studies of these reactions are quite feasible, and very important for understanding the atmospheric fate of •HgBr. Throughout most of the daytime troposphere, HOO is the most abundant radical after NO and NO2. Halogen oxides are important during mercury depletion events,46, 116 in marine-influenced air,15, 117 and in the stratosphere. The approaches to be used here parallel those described in Computational Task 1. As listed in Table 1, these reactions have multiple possible sets of products. Reactions of •HgBr with halogen oxides may form species with structures BrHgOX or BrHgXO, due to the potential for halogens to bind to more than one other atom. The different bonding patterns exhibited by isomers imply differences in stability, photochemistry and atmospheric fates, all of which we will establish from computations. Analogous to reaction (7) on page D-9, there is the potential for these radicals, •Y, to react with the Br atom of •HgBr to form Hg + BrY. These reactions, instead of oxidizing mercury to Hg(II), would reduce the mercury atom in •HgBr to a free atom of Hg(0). If these reaction pathways are important, they would enormously change model predictions of Hg(0) oxidation rates. Additionally, for •HgBr + HOO, reaction to form BrHgOOH may have competition from the reaction to form BrHgH + O2(3 ). BrHgH has never been studied, although its chlorine analogue (ClHgH) is known.118

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The rate constants for all reaction pathways of •HgBr with these radicals will be determined for a wide range of temperatures and pressures. The information gained from this research will enable predictions of the rate of Hg(0) oxidation, and, therefore, of Hg(II) deposition, over the full range of conditions relevant to the entire atmosphere.

Project Timelines and Work Designation The proposed work will be conducted in a period of 36 months and each PI has designated activities toward this integrated program. Table 3 outlines the project timelines and work designations.

Table 3. Projected timelines and work designations.

Yr. Experiments (MSU) Calculations (ESF)

1Assemble apparatus, obtain quantum yields for HgBr2 photolysis, and optimize •HgBr spectra. Begin survey of •HgBr kinetics.

Determine k(P,T) for •HgBr + NO/NO2. Initiate analogous studies of •HgBr reactions with VOCs and ozone.

2Measure k(P,T) for •HgBr reactions with NO, NO2, and VOCs. Search for product spectra near 254 nm.

Continue studies of •HgBr reactions. Characterize electronic spectra of •HgBr reaction products to support experiment.

3Search for product spectra in broader range of wavelengths (UV to visible). Determine kinetics and product spectra of •HgBr + O3.

Compute k(P,T), and product spectra for •HgBr + HOO, ClO, BrO, and IO. Studies of CI-MS for quantitation of products.

Safe Handling of Mercury: The co-PI has extensive experience with, and certification in, handling dangerous materials, including mercury and mercury compounds.50-52

VI. TEAM AND MANAGEMENT PLAN The PI and co-PI have a long-standing record of success in collaborative research integrating

advanced computational methods and cutting-edge experimental techniques. The proposed research will continue this integrative effort. For example, computational predictions of spectra to be observed in experiments will depend on rate constants, computed yields of products, and computed spectra. The combined uncertainties in all of these results will be assessed by both research teams, together, to enable critical evaluation of the experimentally observed product spectra. Similarly, uncertainty in experimentally measured rate constants will be assessed jointly. To ensure productivity and smooth flow of information between the two groups, communication will take place through email, video conference calls (monthly), visits, and meetings at conferences.

VII. BROADER IMPACTS OF THE PROPOSED WORK

VII.A. Broader Impacts on Atmospheric Mercury Science Individual scientists are already incorporating the reactions of •HgBr with •Y to form BrHgY, as first proposed by the PI,13 into their chemical mechanisms.7, 15, 16, 18-21 The inclusion of these reactions with guesses for the rate constants enormously changes the predictions of these models: the rate of oxidation is much faster and the atmospheric lifetime of mercury is much shorter than previously modeled.117, 119 Clearly, the rate constants and product identities to be determined in the proposed research are critically important inputs if models are to be reliable. We will collaborate directly with two leaders in atmospheric mercury chemistry, Dr. Daniel Jacob of Harvard University and Dr. Huiting Mao of SUNY-ESF, to incorporate the results of the proposed research into two of the most widely used models (see letters of commitment): 1) Community Multi-scale Air Quality Model (CMAQ): used by and for the U.S. EPA120 2) GEOS-Chem: used by researchers internationally121 and managed by researchers at Harvard122 We will disseminate results widely to ensure their inclusion into additional models.

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This research will provide a means for experimentalists to reliably identify and quantify individual Hg(II) compounds in the field, something that has never been achieved before. This will enable the direct comparison of model results and field work, providing a synergism that will speed further advances in atmospheric mercury chemistry. The improved capabilities of both field studies and models may make it possible to resolve the controversy over the role of ozone on Hg(0) oxidation (see Figure 1 on page D1).

VII.B. Broader Impacts on Mercury Science in Contexts Other than the Atmosphere Improvements in understanding Hg(0) oxidation in the

atmosphere will lead to a more reliable understanding of Hg(II) entry into ecosystems. Having entered ecosystems, mercury can bio-accumulate to levels that harm wildlife and humans (see Figure 6).123-

124 A major challenge for understanding Hg(II) processing in ecosystems is the fact that Hg(II) can also be reduced to Hg(0) and be re-emitted. Reliable quantification of the rate of Hg(0) oxidation in the atmosphere and Hg(II) entrance into ecosystems will help constrain estimates of Hg(0) emissions from ecosystems.8 Bromine is actively investigated for oxidizing Hg(0) produced in coal-fired power plants.78, 125-126 The proposed research on interactions of •HgBr with ClO, BrO, NO and NO2 could advance understanding of technology for reducing Hg(0) emissions.

VII.C. Broader Impacts in Training Future Researchers This research will provide training in cutting-edge methods of modern spectroscopy and computational chemistry. In addition to the two graduate students to be funded, at least three undergraduate students and one high-school student will participate in research for pay or credit. The PI has a strong record of involving undergraduates in research, often leading to co-authorship of papers.13, 111 The co-PI has had worked with five undergraduates (two by REU) and two high school seniors in the last 3.5 years. These graduate and undergraduate students will be prepared for interdisciplinary research careers transcending the boundaries of molecular-level and environmental research.

VII.D. Broader Impacts in Formal Education in ScienceThe PI will create a learning module that uses Hg(0) oxidation to teach kinetics at the level of

introductory college and advanced high school chemistry. This learning module will consist of learning goals, background material for instructors, lecture materials (including worked examples and figures), and homework questions/answers. In year 1, the learning module will be evaluated in ESF’s General Chemistry II course after bring presented by the PI (as a guest lecturer). In year 2, the regular instructor will present the material to verify its usability by non-experts. Subsequently, a high-school teacher will use the learning module in her AP Chemistry class (see letters of commitment). This learning module will be evaluated qualitatively (by course instructors and teaching assistants) and quantitatively (from historical data on class performance on standardized kinetics questions). Evaluations will lead to revisions and publication in the Journal of Chemical Education. The co-PI helps teach high school physics (AP Physics) at the Mississippi School of Math and Science (MSMS) and hosts a summer workshop to train teachers at MSMS. This research project will be presented to teachers and students in MSMS.

VII.E. Broader Impacts in Public Engagement with Science and Technology The research groups at both SUNY-ESF and MSU will reach out to local communities via existing initiatives of their departments, Outreach Offices, and scientific societies, and also at local science fairs. For example, the PI and his students annually do outreach at the New York State Fair, where 2000 children engage in hands-on chemistry activities each year. The co-PI gives research lab tours to students from local schools during the annual State Spring Physics Competitions and the Discovery Day Festival at MSU. The co-PI has been serving on the Spring Physics Competition Committee and will add a new

Figure 6. Sign in the Florida Everglades (nicholas.duke.edu wetland/mercury.htm).

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demonstration (based on this research) to those activities. In addition, the co-PI will create a pair of five-minute movies entitled: “Mercury and human health” and “How light can measure mercury?” These movies will be posted to the Internet and advertised on the websites of the PIs and their departments.

VIII. RESULTS OF PRIOR NSF RESEARCH VIII.A. The PI recently completed an NSF grant (Atmospheric Sciences #0937626): Isotope Effects in Methoxy Radical Kinetics ($468,932, 1/1/2010 - 12/31/2013). Intellectual Merit: This research focused on complementary experimental and computational investigation of deuterium isotope effects in reactions of methoxy radical + O2 (with •HgBr chemistry as a side-project). This grant resulted in eight published papers 13, 14, 101, 111, 127-130 as well as 19 oral and poster presentations. In addition, the PI has submitted a critical review article for a book series.129 Broader impacts: The methoxy + O2 reaction is the prototype for a host of atmospherically important alkoxy radical + O2 reactions. The competition between unimolecular reactions (isomerization and decomposition) and O2 reactions of alkoxy radicals influences NO-to-NO2 conversions and the tendency of the eventual stable products to form organic aerosol. The rate constants for alkoxy radical reactions are only known for a handful of alkane-derived species. The research completed here validated a computational method that will enable predictions of O2 rate constants for a wide variety of functionalized alkoxy radicals of atmospheric interest. The results of this research will lead to better prediction of the formation of ozone,130, 131 organic aerosol,132 and other pollutants. One M.S. and two Ph.D. degrees were awarded to students supported by this grant. One undergraduate supported by this grant co-authored two papers.13, 111 Our first study of •HgBr + •Y reactions13 generated intense interest among scientists doing field work and modeling in atmospheric chemistry (24 citations in the 36 months since publication). It has also led to collaboration with scientists at Harvard and internationally.7

VIII.B. The co-PI of this proposal was the sole PI on an NSF grant entitled Quantitative survey of combustion intermediates toward understanding of plasma-assisted combustion mechanism (Grant # CBET-1066486, $ 420,016, 5/1/2011- 04/30/2015). Intellectual Merit: In this project, we used CRDS combined with other optical tools to obtain information on plasma and combustion intermediates (free radicals, excited neutral species, and ions) in time and in space to understand low-temperature combustion kinetics and reaction pathways, which are not known currently. Broader impacts: 11 peer-reviewed journal papers,51, 52, 135-143 one book chapter,144 and 14 conference papers have been generated from this project.145-158 Two students supported by this project received PhD degrees. Two undergraduate students received training from this grant. Tours of this lab were provided to over 200 high school students. This work will contribute to more efficient and cleaner combustion, thereby reducing energy use, greenhouse gas emissions, and emissions of pollutants.159-161

IX. CONCLUSION We propose to synergistically use advanced spectroscopic and theoretical techniques to elucidate critical information about the atmospheric fate of mercury. The research plans are built on the combined expertise of the PIs in the areas of CRDS and computational chemistry, and on their previous studies of Hg and kinetics. This project will provide advanced training to graduate and undergraduate students in an interdisciplinary field in atmospheric and environmental chemistry. The rate constants and mechanisms produced from this project will transform our understanding of atmospheric mercury chemistry. The kinetic and mechanistic results of this research will be adopted widely into models of atmospheric mercury oxidation, enabling modelers to realistically predict the fate of •HgBr under the full range of conditions relevant to the entire troposphere and stratosphere. Mercury transfer from the atmosphere to ecosystems occurs mostly as Hg(II), so this work will lead to additional insights into the cycling of mercury in terrestrial and marine environments.

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[135] N. Srivastava and C. Wang, Effects of water addition on OH radical generation and plasma properties in an atmospheric argon microwave plasma jet. J. Appl. Phys., 2011, 110, 053304.

[136] N. Srivastava and C. Wang, Determination of OH Radicals in an Atmospheric Pressure Helium Microwave Plasma Jet. Plasma Science, IEEE Transactions on, 2011, 39, 918-924.

[137] P. Sahay, S. T. Scherrer, C. Wang, A portable optical emission spectroscopy-cavity ringdown spectroscopy dual-mode plasma spectrometer for measurements of environmentally important trace heavy metals: Initial test with elemental Hg, Rev. Sci. Instrum. 2012, 83, 095109 - 095109-14.

[138] N. Srivastava and C. Wang, Effects of water addition on OH radical generation and plasma properties in an atmospheric argon microwave plasma jet, J. Appl. Phys., 2011, 110, 053304.

[139] P. Sahay, S. T. Scherrer, and C. Wang, A portable optical emission spectroscopy-cavity ringdown spectroscopy dual-mode plasma spectrometer for measurements of environmentally important trace heavy metals: initial test with elemental Hg., Rev. Sci. Instrum., 2012, 83, 095109.

[140] C. Wang and W. Wu, Simultaneous measurements of OH( A ) and OH( X ) radicals in microwave plasma jet-assisted combustion of methane/air mixtures around the lean-burn limit using optical emission spectroscopy and cavity ringdown spectroscopy, J.Phys. D. Appl. Phys., 2013, 46, 464008.

[141] C. Wang and W. Wu, Roles of the state-resolved OH(A) and OH(X) radicals in microwave plasma assisted combustion of premixed methane/air: An exploratory study, Combust. Flame, 2014, 161, 2073–84.

[142] P. Sahay and C. Wang, Absolute measurements of electron impact excitation cross-sections of atoms using cavity ringdown spectroscopy, Radiat. Phys. Chem., 2015,106, 165–169.

[143] W. Wu, C. A. Fuh, and C. Wang, Comparative study on microwave plasma-assisted combustion of premixed and nonpremixed methane/air mixtures, Combust. Sci. Technol., 2015, 187, 999-1020.

[144] C. Wang, Cavity ringdown spectroscopy of plasma species, an invited book chapter for Low Temperature Plasma Technology: Methods and Applications, Publisher: CRC Press; 1st edition. ISBN-10: 1466509902. (July 12, 2013)

[145] N. Srivastava and C. Wang, Study of Microwave Plasma Enhanced Methane Flame at Atmospheric Pressure. Bull. Am. Phys. Soc., 2011, 56. http://meetings.aps.org/link/BAPS.2011.GEC.ET2.3.

[146] N. Srivastava and C. Wang. Effect of Different Gases on OH Radical Concentration in Ar and He Atmospheric Pressure Microwave Plasma Jet. Bull. Am. Phys. Soc., 2011, 56. http://meetings.aps.org/link/BAPS.2011.GEC.LW1.13.

[147] N. Srivastava and C. Wang, Study of generation mechanism of OH radical in an atmospheric pressure argon microwave plasma jet with addition of water content. In

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Plasma Science (ICOPS), 2011 Abstracts IEEE Internat. Conf., 2011. DOI: 10.1109/PLASMA.2011.5992963.

[148] W. Wu and C. Wang, Cavity ringdown measurements of OH radicals in microwave induced argon plasma assisted combustion of methane/air mixtures. Bull. Am. Phys. Soc., 2012, 57, http://meetings.aps.org/Meeting/GEC12/Event/173933.

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[152] P. Sahay, S. T. Scherrer, and C. Wang, A Plasma Based OES-CRDS Dual-mode Portable Spectrometer for Trace Element Detection: Emission and Ringdown Measurements of Mercury, in 65th Gaseous Electronics Conference, Austin, TX, Oct 22-26, 2012.

[153] C. Wang and W. Wu, "Microwave plasma assisted combustion" in 65th Gaseous Electronics Conference, Austin, TX, Oct 22-26, 2012.

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[156] C. Wang, Invited Minicourse lecture (60 mins), entitled 'Cavity Ringdown Spectroscopy for Atmospheric Plasma,' in in the International Conference in Plasma Science, Washington DC, May 25-29, 2014.

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[158] C. Fuh and C. Wang, Effects of a microwave induced argon plasma jet on premixed and nonpremixed methane/air mixtures, in 44th American Institute of Aeronautics and

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[161] B. Wolk, A. DeFilippo, J.-Y. Chen, R. Dibble, A. Nishiyama, Y. Ikeda, Enhancement of flame development by microwave-assisted spark ignition in constant volume combustion chamber, Combust. Flame, 2013, 160, 1225-34.

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Theodore S. Dibble Chemistry Department State University of New York - Environmental Science and Forestry Syracuse, NY 13210 Phone: (315) 470-6596 tsdibble@esf.edu FAX: (315) 470-6856 http://www.esf.edu/faculty/dibble/ PROFESSIONAL PREPARATION: University of Michigan Chemistry BS 1987 University of Michigan Physical Chemistry PhD 1992 Postdoctoral, Wayne State University, Department of Chemistry 1992-94 Postdoctoral, Purdue University, Department of Chemistry 1994-95 Postdoctoral, California Institute of Technology 1995-96 APPOINTMENTS: Associate Chair, Department of Chemistry, SUNY-ESF 2011-now Professor of Chemistry, SUNY-ESF 2007-now Associate Professor of Chemistry, SUNY-ESF 2002-2007 Assistant Professor of Chemistry, SUNY-ESF 1996-2002 FIVE RELEVANT PUBLICATIONS: (graduate students, undergraduates *) Quality Structures, Vibrational Frequencies, and Thermochemistry of the Products of Reaction

of BrHg• with NO2, HO2, ClO, BrO, and IO. Y. Jiao and T. S. Dibble. J. Phys. Chem. A, 2015, 119, 10502-10510.

Quantum Chemistry Guide to PTRMS Studies of As-Yet Undetected Products of the Bromine-Atom Initiated Oxidation of Gaseous Elemental Mercury. T. S. Dibble, M. J. Zelie,* and Y. Jiao, J. Phys. Chem. A, 2014, 118, 7847–7854.

Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals. T. S. Dibble, M. J. Zelie,* and H. Mao. Atmos. Chem. Phys., 2012, 12, 10271-10279. http://dx.doi.org/10.5194/acpd-12-17887-2012.

Rate Constants and Kinetic Isotope Effects for Methoxy Radical Reacting with NO2 and O2. J. Chai, H. Hu, T. S. Dibble, G. S. Tyndall, and J. J. Orlando. J. Phys. Chem. A, 2014, 118, 3552–3563.

Quantum Chemistry, Reaction Kinetics, and Tunneling Effects in the Reaction of Methoxy Radicals with O2. H. Hu and T. S. Dibble. J. Phys. Chem. A, 2013, 117, 14230–42.

FIVE OTHER PUBLICATIONS: Quantum Chemical Study of Autoignition of Methyl Butanoate. Y. Jiao, F. Zhang, and T. S.

Dibble. J. Phys. Chem. A, 2015, 119, 7282–7292. Pressure Dependence and Kinetic Isotope Effects in the Absolute Rate Constant for Methoxy

Radical Reacting with NO2. J. Chai and T. S. Dibble, Int. J. Chem. Kinet., 2014, 46, 501-511.

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Temperature-Dependent Branching Ratios of Deuterated Methoxy Radicals (CH2DO•) Reacting With O2. H. Hu, T. S. Dibble, G. S. Tyndall, and J. J. Orlando. J. Phys. Chem. A, 2012, 116, 6295-6302.

Cis-trans isomerization of chemically activated 1-methylallyl radical and fate of the resulting 2-buten-1-peroxy radical. T. S. Dibble, Y. Sha, W. F. Thornton*, and F. Zhang. J. Phys. Chem. A, 2012, 116, 7603-7614.

Impact of tunneling on hydrogen-migration of n-propylperoxy radical. F. Zhang and T. S. Dibble. Phys. Chem. Chem. Phys., 2011, 13, 17969-77.

SYNERGISTIC ACTIVITIES: (1) Editorial Board: International Journal of Chemical Kinetics, 2010-2012. (2) Journal Referee (selected journals):

Science Atmos. Chem. Phys. Atmos. Env. Environ. Sci. Technol. J. Am. Chem. Soc. Chem. Rev. J. Atmos. Chem. J. Chem. Phys. Int. J. Chem. Kinet. J. Phys. Chem. A Theor. Chem. Accts. Int. J. Quant. Chem. J. Chem. Theory Computation ChemPhysChem Chem. Eur. J.

(3) Proposal Reviewer: National Science Foundation (Chemistry, Atmospheric Sciences, Engineering) Department of Energy (Chemical Physics Program, NSF-DOE Plasma Partnership) ACS-Petroleum Research Fund (4) Reviewed book proposal for 2nd and 3rd editions of Atmospheric Chemistry and Physics:

From Air Pollution to Climate Change, by J. H. Seinfeld and S. N. Pandis. (5) REU Site Director, ESF Chemistry REU program, 2003-2005. COLLABORATORS AND OTHER AFFILIATIONS: Collaborators Vincent DeTuri (Ithaca College), Mark Driscoll and Huiting Mao (SUNY-ESF), Helen Amos, Daniel Jacob, and Elsie Sunderland (Harvard), John J. Orlando and Geoffrey S. Tyndall (National Center for Atmospheric Research, Boulder), Franz Slemr (Max Planck Institute for Chemistry, Mainz), Chuji Wang (Mississippi State)

Graduate and Postdoctoral Advisors: Ph.D. advisor: Lawrence S. Bartell (University of Michigan) Postdoctoral advisors: Joseph S. Francisco (Purdue University now at U. Nebraska) M. Matti Maricq (Ford Motor Company) Mitchio Okumura (California Institute of Technology)

Thesis Advisor (total 11), last 5 years: Karen L. Schmitt (MS 2010), Yue Zeng (MS 2012), Yuan Sha (MS 2013), Hongyi Hu (PhD 2013), Jiajue Chai (PhD 2014) Current students: Yuge Jiao (PhD expected 2016), Brian Morgan (PhD expected 2020)

Postdoctoral Scholars (total 4), last 5 years: Dr. Feng Zhang 2010-2011 (now at Assoc. Prof. at Univ. Sci. Technol. China)

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CHUJI WANG Department of Physics and Astronomy 662-325-9455 Mississippi State University (MSU) 662-325-8898 (fax) P O Box 5167 cw175@msstate.edu Mississippi State, MS 39762 http://www.wang.physics.msstate.edu A. PROFESSIONAL PREPARATION Anhui Normal University Physics B. S., 1986 U. of Science and Technology of China Chemical Physics Ph.D., 1998 Postdoctoral: SUNY-ESF Physical Chemistry 1998- 2000 MSU-DIAL Spectroscopy 2000- 2001 B. PROFESSIONAL APPOINTMENTS Senior Laser Scientist, Tiger Optics LLC (Warrington, PA) 2001-2002 Assistant Research Professor, ICET-Mississippi State University 2002-2006 Assistant Professor, Dept. of Physics, Mississippi State University 2006-2010 Associate Professor, Dept. of Physics, Mississippi State University 2010-2013 Professor, Dept. of Physics, Mississippi State University 2013-Now Army Research Lab (Adelphi, MD), one-year sabbatical leave July 2013-June 2014 C. PUBLICATIONS- 5 Most Relevant (From 79 peer-reviewed articles and 7 patents) 1. Peeyush Sahay, Susan T. Scherrer, and Chuji Wang, A portable OES-CRDS dual-mode plasma

spectrometer for measurements of environmentally important trace heavy metals: initial test of elemental Hg, Rev. Sci. Instru. 83, 095109-095122 (2012).

2. Chuji Wang, Susan T. Scherrer, and Peeyush Sahay, Electron impact excitation-cavity ringdown absorption spectrometry of elemental mercury at 405 nm, J. Anal. Atom. Spectrom. 27, 284-292 (2012).

3. Chuji Wang, Peeyush Sahay, and Susan T. Scherrer, A new optical method of measuring electron impact excitation cross section of atoms: cross section of the metastable 6s6p 3P0 level of Hg, Phys. Lett. A, 375, 2366-2370 (2011).

4. Chuji Wang, Susan T. Scherrer, Yixiang Duan, and Christopher B. Winstead, Cavity ringdown measurements of mercury and its hyperfine structures at 254 nm in an atmospheric microwave plasma: spectral interference and analytical performance. J. Anal. Atom. Spectrom. 20(7), 638-644 (2005). (Hot Article)

5. Yixiang Duan, Chuji Wang, Susan T. Scherrer, and Christopher B. Winstead, Development of alternative plasma sources for cavity ring-down measurements of mercury. Anal. Chem. 77(15), 4883-4889 (2005).

Five other significant publications 1. Peeyush Sahay and Chuji Wang, Absolute measurements of electron impact excitation cross-

section of atoms using cavity ringdown spectroscopy, Radiation Physics and Chemistry, 106, 165-169 (2014).

2. Chuji Wang and Wei Wu, Roles of the state-resolved OH (A) and OH (X) radicals in microwave plasma assisted combustion of premixed methane/air: An exploratory study, Combustion and Flame, 161, 2073–2084 (2014).

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3. Chuji Wang, Yongle Pan, and Mark Coleman, Experimental observation of particle cones formed by optical trapping, Optics Letters, 39, 2767-2770 (2014). Selected by the Editor for Virtual Journal of Biomedical Optics, March, 2014.

4. Chuji Wang, Critical Review: Plasma-cavity ringdown spectroscopy (P-CRDS) for elemental and isotopic measurements, J. Anal. Atom. Spectrom.22, 1347-63 (2007). (Featured on the front cover).

5. Wei Deng, Chuji Wang, David. R. Katz, Gregory R. Gawinski, A. J. Davis, and Theodore S. Dibble, Direct kinetic studies of the reactions of 2-butoxy radicals with NO and O2. Chem. Phys. Lett. 330, 541-5 (2000).

D. SYNERGISTIC ACTIVITIES

1. NSF review panelist (NSF CBET, CMMI, 2006, 2010(2), 2011, 2012(3)), 2013(1), 2014(1) DOE grant review (annually).

2. Journal reviewer: Opt. Lett., Appl. Phys. Lett., Appl. Opt., Meas. Sci. Technol., Anal. Chem., Appl. Spectrosc., J. Appl. Phys., IEEE TPS, IEEE Sensors Journal, Eur. Phys. J. D., (21 total).

3. Seven US patents (4 granted and 3 pending) in ringdown technologies. 4. MSU 2011 Outstanding Faculty Research Award; Dean’s Eminent Scholar (2011), James Worth

Bagley Faculty Award (2011), State Pride Award (2010), IEEE Council Best Paper Award (2011). 5. Member and or Chairman of 8 committees at MSU. E. COLLABORATORS AND OTHER AFFILIATIONS 1. Collaborators over the last 48 months Theodore S. Dibble (SUNY-ESF); George P. Miller (Univ. of Tulsa); Chris B. Winstead (Univ.

of Southern Mississippi); Yixiang Duan (Los Alamos National Lab); Gangbing Song (Univ. of Houston), Mike Kadar (George Washington Univ.); Gail Heath (Idaho National Lab); Yongle Pan (Army Research Lab).

2. Graduate and Postdoctoral Advisors Xingxiao Ma, Ph.D. advisor, University of Science and Technology of China, thesis title: LIF of CF2 radicals generated by a pulsed DC discharge and cooled in a supersonic beam Theodore S. Dibble, SUNY-ESF; (LIF spectra and kinetic study of large alkoxy radicals) George P. Miller, University of Tulsa, (Development of plasma-CRDS) 3. Thesis Advisor and Postgraduate-Scholar Sponsor Recent graduate students: (12 in total): Wu (Ph.D., 2010-); Maheshwar (Ph.D., 2012-); Che A. Fuh (Ph.D., 2012-); Zhiyong Gong

(Ph.D. 2014-); Shane Clark (M.S. 2013-). Zhenan Wang (Ph.D., 2014, Assi. Prof.,China); Haifa Alali (M.S., 2013); Peeyush Sahay (Ph.D., 2013, Scientist, Univ. Memphis); Malik Kaya (Ph.D., 2013, Assi. Prof.,Turkey); Nimisha Srivstava (Ph.D., 2011, Intel Inc.), Susan T. Scherrer (Ph.D., 2011, Southern Ionics Inc.), Chamini Herath (M.S., 2010), Armstrong Mbi (M.S., 2006, Georgetown Univ.), Sudip P. Koirala (M.S., 2005, Intel Inc.).

Recent postdocs: (3 in total) Dr. Meixiu Sun (2014-); Dr. J. Fuller (2004-2005), Dr. P. Cias (2004-2005).

Recent undergraduates: Cameron Andrew (Physics Senior); Diana Hubins (Physics Honor, 2014), Jonathan Miller (Physics Honor, Junior), M. Robins (now, Duke Univ., Biomedical Eng., Fall 2012)

Former high school students: H. Sterling (MIT Class of 2015); C. Wang (Yale Univ. Class of 2016)

F-2

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

1YEAR

1

SUNY College of Environmental Science and Forestry

Theodore

TheodoreTheodore

Dibble

Dibble Dibble

TheodoreTheodoreTheodore S S S Dibble Dibble Dibble - none 0.00 0.45 0.50 9,698

0 0.00 0.00 0.00 01 0.00 0.45 0.50 9,698

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 25,0000 00 00 0

34,6987,991

42,689

02,000

0

0000

0 0

5,000000

90,25512,592

107,847 152,536

42,573a,b,c, e, g1, +25000 of g5 (Rate: 57.0000, Base: 74689)

195,1090

195,1090

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

2YEAR

2

SUNY College of Environmental Science and Forestry

Theodore

TheodoreTheodore

Dibble

Dibble Dibble

TheodoreTheodoreTheodore S S S Dibble Dibble Dibble - none 0.00 0.45 0.50 9,988

0 0.00 0.00 0.00 01 0.00 0.45 0.50 9,988

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 25,7500 00 00 0

35,7388,791

44,529

03,500

0

0000

0 0

3,0001,000

00

87,36013,096

104,456 152,485

29,657a,b,c, e, g1, g2 (Rate: 57.0000, Base: 52029)

182,1420

182,1420

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

3YEAR

3

SUNY College of Environmental Science and Forestry

Theodore

TheodoreTheodore

Dibble

Dibble Dibble

TheodoreTheodoreTheodore S S S Dibble Dibble Dibble - none 0.00 0.45 0.50 10,288

0 0.00 0.00 0.00 01 0.00 0.45 0.50 10,288

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 26,5230 00 00 0

36,8119,501

46,312

03,500

0

0000

0 0

3,0001,000

00

91,07513,620

108,695 158,507

30,673a,b,c, e, g1, g2 (Rate: 57.0000, Base: 53812)

189,1800

189,1800

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

Cumulative

C

SUNY College of Environmental Science and Forestry

Theodore

TheodoreTheodore

Dibble

Dibble Dibble

TheodoreTheodoreTheodore S S S Dibble Dibble Dibble - none 0.00 1.35 1.50 29,974

0.00 0.00 0.00 01 0.00 1.35 1.50 29,974

0 0.00 0.00 0.00 00 0.00 0.00 0.00 03 77,2730 00 00 0

107,24726,283

133,530

09,000

0

0000

0 0

11,0002,000

00

268,69039,308

320,998 463,528

102,903

566,4310

566,4310

William nicholson

BUDGET JUSTIFICATION SUNY-ENVIRONMENTAL SCIENCE AND FORESTRY

Personnel A portion of the salary and fringe benefits of the principal investigator, Professor Theodore S. Dibble, is requested for his efforts in this project. He will carry out quantum and theoretical kinetic calculations and train and supervise one graduate student and multiple undergraduate students in carrying out similar calculations. The PI will also carry out kinetic simulations to gain insight into the design of experimental conditions, and work with the co-PI and his students to design and trouble-shoot experiments. One graduate student will be supported by this grant for three years. The student will commit 100% of his/her research time in this project as a Research Assistant during the 36-month period. Reimbursement of the graduate student’s salary and fringe benefits is requested in each of the three years. Equipment No equipment is requested. Travel Travel will be necessary to disseminate the results of this research. Conference travel will also provide opportunities for the PI’s and their graduate students to interact face-to-face. These funds will cover the cost of airfare, registration, food, and housing. $2,000 is requested in Year 1 to cover the cost of the PI to attend a National Meeting of the American Chemical Society and the Fall National Meeting of the American Geophysical Union. $3,500 is requested in each of Years 2 and 3 to cover conference costs for the PI and his student. Travel in Year 2 will be to the International Conference on Mercury as a Global Pollutant (in Providence, RI), the Gordon Conference on Atmospheric Chemistry (PI only), and a National Meeting of the American Chemical Society National Meeting (student, only). Travel in Year 3 will be to the Fall National Meeting of the American Geophysical Union and a National Meeting of the American Chemical Society National Meeting (student, only). Supplies $5,000 is requested in year 1, and $3,000 in each of years 2 and 3 to cover various expenses: - upgrade single-machine license of Gaussian to additional machine type - upgrade site license for Gaussview4 to Gaussview5 - acquisition of MOLPRO - spare parts for the servers that run quantum chemistry calculations - software for routine word and data processing, etc., on desktop PCs Publication Costs $1,000 is requested in both year two and year three to cover publication fees. Tuition

1 Budget Justification-ESF

Approximately $13,000 per year is requested for tuition reimbursement for the PhD student who will be working on this project. Subcontract The subcontract with Mississippi State University is fully described in their budget and corresponding budget justification. Indirect costs ESF’s federally negotiated on-campus indirect cost rate is 57%. In this project, the indirect cost rate is applied to all project costs, excluding tuition and excluding all but the first $25,000 of the subcontract with Mississippi State University.

2 Budget Justification-ESF

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

1YEAR

1

Mississippi State University

Chuji

ChujiChuji

Wang

Wang Wang

ChujiChujiChuji Wang Wang Wang - Co-PI 0.00 0.00 1.00 9,807

0 0.00 0.00 0.00 01 0.00 0.00 1.00 9,807

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 22,0001 3,2000 00 0

35,0073,202

38,209

6,500$Reactor

6,5001,780

0

0000

0 0

9,2001,000

000

9,803 20,003 66,492

23,763MTDC (Rate: 45.5000, Base: 52226)

90,2550

90,2550

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

2YEAR

2

Mississippi State University

Chuji

ChujiChuji

Wang

Wang Wang

ChujiChujiChuji Wang Wang Wang - Co-PI 0.00 0.00 1.00 10,298

0 0.00 0.00 0.00 01 0.00 0.00 1.00 10,298

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 23,1001 3,2000 00 0

36,5983,348

39,946

03,260

0

0000

0 0

7,9001,000

000

10,485 19,385 62,591

24,769MTDC (Rate: 45.5000, Base: 54437)

87,3600

87,3600

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

3YEAR

3

Mississippi State University

Chuji

ChujiChuji

Wang

Wang Wang

ChujiChujiChuji Wang Wang Wang - Co-PI 0.00 0.00 1.00 10,813

0 0.00 0.00 0.00 01 0.00 0.00 1.00 10,813

0 0.00 0.00 0.00 00 0.00 0.00 0.00 01 24,2551 3,2000 00 0

38,2683,502

41,770

03,260

0

0000

0 0

8,3001,000

000

10,944 20,244 65,274

25,801MTDC (Rate: 45.5000, Base: 56706)

91,0750

91,0750

William nicholson

SUMMARYPROPOSAL BUDGET

FundsRequested By

proposer

Fundsgranted by NSF

(if different)

Date Checked Date Of Rate Sheet Initials - ORG

NSF FundedPerson-months

fm1030rs-07

FOR NSF USE ONLYORGANIZATION PROPOSAL NO. DURATION (months)

Proposed Granted

PRINCIPAL INVESTIGATOR / PROJECT DIRECTOR AWARD NO.

A. SENIOR PERSONNEL: PI/PD, Co-PI’s, Faculty and Other Senior Associates (List each separately with title, A.7. show number in brackets) CAL ACAD SUMR

1.

2.

3.

4.

5.

6. ( ) OTHERS (LIST INDIVIDUALLY ON BUDGET JUSTIFICATION PAGE)

7. ( ) TOTAL SENIOR PERSONNEL (1 - 6)

B. OTHER PERSONNEL (SHOW NUMBERS IN BRACKETS)

1. ( ) POST DOCTORAL SCHOLARS

2. ( ) OTHER PROFESSIONALS (TECHNICIAN, PROGRAMMER, ETC.)

3. ( ) GRADUATE STUDENTS

4. ( ) UNDERGRADUATE STUDENTS

5. ( ) SECRETARIAL - CLERICAL (IF CHARGED DIRECTLY)

6. ( ) OTHER

TOTAL SALARIES AND WAGES (A + B)

C. FRINGE BENEFITS (IF CHARGED AS DIRECT COSTS)

TOTAL SALARIES, WAGES AND FRINGE BENEFITS (A + B + C)

D. EQUIPMENT (LIST ITEM AND DOLLAR AMOUNT FOR EACH ITEM EXCEEDING $5,000.)

TOTAL EQUIPMENT

E. TRAVEL 1. DOMESTIC (INCL. U.S. POSSESSIONS)

2. INTERNATIONAL

F. PARTICIPANT SUPPORT COSTS

1. STIPENDS $

2. TRAVEL

3. SUBSISTENCE

4. OTHER

TOTAL NUMBER OF PARTICIPANTS ( ) TOTAL PARTICIPANT COSTS

G. OTHER DIRECT COSTS

1. MATERIALS AND SUPPLIES

2. PUBLICATION COSTS/DOCUMENTATION/DISSEMINATION

3. CONSULTANT SERVICES

4. COMPUTER SERVICES

5. SUBAWARDS

6. OTHER

TOTAL OTHER DIRECT COSTS

H. TOTAL DIRECT COSTS (A THROUGH G)

I. INDIRECT COSTS (F&A)(SPECIFY RATE AND BASE)

TOTAL INDIRECT COSTS (F&A)

J. TOTAL DIRECT AND INDIRECT COSTS (H + I)

K. SMALL BUSINESS FEE

L. AMOUNT OF THIS REQUEST (J) OR (J MINUS K)

M. COST SHARING PROPOSED LEVEL $ AGREED LEVEL IF DIFFERENT $

PI/PD NAME FOR NSF USE ONLYINDIRECT COST RATE VERIFICATION

ORG. REP. NAME*

*ELECTRONIC SIGNATURES REQUIRED FOR REVISED BUDGET

Cumulative

C

Mississippi State University

Chuji

ChujiChuji

Wang

Wang Wang

ChujiChujiChuji Wang Wang Wang - Co-PI 0.00 0.00 3.00 30,918

0.00 0.00 0.00 01 0.00 0.00 3.00 30,918

0 0.00 0.00 0.00 00 0.00 0.00 0.00 03 69,3553 9,6000 00 0

109,87310,052

119,925

6,500$

6,5008,300

0

0000

0 0

25,4003,000

000

31,232 59,632 194,357

74,333

268,6900

268,6900

William nicholson

MSU BUDGET JUSTIFICATION A. Senior Personnel A portion of the salary ($9,853 (yr1), $10,346 (yr2), $10,863 (yr3)) of the principal investigator, Professor Chuji Wang, are requested for his efforts in this project. The requested funds will support his summer salary for 1.0 month/yr in each of the three years. He will conduct experiments, advise the graduate student, and train the undergraduate student. Requested amounts are based on a base salary (9 month) of $88,677, with 5% adjustments for years 2 and 3. B. Other Personnel One graduate student from Physics (MS) or Engineering Physics (PhD) will be supported in this project. The student will commit 100% of his/her research time in this project as a Research Assistant during the 36-month period. Requested amounts are based on a base stipend (12 month) of $22,000, with 5% adjustments for years 2 and 3.

One undergraduate student will be supported for 2 months in summer for the three years ($1,600/month; $3,200/year). C. Fringe Benefits Fringe benefits are charged at the university approved rates of 24.13% for the PI, at 0.73% for the graduate student during the academic year, and at a rate of 8.48% for the graduate student in the summer (not enrolled) and the undergraduate.

D. Equipment $6,500 is requested in Year 1 to purchase a reactor for study of reaction kinetics. E. Travel Domestic $1,780 is requested to cover the cost of the PI to attend one conference in the first year. Hotel, per diem, ground transportation, and flight tickets will be covered. In addition, $3,260 is requested in years 2 and 3 to cover the cost of the PI and one graduate student to attend the American Chemical Society conference. The travel costs will include ground transportation, flight tickets, hotel, and per diem. G. Other Direct Costs Materials and Supplies A total of $25,400 is requested to order materials and supplies, including a detector ($900), six pairs of ringdown mirrors ($12,000), 2 quartz cuvette and filters ($2,000), chemical reaction gas samples ($4,500) and Nd:YAG laser optics and samples ($2,000/yr, $6,000 total). Publication Costs $1,000 is requested per year to cover the cost of publishing results in a journal. Other Graduate Student Tuition Nine months of the graduate student’s tuition will be covered at the university approved rate of $834/month, $875/month, and $919/month in each of the three years, respectively. Graduate Student Insurance

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Nine months of the required graduate student’s insurance will be covered at $89, $94, and $98 per month for each of the three years, respectively. Conference Registration Fees Funds are requested for conference registration fees for the PI ($600/yr) in each of the three years of the project and for the student ($250/yr) in each of the last two years. Hazardous Materials Disposal Fee $500 per year is requested for waste disposal fees for the last two years. Indirect costs MSU’s federally negotiated indirect cost rate is 45.5% of modified total direct costs, which excludes tuition and equipment.

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Current and Pending Support (See GPG Section II.D.8 for guidance on information to include on this form.)

The following information should be provided for each investigator and other senior personnel. Failure to provide this information may delay consideration of this proposal. Other agencies (including NSF) to which this proposal has been/will be submitted. Investigator: Theodore Dibble Support: Current Pending Submission Planned in Near Future *Transfer of Support Project/Proposal Title: SISGR: Dynamics of Radical Reactions in Biodiesel Combustion Source of Support: US Department of Energy Total Award Amount: $407,001

Total Award Period Covered: 9/15/09 - 12/14/15 Location of Project: SUNY College of Environmental Science and Forestry, Syracuse, New York Person-Months Per Year Committed to the Project.

Cal: Acad: .45 Sumr: 3 wks

Support: Current Pending Submission Planned in Near Future *Transfer of Support Project/Proposal Title: This Proposal: Molecular Insights into the Oxidation of Atmospheric Mercury: The Next Frontier in Atmospheric Mercury Science Source of Support: National Science Foundation Total Award Amount: $566,430

Total Award Period Covered: 5/1/16 - 4/30/19 Location of Project: SUNY College of Environmental Science and Forestry, Syracuse, New York Person-Months Per Year Committed to the Project.

Cal: Acad: .45 Sumr: 2 weeks

Support: Current Pending Submission Planned in Near Future *Transfer of Support Project/Proposal Title: Source of Support: Total Award Amount: $

Total Award Period Covered: Location of Project: SUNY College of Environmental Science and Forestry, Syracuse, New York Person-Months Per Year Committed to the Project.

Cal: Acad: Sumr:

Support: Current Pending Submission Planned in Near Future *Transfer of Support Project/Proposal Title: Source of Support: Total Award Amount: $

Total Award Period Covered: Location of Project: SUNY College of Environmental Science and Forestry, Syracuse, New York Person-Months Per Year Committed to the Project.

Cal: Acad: Sumr:

Support: Current Pending Submission Planned in Near Future *Transfer of Support Project/Proposal Title: Source of Support: Total Award Amount: $

Total Award Period Covered: Location of Project: SUNY College of Environmental Science and Forestry, Syracuse, New York Person-Months Per Year Committed to the Project.

Cal: Acad: Sumr:

*If this project has previously been funded by another agency, please list and furnish information for immediately pre-ceding funding period. NSF Form 1239 (10/99) USE ADDITIONAL SHEETS AS NECESSARY

Current and Pending Support(See GPG Section II.D.8 for guidance on information to include on this form.)

The following information should be provided for each investigator and other senior personnel. Failure to provide this information may delay consideration of this proposal.

Investigator: Chuji Wang Other agencies (including NSF) to which this proposal has been/will be submitted.

Support: Current Pending Submission Planned in Near Future *Transfer ofSupport

Project/Proposal Title: the Oxidation of Atmospheric(This proposal)

Source of Support: NSF PD 09-6882Total Award Amount: $56 Total Award Period Covered: 0 /01/2016- /3 /201Location of Project: SUMY-ESF, Syracuse, NY and Mississippi State University, Starkville, MSPerson-Months Per Year Committed to the Project. Cal: Acad: Sumr:1.0

Support: Current Pending Submission Planned in Near Future *Transfer ofSupport

Project/Proposal Title: Physical and chemical study of single aerosol particles using optical trapping-cavity ringdown spectroscopySource of Support: Department of DefenseTotal Award Amount $309,177 Total Award Period Covered: (09/01/2013 – 08/31/2016)Location of Project: Mississippi State University, Starkville, MSPerson-Months Per Year Committed to the Project. Cal: Acad: Sumr: 1.0

Support: Current Pending Submission Planned in Near Future *Transfer of

Support 1.0Project/Proposal Title: Investigation of chemical agitations on single chemical and biological aerosol particles in air using optical trapping-Raman spectroscopySource of Support: Department of DefenseTotal Award Amount $ 338,512 Total Award Period Covered: (05/01/2015-04/30/2018)Location of Project: Mississippi State University, Starkville, MSPerson-Months Per Year Committed to the Project. Cal: 0 Acad: 0 Sumr: 1.0

I. Facilities, Equipment, and other Resources SUNY-Environmental Science and Forestry Laboratory/ Office / Computer

The proposed research will be carried in graduate student research offices located in Jahn Laboratory, which was completed in 1997. Offices are wired for data transmission and access to the Internet, and cabling was upgraded in Summer 2012 to increase bandwidth. Offices house PCs used for routine word processing and data analysis

The PI’s group operates a 16-processor quad-core 64-bit Opteron QuantumCube from Parallel Quantum Systems with 96 GB RAM and 4 TB of disk space. The following quantum chemistry software is currently installed on this system:

GAMESS, CFOUR, GAUSSIAN09, NWChem 6.5, NBO4.1 The following kinetics software is currently installed on this system POLYRATE, GAUSSRATE, MultiWell Multiple PCs in graduate student research offices run Gaussian03 for Windows, Gaussview4,

Spartan, and software for RRKM/Master Equation calculations (UNIMOL, MESMER, Multiwell).

ESF also supports a Linux-based cluster consisting of 21 nodes with 168 processor cores and 3 GB of RAM per core, yielding a peak performance of 1.3 TFLOPS. Both local and networked storage are available to users. Currently there is a combined 5 TB of storage attached. NWChem 6.5 and CMAQ-Hg is available on this cluster.

Large Scale Computing

For projects that exceed local resources, the PI has routinely obtained grants of computer time from NSF-sponsored Teragrid (now XSEDE) resources. Other Resources ESF has an electronics technician and support staff for computer hardware and software. Mississippi State University Laser Spectroscopy and Plasma Lab at Mississippi State University (MSU) founded by the co-PI consists of four research laboratories, which are equipped with state-of-the-art equipment and available to support the proposed research. Two 700 sq. ft. new laboratories are in the Department of Physics and Astronomy in the College of Arts and Sciences and two labs are located in the Institute for Clean Energy Technology (ICET) within the College of Engineering at MSU.

I-1

Major Equipment Laser diagnostics and spectroscopy, especially CRDS, is a primary component of the co-PI’s research program. The major equipment housed in the co-PI’s four laboratories are: five 4 × 6 ft2 optical tables; one recently acquired OPO system (Spectra-Physics, MOPO-HF with PRO-270-10, linewidth < 0.075 cm-1, spectral range 227 nm – 4.3 µm); two sets of Nd:YAG pumped dye laser systems (one with frequency doubling and the other with tripling), covering wavelength from 197 nm to 740 nm; one spectrograph with an EMCCD (Princeton Instrument); one external cavity diode laser (ECDL ) from New Focus; one ECDL from New Port with two gratings and three laser heads at different wavelength; two sets of diode laser drivers (IXL and New Focus); several DFB laser diodes; two free space double-stage optical isolators (1570, 1650 nm); two PMTs covering UV to VIS; one fast NIR photo-receiver; one MIR detector; one double grating monochromator equipped with fiber waveguides; two digital oscilloscopes (Tektronix 410, 460A); two pulse generators; one vacuum-pumped CRDS cell, one vacuum-free flow CRDS cell; one supersonic slit jet CRDS system; ringdown mirrors cover major wavelengths from 226 nm to 1650 nm; self-developed CRDS software; one inductively coupled plasma; one microwave induced plasma system; one set of cold plasma jets; one mass spectrometer (QMS200); one ultra nebulizer; one fiber splicer; one fiber cleaver, one set of fiber fabrication kit; five computers. Other Resources

ICET is located at 58,000 ft2 facilities housing fifteen research laboratories operated by faculty members from different academic departments. ICET has a full machine shop, digital and analog electronics shops, and a high-bay testing facility. These resources will be also available for the proposed research.

Unfunded Collaborations Unfunded collaborations are described here (see also Letters of Commitment) as specified in the NSF Grant Proposal Guide (II.C.2.d.iv). Dr. Dibble will work with his ESF colleague Dr. Huiting Mao and her students to incorporate the results of this research into Dr. Mao’s box model and a version of CMAQ-Hg. As Dr. Mao and her students have offices within steps of Dr. Dibble’s office, this collaboration requires no special effort to manage. Dr. Dibble will work with Dr. Daniel Jacob and his graduate student, Hannah Horowitz, to incorporate the results of this research into the global 3-D GEOS-Chem model. Much of the collaboration will be managed by email and phone/video conference. There will also be opportunities to meet in person at, for example, the Gordon Conference on Atmospheric Chemistry or the International Conference on Mercury as a Global Pollutant.

I-2

SUNY-ESF & Mississippi State University - Data Management Plan

The goal of our data management plan is to establish a standard policies and procedures for both the ESF and MSU teams for collecting, generating, sharing and archiving data and metadata in all formats. The data in electronic and hardcopy format will be properly managed and indexed to be readily accessed by group members and collaborators, and stored securely for more than five years after the conclusion of the project. Public access to the data will be available in forms of journal publications, supplementary data to publications, conference presentations, and the PIs’ research websites. Types of Data Data generated from the proposed research will mainly include:

1) raw data consisting of experimental results, computational input and output files, and metadata which includes but is not limited to computational parameters and software specifications, sample preparation conditions, experimental system design details, data processing procedures, etc. A custom-designed experimental system will be constructed, and the plots and drawings on which the designs are based will also be considered as data generated from the project;

2) processed data, publications, and intellectual properties;

3) chemical samples.

Data Standards Measurement and computational data will be stored in both .txt and binary formats. Images and video clips will be stored in .tif and .mpg formats, respectively. Metadata associated with the data files will be stored in MS Word files. Original files of processed data for publications and reports such as tables, figures, charts, etc. will also be stored along with the corresponding raw data. Metadata will be documented in hardcopy notebooks as well in accordance with the policy on Custody, Maintenance and Retention of Research Data at both universities.

Data Archiving and Sample Handling All electronic data will be archived on computers and external backup hard drives in both PIs' laboratories. Electronic data that is acquired with computers will be stored locally and then backed up daily using automatic software to a remote storage server connected to the network for future referencing. Daily research procedures, operation details, comments, plans, new findings, etc. will be written down in designated a lab notebook. Hardcopy of notebooks will be stored in secure locations in laboratories or offices; photocopies and electronic scan of the notebooks will be made on a regular basis and stored separately as additional backups. We will adhere to the data and metadata standards detailed above for consistency. A long-term data preservation plan to store the data beyond the lifecycle of the project will be implemented through the institutional repository resources, run by the university libraries, which are an open access platform for wide distribution and access to university scholarship. Operational device samples on which key measurement data are collected will be labeled, packaged, and stored in cabinets in the PIs' laboratories for future reference. Data transfer between SUNY-ESF and MSU will follow security procedures and make sure 100% completeness of quality and quantity during the transfer processes. A small quantity of data, such as, tables, figures, and manuscripts for discussion and data processing will be transferred through office mailboxes set at the two universities. Dissemination and Sharing of Research Results will be published in a timely fashion on high-impact, peer-reviewed journals and presented at conferences. The PIs have a record of publication in journals of major scientific societies and publishers,

DMP-1

including Optical Society of American (OSA), American Physics Society (APS), American Institute of Physics (AIP), and American Chemical Society, etc. The PIs will also maintain and update their group websites to reflect latest advances of the groups' research. Knowledge and findings gained through this program will also be integrated into classroom teaching at SUNY-ESF and MSU, as well as presentations in professional communities. Upon request, results obtained from this research will be shared with other researchers once they are publicly disclosed in papers or presentations. Computer methods and programs will also be publicly available through publications, presentations, and web site posts.

Intellectual Properties For potentially patentable ideas and findings, the National Science Foundation Patent Policies and intellectual property policies set at the two universities will be followed. We will also adhere to the standard NSF Rights to Copyrightable Material rules for copyright material produced from the program.

DMP-2

Harvard University School of Engineering and Applied Science

Pierce Hall, 29 Oxford St., Cambridge MA 02138

Daniel J. JacobVasco McCoy Family Professor of Atmospheric Chemistry and Environmental Engineeringdjacob@fas.harvard.edu

May 5, 2015

Prof. Theodore S. DibbleSUNY/ESF

Dear Ted:

This letter is to confirm my interest in collaborating with you on improving understanding of the atmospheric fate of the HgBr radical through simulations with the global 3-D GEOS-Chem model. My student Hannah Horowitz, supported by a NSF Graduate Fellowship, has already started working with you.

A reliable representation of Hg(0) oxidation to Hg(II) in the atmosphere is necessary for accurately coupling atmospheric processes with marine and terrestrial processes. As your recent paper pointed out, the reactions that produce Hg(II) compounds following the bromine atom-initiated oxidation of Hg(0) are not well known. I look forward to incorporating into GEOS-Chem the mechanisms and rate constants determined in your proposed research. I will then carry out simulations to assess the implications of your results to both atmospheric mercury processing and deposition of mercury.

GEOS-Chem is used by over thirty (30) research groups in the U.S. and another thirty (30) research groups abroad. Your results will impact research on mercury done by these research groups by virtue of being included in GEOS-Chem.

Sincerely,

Daniel J. Jacob

State University of New York College of Environmental Science and Forestry

Department of Chemistry May 5, 2015 To whom it may concern, Since the early 2000s, there have been extensive measurements of gaseous elemental mercury (GEM), reactive gaseous mercury, and particulate mercury in various geographical environments. However, mercury research has reached a point where little progress can be made without knowing detailed chemistry involving specific reactive mercury species in mercury cycling. Dr. Dibble, his student, and I published a paper entitled “Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals” in ACP in 2012. In the paper, using quantum calculation, we identified reactive gaseous mercury species that may be formed through HgBr, from Br-initiated GEM oxidation, reacting with abundant atmospheric radicals including NO2, HO2, ClO, and BrO. We have included these reactions in our mercury box model (with estimated rate constants) and found a significant change in the composition of reactive gaseous mercury. I look forward to continuing to collaborate with Dr. Dibble to improve the representation of mercury chemistry in our box-model and in CMAQ-Hg. I will conduct simulations using CMAQ to determine the implications of Dr. Dibble’s research results for Hg(0) oxidation and mercury deposition to ecosystems. CMAQ-Hg is widely used for air quality modeling, especially for regulatory purposes. So the inclusion of the results of Dr. Dibble’s proposed research will affect scientific input to policy-makers. Sincerely, Huiting Mao Associate Professor Department of Chemistry SUNY ESF

420 Jahn • 1 Forestry Drive • Syracuse, NY 13210 • 315-470-6823 • www.esf.edu/chemistry/mao.htm www.esf.edu

From: Hannah RogersTo: Theodore S. DibbleSubject: Re: Kinetics Modules Still interestedDate: Thursday, October 08, 2015 11:04:07 AM

Dr. Dibble,This letter is to confirm that I will be willing to participate in a test run of your kinetics modules on atmospheric mercury. The new AP chemistry curriculum component 3d states that the course provides students with opportunities outside the laboratory environment to meet the learning objectives within Big Idea 4: Rates of chemical reactions. Kinetics modules on atmospheric mercury will be a good opportunity for my AP chemistry students to explore kinetics outside the laboratory setting.

-Hannah RogersFabius-Pompey High SchoolAP Chemistry Teacher(315) 683-5811hrogers@fabius.cnyric.org

Department of Chemistry

1 Forestry Drive Syracuse, NY 13210

October 20, 2015 Dear Reviewers: It is my pleasure to support Dr. Theodore Dibble’s proposal to create and test a learning module that uses the chemistry of Hg(0) oxidation as a real-life environmental example for the kinetics section of my general chemistry course. I have been an instructor for general chemistry for 20 years and the single most difficult concept for many students to grasp in that first year is kinetics. There is a lack of good examples and problems that are engaging for either the instructor or the student. It seems like the only kinetics problem in the world is ozone depletion! It will be refreshing to have a new model with interesting new applications and data to engage my students’ minds and to get them excited about what is often a very dry topic. The collaborating AP Chemistry teacher is a former teaching assistant of mine who has successfully transitioned to teaching at the high school level in a rural community. This will be a nice test class for this as it is small and Ms. Rogers is the only instructor for AP Chemistry. Ms. Rogers and I are committed to test-piloting the modules and to collecting student feedback. In my course, I will be sure to collect data from the American Chemical Society standardized 2-semester general chemistry exam and compare it with my previous courses. I am excited to have this opportunity to work with Dr. Dibble as he expands the repertoire of kinetics materials for introductory college chemistry and AP chemistry! Sincerely,

Kelley J. Donaghy Associate Professor of Chemistry

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Theodore S. Dibble

From: Wang, Chuji <cw175@msstate.edu>Sent: Sunday, November 01, 2015 8:55 PMTo: Theodore S. DibbleSubject: MSU Letter of Commitment

Dear Professor Dibble,

As the Co PI of the proposal, I will participate in the proposed research activities as proposed in the proposal entitled"Molecular insights into the oxidation of gaseous mercury: The next frontier in atmospheric mercury science". The Co PIwill commit his time and effort to the designated work in the project.

SincerelyChuji Wang

Department of Physics and AstronomyMississippi State UniversityMississippi State, MS 39762Tel 662 325 9455Email: cw175@msstate.edu