Atmospheric Reactivity of Fullerene (C60) Aerosols - ACS Earth and

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Atmospheric Reactivity of Fullerene (C ) Aerosols Dhruv Mitroo, Jiewei Wu, Peter F Colletti, Seung Soo Lee, Michael Walker, William H. Brune, Brent J. Williams, and John D. Fortner ACS Earth Space Chem., Just Accepted Manuscript • DOI: 10.1021/ acsearthspacechem.7b00116 • Publication Date (Web): 30 Nov 2017 Downloaded from http://pubs.acs.org on December 9, 2017

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ACS Earth and Space Chemistry

Title

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Atmospheric Reactivity of Fullerene (C60) Aerosols

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Author List

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Dhruv Mitroo,†,‡ Jiewei Wu,† Peter F. Colletti,† Seung Soo Lee,† Michael J. Walker,† William H.

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Brune,§ Brent J. Williams,*,† and John D. Fortner,*,†

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†

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Louis, St. Louis, Missouri 63130, United States

Department of Energy, Environmental and Chemical Engineering, Washington University in St.

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§

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University Park, Pennsylvania 16802, United States

Department of Meteorology and Atmospheric Sciences, The Pennsylvania State University,

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Table of Contents Graphic

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Abstract

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Rapid growth and adoption of nanomaterial-based technologies underpins a risk for unaccounted

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material release to the environment. Carbon based materials, in particular fullerenes, have been

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widely proposed for a variety of applications. A quantitative understanding of how they behave

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is critical for accurate environmental impact assessment. While their aqueous phase reactivity,

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fate, and transport has been studied for over a decade, aerosol phase reactivity remains

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unexplored. Here, the transformation of C60, as nanocrystal (nC60) aerosols, is evaluated over a

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range of simulated atmospheric conditions. Upon exposure to UV light, gas-phase O3, and ·OH,

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nC60 is readily oxidized. This reaction pathway is likely limited by diffusion of oxidants

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within/through the nC60 aerosol. Further, gas-phase oxidation induces disorder in the crystal

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structure without affecting aerosol (aggregate) size. Loss of crystallinity suggests aged nC60

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aerosols will be less effective ice nuclei; but, an increase in surface oxidation will improve their

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cloud condensation nuclei ability.

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Keywords: fullerenes, nC60, nanocrystals, oxidation, potential aerosol mass (PAM) reactor,

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atmospheric aging

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Introduction

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Industrial scale production and adoption of engineered nanomaterials raises concerns over their

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inadvertent impacts on human health and natural systems.1,2 Of these, carbon based nanoscale

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materials such as fullerenes, carbon nanotubes (CNTs), and graphene are being developed for a

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variety of applications.3–5 Fundamental understanding of how such materials behave when

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released in fluvial, marine, or atmospheric systems is critical for material design, life cycle

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analyses, risk assessment, and eventual effective waste management scenarios. In contrast to

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aqueous systems, atmospheric aerosol release scenarios have only recently been considered for

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engineered nanomaterials, such as carbon nanotubes (CNTs) and fullerenes, and inorganic

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nanoparticles, such as TiO2.2,6,7 In particular, the fate of fullerenes in aqueous systems is being

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studied extensively. 8–10 In the atmosphere, fullerenes have been identified in sooty flames11 and

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lightning12: high energy (and high temperature) processes. To date, there is little understanding

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of how low energy events (relative to formation events) such as atmospheric processing (e.g.,

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photo-oxidation)13 of fullerenes significantly alter their physicochemical properties – and thus

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their behavior, which is a critical knowledge gap for accurate modeling of solubility,

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(bio)availability, reactivity, stability, and toxicity.

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In the aqueous phase, C60 (as nC60) is readily oxidized in absence of light with both

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ozone, yielding hemiketal and hydroxyl functionalities proposed via a modified Criegee

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mechanism, and by hydroxyl radicals, forming hydroxylated fullerenes.8,14 Recently, Wu et al.

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found that free chlorine also oxidizes nC60 in aqueous media, eventually altering the

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nanoparticles’ crystal structure.15 Because the cage structure imposes strain on its aromatic rings,

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epoxide formation is unstable, and water hydrolyzes intermediate C-O-O● structures to yield



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C=O or C-OH functional groups.16–18 Further, UV light has been shown to sensitize aqueous

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phase reactions leading to oxidation products including epoxides and ethers.19 A decade before

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this discovery, Foote et al. proposed an energy transfer mechanism whereby photons excite 1C60

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to an excited state, 1C60*, leading through intersystem crossing (ISC) to the triplet excited state

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3

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oxygen 3O2 to singlet oxygen, 1O2.20 Krusic et al. instead proposed a type I mechanism where

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3

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shown to generate reactive oxygen species (ROS).22 The generation of the radical anion has been

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also observed in aqueous phase nC60 aggregates as well, also generating ROS.23

C60*.20 Then, through a type II energy transfer mechanism, this can convert excited triplet

C60* forms the anion C60-● in the presence of an electron donor.21 Both pathways have been

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With regard to the atmosphere (troposphere), nC60 chemistry is largely unexplored. To

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date there are two reported field observations of airborne fullerenes (without distinguishing

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between their molecular and aggregated states),24,25 one systematic laboratory study of

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atmospheric ozonolysis of fullerene,26 and one of atmospheric ozonolysis / photooxidation of

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CNTs.27 Utsunomiya et al. observed fullerenes in samples from coal-fired power plants collected

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in Detroit, MI,24 and Sanchis et al. report observations of aerosol-bound fullerene in all samples

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collected in two campaigns covering different regions of the Mediterranean.25 It is worth noting

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that in addition to the two campaigns, fullerenes have been identified in other airborne samples,28

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further highlighting the importance of constraining fullerene mobilization in the atmosphere.

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However, atmospheric processing of these fullerenes has not been investigated or discussed.

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Recently, Tiwari et al. explored atmospheric ozonolysis of C60 bulk fullerene powder through lab

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studies, showing that atmospheric timescales can accommodate surface reaction of potential

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fullerene aerosols.26 Similarly, Liu and coworkers investigated atmospheric photo-oxidation of

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CNTs via both ozone and hydroxyl attack, suggesting evidence of processing, and raising


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concern over gas-particle partitioning of organics in CNTs during atmospheric evolution.27 In

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both studies, commercially available C60 powder and CNTs of fixed (commercial grade) purity

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and aggregate size were used. Other studies concerning aerosol-phase heterogeneous (gas-phase

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reaction on the surface of a solid particle) oxidation via ozone or hydroxyl radicals have

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investigated the chemistry of non-aromatics such as oleic / stearic acid particles,29 squalene,30

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palmitic acid,31 and erythritol and levoglucosan;32 aromatics including surface-bound polycyclic

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aromatic hydrocarbons (PAHs).33–35 To date, to the best of our knowledge, none have looked at

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engineered nanoparticles.

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Here, we present direct evidence of atmospherically relevant heterogeneous reactions of

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nC60 aerosols by simultaneous ozone and hydroxyl radical oxidation in presence of UV light

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using a Potential Aerosol Mass (PAM) reactor,36 an oxidative flow-tube reactor (OFR).

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Atmospheric exposure, or mimicked ‘age’, of the aerosol spans between ~ 0 – 2 weeks, over

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which, we monitor physical and chemical changes to the nC60 aerosols. Surface oxidation, crystal

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structure, and aggregate (aerosol) size are described as a function of exposure in the gas-phase.

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Materials and Methods

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Setup. For this study, nC60 was synthesized as described previously in detail by Fortner et al.8

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The experimental setup schematic for the aerosol-phase oxidation study is available in the

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Supporting Information (Figure S1), alongside a description of the nC60 synthesis (section titled

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nC60 nanocrystal synthesis). Briefly, a 25mgL-1 nC60 suspension was atomized in a 6-jet Collison

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Nebulizer (BGI, Inc; Waltham, MA) and passed through an inlet heated to ~100°C to drive

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surface water off the aerosolized particles. Half of the flow (corresponding to 5.0 L min-1) was



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sent to the PAM reactor via a custom-built diffusion dryer to remove water vapor from the

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aerosol stream. Relative humidity (RH) control in the PAM chamber was achieved by adding

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4.6 L min-1 of N2 flow with fixed humidity. Additional details can be found in the Setup details

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section in the Supporting Information. Reported negative ζ-potential measurements in nC60

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aqueous suspensions37 suggest that electrostatic repulsion is important in stabilizing the

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suspensions. If aggregation of primary nC60 nanoparticles does not occur in suspension, then

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drying should not induce further clustering. This was the case for our system (see Supporting

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Information Figure S2), where the mode of the size distribution in the aerosol phase was

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comparable to that of the aqueous phase.

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Reactor. The custom built PAM reactor is an iridite-treated aluminum cylinder, 18

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inches in length and 8 inches in inner diameter, giving it a total volume of 13 L. The chamber is

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equipped with two 12 inch mercury lamps with peak wavelengths at 185 nm and 254 nm (BHK

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Inc. Analamp Model No. 82-9304-03; Ontario, CA) housed in Teflon sheaths. There is an

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annular flow of N2 through the sheaths to prevent direct contact with the lamps and purge any

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outgas products. The mercury lamps are connected to a variable voltage supply (BHK Inc.;

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Ontario, CA) to regulate light intensity. The former wavelength is necessary for the O2

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photolysis to produce O3, and the latter dissociates O3 to form singlet oxygen, O(1D), which in

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the presence of H2O forms the hydroxyl radical.36 Teflon sheaths are transparent to both

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wavelengths. Additional ozone is delivered to the inlet of the PAM to accelerate production of

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hydroxyl radicals. A simplistic mechanism of oxidant formation can be found in the Supporting

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Information, equations (3) – (7) and more refined mechanisms are available in the literature.38–42

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At a fixed 10 L min-1 flowrate, the mean residence time for the nC60 aerosol in the reactor, τres,

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(defined by the volume of the reactor divided by the outlet flowrate) is approximately 78 s. This


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parameter is held constant throughout the study. Typically, heterogeneous reactions in OFRs

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conducted by other groups are performed at RH in the range of ~10-60%.39,40,43,44 For our study,

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RH was chosen at ~30% (dry conditions to avoid potential deliquescence of aerosols, yet high

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enough to promote ·OH formation) and kept constant since the mixing ratio of water directly

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affects hydroxyl radical production (as per Supporting Information eq. (7)).40

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OH Exposure. The reactor can generate hydroxyl radicals in mixing ratios >1000 ppt,

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which is several order-of-magnitudes higher than atmospheric concentrations (typically 10-19 cm2s-1, typical for crystalline

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solids60), which is considerably longer than atmospheric reaction timescales. However, if

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aerosol-phase surface reaction morphs the pristine structure, the diffusion timescales can be

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greatly affected, and the observed rate of reaction would also change. For example, trace levels

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of hydrogen chloride (HCl) gas have shown to induce disorder on ice surfaces in a temperature

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range of 186 K to 243 K.61 This process explains why reported values for diffusion coefficients

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of HCl on ice vary dramatically on different ice surfaces.62,63 If atmospheric photo-oxidants

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could have similar effects on nC60 surfaces, reaction rates would not be as slow as expected. To

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explore this, high resolution transmission electron microscopy (HR-TEM) images (Figure 5) and

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X-ray diffraction (XRD) patterns (Figure S4) were evaluated for parent and oxidized samples.

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Results suggest that crystallinity is lost upon oxidation; however, persistence of peaks at ca. 520

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cm-1 and 570 cm-1 (parent peaks) in FTIR spectra suggest that parent C60 does exist, to some

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degree in the aggregate (likely in the aerosol core). While this would challenge the suggestion

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that reaction (chemical or physical) is surface-limited, without further investigation, it is not

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straightforward to assess the underlying mechanism that drives the observed disorder.

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Underpinning this process, several phenomena may be responsible, including: i) increased

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surface disorder, either allowing oxidants to diffuse to the core more readily, or ii) rearrangement



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of product molecules to the core that, although involving an enthalpic penalty, are entropically

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preferred. Owing to the cage structure of a C60 molecule and its (caged) products, the enthalpic

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cost of breaking a π−π stacking interactions is likely not strong enough to hinder disorder in the

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nanoparticle. Other possibilities include iii) intercolated water within the nanoparticle aggregate,

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which upon UV light irradiation, releases ROS that readily react with the core, or unexpected

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ligand-induced rearrangements64 or iv) a purely UV-light sensitized rearrangement of the

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nanoparticle structure that, although interesting, is not relevant to tropospheric chemistry. We

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suggest excluding possibility ii) due to the unlikeliness of entropy outweighing enthalpy and iii)

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due to FTIR data not showing dramatic decrease in the parent peaks upon oxidation. The only

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way possibility iv) would be excluded is by assuming that work done by Lee et al.19, implying

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that the free oxygen’s role has a fundamental effect on crystal structure too. OFRs like the PAM

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reactor operate on τres values on the order of seconds to minutes, which is short compared to an

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average aerosol lifetime in the troposphere. Therefore we can not quantify the effect of diffusion

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on atmospheric photo-oxidation for nC60. David et al. suggest that >260 K, C60 molecules

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undergo (continuous) reorientation;65 therefore, although atmospheric photooxidation is not a

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high energy process, it may be enough to destabilize π – π stacking in the outer lattice and

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induce disorder in the crystal structure.

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For reacted samples, XPS spectra are different from those observed for samples produced

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by the aqueous phase reaction of nC60 with ozone, as published by Fortner et al.8 Ozonation of

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aqueous nC60 yields more di-oxidized than mono-oxidized carbon (30% and 18%, respectively,

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from XPS fitted peak area), whereas in this study, fullerenes subject to the highest ·OH exposure

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of ~2.24E+12 molec. cm-3 s (~17.3 equivalent days of aging) yielded comparatively more mono-

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oxidized than di-oxidized carbon (27.8% and 12.3%, respectively, from XPS peak area), and the


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remaining un-derivatized carbon fraction was higher (52% for the aqueous study and 60.0% for

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this study). For these, resulting apectra are more similar to that of the aqueous phase reaction of

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nC60 with ·OH as described by Lee et al., although the mono-oxidized carbon fraction of the area

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is much higher for aqueous-phase oxidation (53.64% for the aqueous study and 27.8% for this

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study at ~17.3 equivalent days of aging).

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Environmental Implications. In this report, we observe direct evidence of atmospheric

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oxidation of C60. However, in relatively dry conditions (~30% RH), even a very strong oxidizing

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atmosphere yields a limited reaction of the material. Based on the decay of un-derivatized carbon

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via XPS analysis, we estimate the atmospheric photochemical lifetime of nC60 to be 1-2 months,

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meaning wet and dry deposition would remain the dominant atmospheric loss pathways. Such a

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slow oxidation mechanism helps explain detection of aerosol-bound fullerenes even in the

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Mediterranean basin,25 far removed from anthropogenic sources. The reactive and effective

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uptake coefficients for nC60 to O3 or ·OH has not been calculated due to coupling of the oxidants

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(hydroxylation photochemistry versus ozonolysis) as well as complex mixing patterns in the

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reactor, and while important, are beyond the scope of this work. It is worth mentioning that Pillar

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et al.66 assessed that, using an effective uptake coefficient of ozone on catechol at the air-water

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interface of 2.73E-7 and an effective uptake of ·OH between 0.01 and 1, the rate of reaction of

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O3 to catechol can be 1 – 100 times that of ·OH to catechol for mean tropospheric values.

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However, this is dependent on forming the initial ozonide, which given C60’s caged structure,

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becomes less favorable. Given our estimate of nC60’s photochemical lifetime is on the order of

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months, compared to hours for catechol from Pillar et al., we take caution in extending their

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values to our system. Taken together, with light sensitizing the reaction by both producing ·OH

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and promoting C60 to its excited triplet state, we believe both in the PAM and in the troposphere,



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that ·OH oxidation accounts for more nC60 depletion than O3 oxidation. We do however

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recognize that in the PAM this reaction could be augmented artificially due to the UV light

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required in ·OH generation.

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Of interest in future work is to understand interactions with fog water or cloud water

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(e.g., how uptake kinetics vary as a function of dry aerosol age) using both dry aerosolization

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techniques (Tiwari et al.) and wet aerosolization techniques (this work). Functionalizing the

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surface should increase the hydrophilicity of the nanoparticle, however if, once scavenged, the

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outer layer sheds (is solubilized) into solution, the freshly exposed hydrophobic surface may

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repartition to the aerosol phase, where it can undergo further aerosol phase oxidation. This could

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be important for reactions in deliquesced aerosols. Cloud seeding, where an increase in polarity

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on the surface of the nanoparticles may cause them to act as more efficient cloud condensation

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nuclei (CCN), can become important at tropical latitudes where clouds are warmer, but not as

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effective at higher latitudes or altitudes where ice nuclei (IN) become more important.

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Furthermore, wildfires and agricultural activity at those latitudes result in a consistent source of

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soot aerosols, likely containing fullerene. Increased light exposure yields consistent vertical

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profiles of ·OH45 which can become a dominant oxidant at higher altitudes, resulting in

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hydroxylation photochemistry driving fullerene reactivity in the free troposphere.

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Figure 1: Change in the geometric mean mobility diameter (Dpg) of aerosolized nC60 as a

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function of OH Exposure for mixed OH / O3 oxidation. Values are normalized by an average Dpg

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for unoxidized nC60 (control, see SI), and the bias associated with the control Dpg is subtracted.



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Figure 2: Offset FTIR spectra for nC60 samples collected on PTFE filters at different levels of

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OH Exposures for mixed OH / O3 oxidation. Peaks around ca. 1400 cm-1 and 1700 cm-1 indicate

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of C – OH and C = O groups respectively.

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Figure 3: XPS data on nC60 for a) aqueous sample and b) aerosol sample without exposure, and

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for aerosol nC60 exposed at c) 2.4 d) 7.9 e) 13.3 and f) 17.2 equivalent days of aging. Peaks 1, 2,

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and 3 correspond to underivatized, mono-oxidized, and di-oxidized carbon in that order.

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Figure 4: Integrated peak areas from XPS data as a function of OH Exposure for differently

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hybridized carbon.

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Figure 5: Transmission electron microscopy data for unoxidized nC60 displayed as a) HR-TEM

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image and b) fast Fourier Transform (FFT) pattern, and oxidized nC60 (16.1 equivalent days of

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aging) displayed as c) HR-TEM image and d) FFT pattern.

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TABLES

-3

OH Exposure (molec. cm s) (3.14±0.16) E+11 (1.02±0.01) E+12 (1.73±0.02) E+12 (2.24±0.03) E+12

Equivalent Age (days)

0 2.42±0.12 7.87±0.10 13.3±0.1 17.2±0.20

Underivatized Carbon % Area 80.00 72.89 68.93 62.12 60.00


Monooxidized Carbon % Area 16.29 22.61 25.05 28.66 27.75

Di-oxidized Carbon % Area 3.72 4.50 6.03 9.22 12.25


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Table 1: XPS Peak fitted data.

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Associated Content

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Supporting Information

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Experimental details and additional data.

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Author Information

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Corresponding Authors

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*Address: One Brookings Drive, Brauer 1015, St. Louis, Missouri, 63130. Email (J.D.F.):

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[email protected]. Telephone: (314) 935-9293.

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*Address: One Brookings Drive, Brauer 3026, St. Louis, Missouri, 63130. Email (B.J.W.):

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[email protected]. Telephone: (314) 935-9279.

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Present Addresses

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‡

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Miami, Florida, 33149, USA.

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Notes

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The authors declare no competing financial interest.

Dhruv Mitroo: Rosenstiel School of Marine and Atmospheric Sciences, University of Miami,

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Acknowledgments

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This work was supported by the National Science Foundation Grant #1236865. We would like to

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thank Adan Montoya, Carl Hinton, and Yining Ou for their help in washing nC60 batches. We

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would also like to thank Dr. Huafang Li and the Institute of Materials Science & Engineering

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(IMSE) at Washington University in St. Louis (WUStL) for her valuable assistance and training

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on the XPS. Finally, we sincerely thank Prof. James Ballard at WUStL and Prof. Dylan Millet at

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the University of Minnesota (UMN) for insightful discussion and valuable feedback.

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References

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