Diurnal variability and emission pattern of

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Characterization of Natural and Affected Environments 5

Diurnal variability and emission pattern of decamethylcyclopentasiloxane (D) from the application of personal care products in two North American cities. Matthew M. Coggon, Brian McDonald, Alexander Vlasenko, Patrick Veres, Francois Bernard, Abigail R. Koss, Bin Yuan, Jessica B. Gilman, Jeff Peischl, Kenneth C. Aikin, Justin DuRant, Carsten Warneke, Shao-Meng Li, and Joost A. de Gouw Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b00506 • Publication Date (Web): 16 Apr 2018 Downloaded from http://pubs.acs.org on April 16, 2018

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Environmental Science & Technology

Diurnal variability and emission pattern of decamethylcyclopentasiloxane (D5) from the application of personal care products in two North American cities. Matthew M. Coggon,∗,†,‡ Brian McDonald,†,‡ Alexander Vlasenko,¶,§ Patrick Veres,†,‡ François Bernard,†,‡ Abigail Koss,†,‡ Bin Yuan,†,‡ Jessica Gilman,† Jeff Peischl,†,‡ Ken Aikin,†,‡ Justin DuRant,k Carsten Warneke,∗,†,‡ Shao-Meng Li,∗,¶ and Joost de Gouw∗,‡ †NOAA Earth Systems Research Laboratory, Boulder, CO, USA ‡Cooperative Institute for Research in Environmental Sciences, Boulder, CO, USA ¶Air Quality Processes Research Section, Environment and Climate Change Canada, Toronto, Ontario, CA §now at Airzoneone Ltd. Mississauga, ON, CA kDepartment of Biology, University of South Carolina, Columbia, SC, USA E-mail: [email protected]; [email protected]; [email protected]; [email protected]

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] Abstract

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Decamethylcyclopentasiloxane (D5 ) is a cyclic volatile methyl siloxane (cVMS) that

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is widely used in consumer products and commonly observed in urban air. This study

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ACS Paragon Plus Environment


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quantifies the ambient mixing ratios of D5 from ground sites in two North American

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cities (Boulder, CO, USA and Toronto, ON, CA). From these data, we estimate the

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diurnal emission profile of D5 in Boulder, CO. Ambient mixing ratios were consistent

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with those measured at other urban locations; however, the diurnal pattern exhibited

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similarities with those of traffic-related compounds such as benzene. Mobile measure-

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ments and vehicle experiments demonstrate that emissions of D5 from personal care

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products are coincident in time and place with emissions of benzene from motor ve-

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hicles. During peak commuter times, the D5 /benzene ratio (wt/wt) is in excess of

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0.3, suggesting that the mass emission rate of D5 from personal care product usage

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is comparable to that of benzene due to traffic. The diurnal emission pattern of D5

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is estimated using the measured D5 /benzene ratio and inventory estimates of benzene

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emission rates in Boulder. The hourly D5 emission rate is observed to peak between

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6:00 – 7:00 AM and subsequently follow an exponential decay with a time constant of

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9.2 hr. This profile could be used by models to constrain temporal emission patterns

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of personal care products.

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Introduction

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Cyclic volatile methyl siloxanes (cVMSs) are compounds widely used in the manufactur-

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ing of consumer products, including shampoo, lotions, deodorants, and antiperspirants. 1,2

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Cyclic siloxanes are also produced as intermediates for the synthesis of polydimethylsiloxane

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(PDMS), which is used as a sealant, elastomer, and anti-foaming agent in industries such

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as petroleum processing. 3–7 The widespread use of these compounds has led to numerous

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government studies and academic reviews aimed at assessing the environmental and health

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impacts of cVMS compounds, particularly octamethylcyclotetrasiloxane (D4 ), decamethyl-

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cyclopentasiloxane (D5 ), and dodecamethylcyclohexasiloxane (D6 ). 1,6–12 Most assessments

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conclude that D4 presents environmental risks and steps have been taken to phase out the

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substance in personal care products; in contrast, the conclusions for D5 have been mixed. In

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a review by the UK Environmental Agency, 11 D5 was not identified to pose serious human

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health effects, though it qualified as a very persistent and very bioaccumulative substance.

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In a 2011 review, Environment Canada 10 concluded that D5 is persistent in the environment,

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but not bioaccumulative and not a health threat to Canadian citizens. More recently, D5

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has been found to accumulate in the livers of Atlantic cod 13,14 and a review by Rücker and

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Kümmerer 7 has highlighted the persistence of cVMSs in different environmental media. Re-

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cent restriction proposals by the EU Council on the Registration, Evaluation, Authorization,

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and Restriction of Chemicals (REACH) have been implemented to limit D4 and D5 content

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in wash-off personal care products to 0.1% by 2020. 15

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D5 is of particular interest because its presence in the atmosphere largely results from

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the evaporative emissions of personal care products. 6,7,16–18 Mackay et al. 6 estimates that

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over 90% of D5 emitted to the atmosphere results from personal care product application;

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however, residual amounts lost through product disposal may be emitted by wastewater

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treatment plants 19 and landfills. 19–21 Release of D5 from PDMS is considered negligible. 5,6

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Once released to the atmosphere, D5 is oxidized by OH radicals through hydrogen abstrac-

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tion, 22 forming silanols 23 and dimeric oxidation products 24 which may partition favorably

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into condensed phases. The global half-life for D5 is estimated to be around a week; con-

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sequently long-range transport of D5 to rural and remote regions, including the Arctic, 25 is

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possible. Recent atmospheric modeling of cVMS chemistry has demonstrated that siloxane

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oxidation products could be ubiquitous throughout the US. 17 These results are consistent

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with recent field measurements that have demonstrated a frequent occurrence of silicon-

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containing nanoparticles in rural and urban areas. 26 Such particles are too small to originate

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from mineral dust and are possibly secondary aerosols formed by siloxane oxidation. 24,26

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Due to its strong association with personal care product usage and relatively long atmo-

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spheric lifetime, D5 may act as a useful tracer for monitoring personal care product emissions

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in indoor and outdoor environments. For example, a recent study by Tang et al. 27 demon-

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strated that D4 , D5 , and D6 evaporated from personal care products constituted the largest

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component of indoor volatile organic compounds (VOCs) measured in an engineering class-

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room. Recent work has suggested that personal care product emissions could significantly

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contribute to the VOC burden in urban areas; 18,28 thus, constraining D5 emission rates,

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and its relationship to other urban VOCs, could help to improve VOC emission invento-

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ries. Urban D5 emission rates have been previously estimated based on modeling of ambient

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measurements (190 mg person−1 d−1 , Chicago, IL, USA; 310 mg person−1 d−1 , Zurich,

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Switzerland) 29 and sales of personal care products (260 mg person−1 d−1 , Canada). 6,29

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D5 has been measured in urban (e.g. Chicago, USA, Toronto, Canada, and Zurich,

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Switzerland) 30–32 and rural/remote atmospheres (e.g. Sweden, Arctic) 25,33,34 using low-time

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resolution instrumentation. To date, one study has reported average D5 flux measurements

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by high time-resolution mass spectrometry. 28 Measurements of hourly concentrations are

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needed to evaluate the variability of D5 concentrations, infer emission mechanisms, and

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constrain emission profiles in regional atmospheric models. Here, we report fast, real-time

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measurements of ambient D5 in two urban, North-American locations (Boulder, Colorado,

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USA and Toronto, Ontario, CA). From these data, we investigate D5 emission mechanisms,

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calculate diurnal D5 emission patterns, and estimate city-wide D5 emissions for Boulder, CO.

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Methods

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Instrumentation

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Measurements of VOCs in Toronto were conducted using a high mass-resolution proton-

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transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS, Ionicon Analytik). A gen-

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eral description of the instrument is published elsewhere. 35,36 Data were acquired on a 1

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min accumulation period using TofDaq software (Tofwerk AG) and post-processed using the

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PTRMS TOF Viewer software (Ionicon Analytik). Twenty background measurements were

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conducted over the course of the campaign by passing air through a charcoal cartridge and

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platinum catalyst heated to 350◦ C to remove VOCs. All data presented here have been 4


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background-corrected assuming a linear interpolation between zeroed samples.

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The instrument response to a D5 standard was measured by the addition of a certified

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gas mixture (1 ppm, Air Liquide). The sensitivity of the PTR-ToF-MS to the D5 signal at

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the parent ion (m/z 371.10 H+ C10 H30 O5 Si5 ), was found to be 10±0.3 ncps/ppb at a reagent

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ion signal of 1×106 cps. The instrument detection limit was found to be 2 ppt for a 10 min

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data accumulation period.

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Measurements in Boulder were also conducted using a PTR-ToF-MS (Tofwerk AG, Aero-

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dyne Research Inc. ). 37 For clarity, we refer to this instrument as the NOAA PTR-ToF-MS.

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A complete description of the instrument is provided by Yuan et al. 37 The acquired data

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were processed following the recommendations of Stark et al. 38 using the CIMS Tofware

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package (v. 2.5.7) in Igor Pro (WaveMetrics, Lake Oswego, OR). In this study, the NOAA

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PTR-ToF-MS was deployed twice to measure ambient D5 concentrations (see Measurement

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Description). In 2015, the instrument was operated using the configuration described by

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Yuan et al.; 37 in 2017, the instrument was operated in the absence of the small segmented

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quadrupole (SSQ). We refer to this instrumental configuration as the "modified" NOAA

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PTR-ToF-MS. The SSQ was removed to reduce the VOC humidity dependence associated

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with the previous instrument design. 37 All data presented here have been corrected for hu-

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midity using the water cluster ratio (m/z 37/m/z 19), as prescribed by Yuan et al. 37 A full

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description of this correction is provided in the Supporting Information.

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In both Boulder deployments, data were acquired on a 30 s accumulation period. Every

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two hours, an instrument zero was conducted by passing ambient air through a platinum

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catalyst heated to 350◦ C. These data have been background-corrected assuming a linear

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interpolation between zeroed samples. Every six hours, the instrument was calibrated with

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a 10 component, gravimetrically prepared gas standard containing VOCs with known sensi-

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tivities. The instrument response to this calibration standard was stable to within 15% over

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the course of each deployment. These fluctuations in instrument response are influenced

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by uncertainties in the calibration standard (20%) and normal variations in the instrument

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transmission curve. 39

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In 2015, the NOAA PTR-ToF-MS response to D5 at the parent ion (m/z 371.10) was

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calibrated by permeation cell followed by catalytic conversion to CO2 . 40 This method is a

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standard technique for calibrating the response of proton-transfer-reaction mass spectrome-

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ters to many VOCs; 37,40 however, employing this method with silicon-containing compounds

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presents uncertainties due to the potential for catalytic poisoning by SiO2 formed during

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the combustion process. Here, the catalyst was operated at a temperature of 350◦ C and

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a flow rate of 14 sccm. Prior to instrument calibration, the CO2 concentration resulting

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from D5 combustion was stable at 0.94±0.04ppm for over 6 hr. Because this method has

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the potential to negatively bias the conversion of D5 to CO2 , the resulting calibration factor

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(7.1±0.5 ncps/ppb at a reagent ion signal of 1.3×106 cps, Fig. S1C) should be treated as

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an upper-limit. The limit of detection (3σ), determined based on the signal noise during

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background measurements, was 5 ppt for a 30 s data accumulation period.

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In 2017, the modified NOAA PTR-ToF-MS was calibrated using a home-built liquid

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calibration unit (LCU). This method was employed to avoid the uncertainties associated

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with catalytic conversion of D5 to CO2 . Briefly, D5 and benzene (added as a reference

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standard) were mixed with n-hexane (used as a solvent) and injected into a steady stream

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of N2 (∼ 0.5 L min−1 ) using a high precision syringe pump (Harvard Apparatus). The

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temperature of the septum and injection port was maintained at 50 – 60◦ C to ensure complete

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compound volatilization. Before entering the NOAA PTR-ToF-MS, the VOC mixture was

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diluted by an additional stream of N2 . Calibration experiments were conducted for a variety

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of benzene and D5 concentrations (0.01–0.1 wt%) and N2 dilution flows (1.5-3 L min−1 ),

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resulting in a range of D5 concentrations (50 ppt – 20 ppb). This calibration method was

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tested for VOCs routinely monitored by the NOAA PTR-ToF-MS (e.g. benzene, toluene,

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and acetone) and was found to reproduce the sensitivity to within 5%. Benzene, toluene, and

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acetone are typically calibrated by gravimetrically prepared gas standards with uncertainty

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of 20%; consequently, we assume 20% uncertainty for the D5 calibration. The sensitivity of

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the PTR-ToF-MS to D5 was measured to be 27 ncps/ppb at a reagent ion signal of 9×106 cps

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(Fig. S1C). The limit of detection of the modified NOAA PTR-ToF-MS was found to be 2 ppt

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for a 30 s data accumulation period. We note that the difference in sensitivity and detection

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limits between the 2015 and 2017 measurements results from differences in instrumental

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setups. Despite these differences, the D5 /benzene ratio, which we use to constrain the D5

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emission pattern, agree to within 30% between both sampling periods (see Results Section

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and Fig. S8).

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We also report PTR-ToF-MS measurements of benzene (m/z 79.05), which is largely

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associated with vehicle exhaust when measured in urban air. For both instruments, the re-

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sponse to benzene was calibrated by the addition of certified or gravimetrically prepared gas

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standards. We note that the calibration ranges described above do not extend to the lowest

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ambient D5 and benzene concentrations measured (

Diurnal variability and emission pattern of

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