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Apr 27, 2017 - wiping paper towel in a trash can was able to transform ammonium sulfate and ammonium nitrate into (MEA)2SO4 and (MEA)NO3. This...
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A single usage of a kitchen degreaser can alter indoor aerosol composition for days Jaroslav Schwarz, Otakar Makeš, Jakub Ondrá#ek, Michael Cusack, Nicholas Talbot, Petr Vodi#ka, Lucie Kubelova, and Vladimir Zdimal Environ. Sci. Technol., Just Accepted Manuscript • Publication Date (Web): 27 Apr 2017 Downloaded from http://pubs.acs.org on April 27, 2017

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A single usage of a kitchen degreaser can alter indoor

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aerosol composition for days

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Jaroslav Schwarz*, Otakar Makeš, Jakub Ondráček, Michael Cusack, Nicholas Talbot, Petr

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Vodička, Lucie Kubelová, Vladimír Ždímal

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Institute of Chemical Process Fundamentals of the CAS, Prague, Czech Republic

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Abstract

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To the best of our knowledge, this study represents the first observation of multi-day persistence

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of an indoor aerosol transformation linked to a kitchen degreaser containing mono-ethanol amine

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(MEA). MEA remaining on the cleaned surfaces and on a wiping paper towel in a trash can was

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able to transform ammonium sulfate and ammonium nitrate into (MEA)2SO4 and (MEA)NO3. This

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influence persisted for at least 60 hours despite a high average ventilation rate. The influence was

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observed using both offline (filters, impactors, and ion chromatography analysis) and online

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(compact time-of-flight aerosol mass spectrometer) techniques. Substitution of ammonia in

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ammonium salts was observed not only in aerosol but also in particles deposited on a filter before

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the release of MEA. The similar influence of other amines is expected based on literature data.

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This influence represents a new pathway for MEA exposure of people in an indoor environment.

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The stabilizing effect on indoor nitrate also causes higher indoor exposure to fine nitrates.

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TOC art

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Introduction

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Indoor aerosol studies are important because people spend approximately 80% of their lives

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indoors, and aerosols can have negative health effects, as observed in many studies1. Indoor

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aerosols can originate as outdoor aerosol transported through windows and wall leaks2. In the

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absence of indoor aerosol sources, the levels of indoor aerosol are always lower than outdoor

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aerosol levels, and the difference depends on the natural air exchange rate in the absence of

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filtration devices. The size dependence of the indoor/outdoor ratio resulting from different particle

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removal processes is well known.

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However, when indoor sources, such as smoking, cooking, open fire heating or cleaning, are

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present, these sources can easily dominate indoor aerosol concentrations and affect the overall

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aerosol chemical composition. Even humans act as aerosol source that adds particles to the overall

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indoor aerosol content.

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The chemical transformation of particles transported from outside to the indoor environment is

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well known and frequently observed for the case of ammonium nitrates3–5. However, little is

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known about transformations of indoor aerosols under the influence of the broad collection of

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chemicals we use to keep our homes clean and at the desired level of sterility.

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One family of substances often found in the domestic environment is aminium salts, which are

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used in different surface active detergents. By examining manufacturer data and chemically

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analyzing this cleaner, we found that not only aminium salts are used in the water solution of

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degreasing solutes but also free amines such as mono-ethanol amine (MEA).

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The role of amines and aminium salts in ambient atmospheric aerosols has been recognized

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relatively recently6, leading to a growing number of papers dealing with this subject. The influence

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of amines on ambient atmospheric nucleation has been studied both theoretically7 and

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experimentally8,9. Amines have been found in the ultrafine fraction of ambient aerosol, and there

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are only a few papers dealing with their possible effects. Recently, aminium salts were suggested

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to be at least partially responsible for new particle formation events10, and their ability to thermally

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stabilize nitrates was studied by Salo et al. (2011)11. The growing interest in aminium salts in

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atmospheric aerosol has also led to studies of their relevant properties12–14 and their chemical

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reactions with atmospherically relevant compounds9,15–19. Very recently Chu and Chan (2017)20

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studied uptake of dimethyl amine by ammonium sulphates and its mixture with sucrose. The

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toxicology of amines was reviewed by Knaak et al. (1997)21; more recently, the toxicology of

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MEA was studied by Kamijo et al. (2007)22.

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Two papers have also described the influence of sulfuric acid emissions on MEA aerosol during

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the CO2 capture process23,24, suggesting the formation of MEA sulfate in the aerosol phase.

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In this study, and we believe for the first time in the context of a common indoor environment, we

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describe the ability of mono-ethanol amine, a constituent of a commercial degreaser solution for

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cleaning kitchens, to replace ammonium in inorganic salts in the indoor environment. In this case,

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ammonium is replaced mainly in its sulfate and nitrate salts in the inorganic aerosol that usually

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forms up to half of PM2.5 aerosol mass in indoor environments. Both complete and partial

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replacement was recorded in our experiment, depending on the mode of degreaser usage and the

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indoor activities that followed. Moreover, the dynamics of the pollution are described using a

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combination of different aerosol instrumentation and analytical techniques during a

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comprehensive indoor/outdoor experiment using both offline and online sampling techniques in

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an experimental room at an Institute of Chemical Process Fundamentals (ICPF) facility. This

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configuration is similar to one used in our previous paper4, but here, the investigation was

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substantially enriched using a in house built humidity tandem differential mobility analyzer

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(HTDMA)25, field OC/EC analyzer (Sunset Laboratory Inc., Tigard, USA), and compact time-

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of-flight aerosol mass spectrometer (C-ToF-AMS, referred further as AMS, Aerodyne Research,

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Inc., Billerica, USA)26. A complete overview of the campaign and its results are provided

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elsewhere26. In this paper, the newly recognized effects of cleaning chemicals used indoors are

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described with focus on change in indoor aerosol chemical composition.

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Experimental procedures

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The offline sampling used PM1 and PM10 sampling heads with Leckel pumps (Sven Leckel

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GmbH, Berlin, Germany) and SDI and BLPI cascade impactors to collect aerosol samples in both

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indoor and outdoor environments in parallel. Samples were collected for 23 h. The filter holders

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were loaded with pre-combusted (800°C, 3 h) quartz fiber filters (Pall Tissuquartz, 47 mm). For

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PM1, two filters in series were used to mitigate the possible adsorption artifacts for the OC/EC

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analyses. The filters and BLPI samples were analyzed using gravimetry and ion chromatography.

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More details about the sampling campaign can be found in Talbot et al. (2016)27. Here, the

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description concentrates only on the experimental details relevant to this paper.

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In addition to other sources, the influence of a W5 degreaser (Lidl Stiftung & Co. KG, Neckarsulm,

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Germany) sprayed on kitchen furniture surfaces was studied. Similar degreasers are sold under

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different names globally. The spray composition, as declared by the producer, is as follows

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(without concentrations): water, sodium C13-17 alkane sulfonate, mono-ethanolamine, MEA-

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palm kernelate, trisodium n,n-bis (carboxymethyl)-ß-alanine, perfume, limonene. The IC

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chromatography analysis showed more than 5% (w/w) of MEA in the solution.

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The following experiment was completed twice. During the first cleaner usage on September 1,

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2014, the cleaner was applied at 6:30 p.m. for 1 min. At that time, 24 h filter sampling of PM1 and

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PM10 aerosol was already underway, beginning at 10 a.m. The AMS, SMPS, APS, and HTDMA

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were also continuously running during that whole period. The next day (September 2, 2014),

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between 9 a.m. and 10 a.m., the filters were changed, and the BLPI and SDI were turned on at the

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same time. The micro-ventilation and ventilator above the electrical stove were also turned on. No

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additional indoor source was used over the next 24 h, but the micro-ventilation and ventilator were

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switched off at 15:59 because a coal-burning smell was detected at the site. On the third day

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(09/03/2014) at 9:44 a.m., the surface was wiped, and new filters were loaded. At 16:00, an outdoor

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barbecue was used to visualize the entrainment of aerosols to the indoor space. No impactors were

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running during that time. On September 4th and 5th, other indoor sources were tested. On September

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6th, the same cleaning solution was used at 9:50 a.m., and the doors were closed at 10 a.m. Only

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the online instruments, including the AMS, were running at that point and continued to run until

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the end of campaign, on September 8th at 11:08.

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The quartz fiber filter samples and the BLPI impactor foils were weighted and stored in a freezer

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until the analysis of water soluble ions was completed using a Dionex 5000 system that enables

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parallel analysis of both anions and cations. Two different calibrations were used for cations; one

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of them included six amine standards in addition to the standard cations (Na+, NH4+, K+, Mg2+,

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Ca2+). All amines (mono-ethanolamine (MEA), tri-ethanolamine (TEA), tri-ethylamine (TA), tri-

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methylamine (TMA), methoxypropylamine (MPA), and tetra-methylammonium (TMAH)) used

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in calibration were separated from other cations; however, complete separation of ammonium and

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MEA was not achieved (Fig. 1).

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Figure 1. IC separation of basic cations and six amines.

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AMS determination of MEA aerosol concentrations

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The AMS data were first evaluated using standard procedures described in Allan et al. (2004)28

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and for our instrument in Kubelová et al. (2015)29. Although c-ToF-AMS is not normally used for

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the determination of individual substance concentrations, with the exception of certain inorganic

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species, we have found a semi-quantitative way to determine MEA concentrations in the aerosol

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phase during part of the sampling period. The determination was based on the difference in ratio

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of m/zNO3 30 and m/zNO3 46, for normal ambient conditions (the ratio is normally relatively stable

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in ambient aerosol for a given AMS instrument) and the same ratio for period under the MEA

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influence. The concentration of MEA in aerosol was determined from balance of masses m/zNO3

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30 and m/zNO3 46 originally attributed to nitrates and their ambient ratio and the ratio of same

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masses found during calibration using MEA sulfate aerosol. The details of this procedure are

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similar to those reported by Murphy et al. (2007)30, who characterized aminium nitrate salts

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(including MEA nitrate) in a chamber study using c-ToF AMS and noted the influence of amines

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on m/z 30, and are given in Supplement 1. The ratio is influenced by the presence of other sources

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(particularly combustion); thus, only data without the strong influence of another source are

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presented. Comparison of mass spectra measured for MEA sulfate showed a substantial effect on

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mass m/z 30 that is normally attributed to nitrates (Fig. S2). No species dependent collection

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efficiency (CE) was applied here.

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Results and discussion

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Average ratios of PM1, PM10, and compounds with no indoor sources in the indoor and outdoor

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environments

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Several sampling days throughout the campaign were devoted to determining the indoor/outdoor

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relationship of aerosol without the influence of any major indoor source. Various ventilation

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scenarios were used during these sampling days to test the influence of ventilation rate on indoor

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concentrations. Table 1 contains the results of the average indoor-to-outdoor ratios of the main

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aerosol species in PM1 and PM10.

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Table 1. Average ratios of indoor and outdoor PM1 and PM10 species. PM10_in/PM10_out PM1_in/PM1_out Average

St. dev.

Average

St. dev.

SO42-

58%

4%

60%

9%

NO3-

19%

4%

19%

9%

Oxalate

52%

7%

54%

9%

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Na+

28%

8%

77%

68%

NH4+

46%

6%

45%

8%

K+

37%

10%

63%

40%

Mg2+

23%

9%

37%

15%

Ca2+

31%

18%

55%

100%

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In the case in which the indoor sources are absent, the average indoor concentrations are lower

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than the outdoor concentrations for all the main species. The average ratio is given by the air

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exchange rate and particle losses during the air exchange and by the strength of the indoor particle

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sink. As all particle losses are size dependent, the compounds present in accumulation mode of the

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particle size distribution (sulfates, oxalates, and ammonium) have similar PM1 and PM10 indoor-

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to-outdoor ratios. Nitrates, although also present in accumulation mode in ambient aerosol, have

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much lower ratios in both size fractions. This result is caused by the dissociation of ammonium

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nitrate indoors, which is driven by a shift in thermodynamic equilibrium caused by nitric acid

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deposition on indoor walls3. The results are similar to those presented in Smolik et al. (2008)4,

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which were obtained at the same location. The differences between the two studies are probably

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caused by differences in meteorological conditions, different types of windows (changed between

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studies), and the installation of a cooker hood with a vent made directly through the wall, which

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changed the ventilation rates.

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Degreaser spray source tests (Using a spray)

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Besides other sources, the W5 degreaser spray was tested twice, first on September 1, 2014, at

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6:30 p.m., second on September 6, at 10:00 a.m. The first experiment is described in detail only as

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very similar results were observed in the second test. The compositional results changed

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substantially after using the degreaser spray (Fig. 2). IC results showed almost complete

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replacement of the NH4+ cation with an mono-ethanol aminium cation (MEA+) both in PM1 (Fig.

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2) and PM10 (Fig. S4). The MEA-containing degreaser W5 was applied 8 h after the beginning of

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sampling. However, almost no NH4+ cation was detected in the sample from this day. Hence, the

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replacement of the NH4+ cation happened not only in the airborne aerosol but also on aerosol

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particles that had been deposited on the filter before the degreaser was applied.

168 169 Before W5 usage

After W5 usage

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Figure 2. Relative equivalent ionic composition of PM1 indoor samples for days with no indoor

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source (21/08 – 31/08) and after using an MEA-containing cleaner (01/09-03/09).

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Fig. 2 contains ion chromatography results for PM1 filters on days when no indoor source was

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present and days after the first usage of the degreaser. (Fig. S4 contains similar data for PM10.)

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The results from the first day, when the degreaser was used, indicate almost complete

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transformation of NH4+ to MEA salts. Despite removing the degreaser from the surface and

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ventilating the room on September 2nd, the partial replacement of NH4+ is observed throughout the

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next few days. This finding seems even more striking if the high air exchange rate 1.26 air

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exchanges per hour is taken into account when the no ventilation experiment was performed27.

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However, the amount of MEA needed for complete replacement of ammonium in the indoor

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aerosol inside small kitchen with 28 m3 volume for 24 hours is actually very small – 2.5 mg of

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MEA. The other aerosol sources examined on September 3rd had no influence on this effect as they

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did not content any MEA.

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Ventilation is expected to cause an exponential decrease in the MEA concentration leading to a

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decrease in concentration by orders of magnitude in the indoor environment; thus, there must have

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remained a weak source of MEA. This source was a leftover on the kitchen surfaces after using a

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paper towel or MEA deposited elsewhere and the paper towel used for cleaning and disposed in

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the kitchen wastebasket. Another possibility is the slow release of MEA from the MEA organic

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salt present in the degreaser.

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Nitrate stabilization

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In addition to the replacement of ammonia in sulfate salts, the replacement of ammonia in

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ammonium nitrate was observed, leading to increased stability and increased concentrations of

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fine nitrates indoors. This conclusion was deduced from almost complete replacement of NH4+ in

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nitrates on September 1st and the differences in the average indoor/outdoor ratio of PM1 nitrate

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concentrations in the period without MEA influence (0.18) and the period with MEA influence

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(0.51). It appears that MEA partially stabilized fine nitrates in the aerosol phase. This effect is also

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shown in Fig. 2 (especially September 1st data) and (less visibly) in Figs. 3 and S5 (AMS data).

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This result agrees with that reported by Salo et al. (2011)11, who measured the evaporation rate of

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aminium nitrate compounds for various amines and found a lower rate of evaporation/dissociation

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for aminium salts of nitric acid relative to ammonium nitrate.

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Time-dependent data

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Using the procedure described above, MEA+ concentrations from the AMS spectra were

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determined. Figs. 3 and S5 shows the real concentrations of ammonium, nitrates, sulfates, and

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organics together with the concentration of MEA+ before and after degreaser usage with

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highlighted time of the degreaser usage. Clearly, the indoor MEA+ salt concentrations were

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elevated immediately after using the degreaser, and this effect persisted for several days in the first

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experiment and until the end of the second experiment (Fig. S5). The organic peak that appeared

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just after using the degreaser spray arose from the aerosolized degreaser solution. Its sharp

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decrease illustrates how standard short-term aerosol emissions behave indoors. In contrast, the

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MEA aerosol concentration remained almost constant until the window was opened before 10 a.m.

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on the next day. This persistence is not possible without interactions that are described above, i.e.

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the evaporation of MEA from a surface followed by the replacement of ammonia in salts present

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in the aerosol.

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The rate of ammonium sulfate transformation to aminium sulfate is strongly depending on

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particle phase as shown by Chu et al. 2017. In our case presence of water in particles may be

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supposed as indoor RH was between 40 and 75%, which favors faster transformation.

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A non-zero concentration of MEA+ was found outdoor via AMS analysis but not on the outdoor

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filter. Although part of the data may represent an artifact connected to the uncertainty of the MEA+

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concentration determination, we cannot exclude the possibility of MEA+ transport to the outdoor

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environment. The differences between the outdoor filter data, where no MEA+ was found, and the

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AMS data can be explained by the fact that the filter samplers are located 5 m from the building,

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which is much farther than the outdoor AMS inlet (0.5 m).

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After the windows were opened, the results significantly changed, but some trends remained. The ammonium appeared again, in salts, but part of the ammonium was still replaced by MEA+.

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Figure 3. Time series of recalculated AMS data indoor (top) and outdoor (bottom) environments

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from the first application of the degreaser at 18:30. At 9:45 on September 2nd, the windows were

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opened for 15 min.

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Figure 4. Mass size distribution of ionic species on September 2, 2015.

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Similar MEA behavior with the complete replacement of ammonium with indoor MEA+ was also

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observed via AMS during the second experiment when the room was closed throughout the entire

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weekend after the degreaser application at 10 a.m. on September 6th (Fig. S5).

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Cascade impactor results

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In addition to filter sampling and AMS measurement, the BLPI cascade impactor was used on

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September 2nd. An analysis of the samples, shown in Fig. 4, revealed partial replacement of the

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NH4+ cation with MEA+. The mass ratio of MEA+ to the NH4+ ions from impactor stages with

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geometric mean diameters of 0.08, 0.13, 0.20, 0.33, and 0.61 µm were equal to 3.50, 2.02, 1.40,

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0.46, and 0.12, respectively. The size dependence of this ratio, regardless of any uncertainty caused

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by the incomplete separation of the ammonium and MEA+ peaks especially for low values of the

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ratio, clearly shows that the rate of replacement was higher for smaller particles. This finding

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strongly supports the conclusion that the transformation occurred in the aerosol phase and was

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limited by the available surface area.

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Instruments intercomparisons

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To confirm quantitative agreement between the filter samples, impactor samples, and AMS data,

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the approximation of PM1 on the impactor (impactor stages 1-6, stage 6 upper cut diameter of 0.86

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µm) and AMS (AMS total, CE= 0.7 was applied here, see Talbot et al. 201626) were calculated for

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comparison with indoor PM1 filter results on September 2nd.

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The comparison of the data is shown in Table 2 for the major species.

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Table 2. Comparison of concentrations of PM1 aerosol species for different instruments [µg/m3] SO42Leckel PM1 1.53 impactor 1.52 AMS 1.61

NO30.22 0.16 0.23

NH4+ 0.29 0.53 0.19

MEA 0.82 0.26 0.49

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In general, a good agreement was found for sulfates and nitrates. However, MEA+

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concentrations higher than the ammonium cation concentrations were found on the filter, while

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the opposite was true for the cascade impactor. There are two possible causes that have acted in

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conjunction. First, MEA, similar to other organics, have been adsorbed onto the quartz fiber filter;

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thus, part of the analyzed MEA have come from a gas phase. This effect can be deduced from the

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backup filter analysis used for the PM1 filters in which MEA concentrations were found (1-3% of

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the amount found on the front filter), with the maximum on September 1st. Second, the ammonium

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salts already captured on the filter could have reacted with the MEA in the gas phase and increased

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the MEA salt content on the filter. This mechanism could apply to a lesser extent with the impactor

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samples, but only the particles in the upper layer can directly react with the gaseous phase as was

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observed on the first sampling date when the MEA cleaner was used. This transformation does not

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occur so much on the cascade impactor samples because they are less exposed to the gaseous phase

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relative to particles deposited on a quartz fiber filter. This is also supported by comparison of

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equivalent sum of ammonium and MEA+ for PM1 (30 neqv/m3) and impactor (34 neqv/m3) results

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that further support this explanation differing within experimental uncertainty. The concentration

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of MEA found by AMS was in between the filter and the impactor data. The lowest ammonium

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concentration was found using AMS and may be partially artifactual because of the complex

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corrections applied during the ammonium determination, the indoor environment, and naturally

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similar MEA fragments.

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Implications

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The use of MEA and other less volatile amine-containing mixtures in our homes and other indoor

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environments (similar data were found repeatedly in a machinery workshop) significantly changes

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the chemical composition of indoor aerosols. These changes alter people’s daily interactions with

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amines, exposing them to various aminium salts that may have unexpected consequences for

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human health. Moreover, the use of MEA indoors also stabilizes nitrates in the aerosol phase and

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consequently increases the nitrate exposure to people. The rather insignificant effects of MEA

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exposure for the general population can be multiplied for professionals working with such

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substances e.g. in restaurants. Therefore, studies on the toxicology of aminium salts, especially

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aminium sulfates and nitrates, on human lungs are needed.

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Supporting Information. Text and Figures S1-S3 (PDF)

294 295

Corresponding Author

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*[email protected]

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ACKNOWLEDGMENT

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The authors acknowledge support of this work by the European Union Seventh Framework

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Programme (FP7/2007e2013) under grant agreement No. 315760 HEXACOMM.

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SUPPORTING INFORMATION AVAILABLE 

301 302

C-ToF-AMS procedure description for MEA concentration determination including fragmentation table corrections



303 304

Relative equivalent ionic composition of PM10 indoor samples before and after using an MEA-containing degreaser

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AMS I/O data from the second experiment with MEA containing degreaser

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I/O EC/OC data from both experiments

307 308

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