Atmospheric Environment 297 (2023) 119598

Contents lists available at ScienceDirect

Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

A Modelling Study of Indoor Air Chemistry: The Surface Interactions of

Ozone and Hydrogen Peroxide
Toby J. Carter a , Dustin G. Poppendieck b , David Shaw a , Nicola Carslaw a ,∗
a
Department of Environment and Geography, University of York, Wentworth Way, York, YO10 5NG, United Kingdom
b
The University of Texas at Austin, Austin, TX 78712, United States of America

HIGHLIGHTS

• Over 90% of indoor O3 and H2 O2 deposits onto indoor surfaces.

• Bedroom environments remove more O3 and H2 O2 than kitchens and offices.
• Deposition of O3 increases indoor aldehyde concentrations.
• Surface reactivity should be accounted for when designing indoor air studies.

ARTICLE INFO ABSTRACT

Dataset link: https://doi.org/10.15124/f62de4 Indoor surfaces play a key role in indoor chemistry, including modification of indoor oxidant concentrations.
17-f8e8-4696-823c-fcbddecf150c This study utilises the INdoor CHEmical Model in Python (INCHEM-Py) to investigate the impact of surface
Keywords: transformations and their impact on indoor gas-phase chemistry. INCHEM-Py has been developed to simulate
Surface interactions the surface deposition of ozone and hydrogen peroxide onto nine and six individual surfaces respectively in a
Ozone typical bedroom, kitchen and office for normal indoor concentrations in the absence of household activities.
Hydrogen peroxide The results show that 91 to 96% of these oxidants are deposited onto indoor surfaces under our simulated
Indoor air quality conditions. In the bedroom, 38 to 44% of indoor ozone and hydrogen peroxide is deposited onto soft fabric
Deposition surfaces, with 41 to 54% of ozone deposition occurring on plastic surfaces in the kitchen and office. Total
Indoor air chemistry model indoor concentrations of straight-chained aldehydes (C1 -C10 ) ranged from ≈ 4 to 5 ppb, with nonanal having
the highest individual concentration (1.7, 1.6 and 1.5 ppb in the bedroom, kitchen and office respectively),
primarily as a result of emissions from plastics following ozone deposition. Aldehyde concentrations following
hydrogen peroxide deposition were often less than 0.01 ppb. Understanding how reactions and deposition on
different indoor surfaces impact indoor air chemistry will enable internal surface selection with a view to
improving overall indoor air quality.

1. Introduction secondary pollutants, some of which are harmful to human health (Nør-
gaard et al., 2014).
The recent COVID-19 pandemic has highlighted the need for healthy The impact of internal surfaces on indoor gas-phase chemistry is
indoor environments and the public is much more aware of the benefits
an increasingly important area of focus (Ault et al., 2020). There are
of good indoor air quality. This is important as people spend approx-
a wide range of surfaces indoors, such as carpets, wooden flooring,
imately 90% of their time indoors (Klepeis et al., 2001), whether at
home, at work, or commuting between the two. painted walls, and also the human surface (skin), which can act as both
Sources of indoor pollutants originate from a variety of household sinks and sources of indoor air pollutants (Fischer et al., 2013; Hodgson
activities, including cooking (Kang et al., 2019) and cleaning (Carslaw et al., 1993; Cheng et al., 2015; Katsoyiannis et al., 2008).
et al., 2017; Carslaw and Shaw, 2022). Other notable sources include Indoor materials can emit pollutants either as primary emissions
candle burning (Bekö et al., 2013) and emissions from indoor sur- released directly from the surface, or as gas-phase transformation prod-
faces (Poppendieck et al., 2007b), which we will focus on in this ucts that are formed following a surface interaction. Primary emissions
study. These indoor pollutant sources release volatile organic com-
released directly from indoor surfaces and building materials include a
pounds (VOCs), which can react with oxidants in the gas-phase to form

∗ Corresponding author.
E-mail address: [email protected] (N. Carslaw).

https://doi.org/10.1016/j.atmosenv.2023.119598
Received 12 October 2022; Received in revised form 6 January 2023; Accepted 12 January 2023
Available online 14 January 2023
1352-2310/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Fig. 1. The chemical processes and transformations following deposition of oxidants on internal surfaces in the indoor environment.

wide array of chemical species, including carboxylic acids, aldehydes performed on young adults with an average age of 25 years. Acetone
and alcohols (Chin et al., 2019; Ruiz-Jimenez et al., 2022). Emission and acetic acid had the largest emission rate from skin, contributing
rates of species emitted directly from surfaces are highest for new mate- 16% and 19% of the total VOC emission respectively. The total VOC
rials, but can continue to produce pollutants as they get older (Morrison emission rate increased to 4450 μg hr−1 per person when ozone was
and Nazaroff, 2002). In 30 Korean apartment buildings, approximately present, suggesting that skin oxidation reactions were occurring and
60% of total indoor VOCs arose from flooring and paint materials (Shin contributing to the VOC emissions from the skin surface (Wang et al.,
and Jo, 2013). 2022a). Furthermore, Liu et al. (2021) discovered that products of
Secondary pollutants can also be formed following gas-phase surface ozone-skin lipid chemistry continued to contribute to measured VOC
interactions, whereby a chemical reaction (often oxidation) with the concentrations even in a home that had been empty for five days. This
surface instigates the release of secondary species. The emission rates indicates that surfaces act as sources and reservoirs of VOCs indoors
of these secondary pollutants are important to quantify indoors, as they and can have a considerable effect on indoor chemistry.
can be harmful to human health (Nazaroff and Weschler, 2004) and Ozone can deposit onto a range of materials and surfaces indoors,
include aldehydes and ketones (Wang and Morrison, 2006; Cheng et al., where there are higher surface to volume ratios compared to outdoor
2015; Poppendieck et al., 2007b; Katsoyiannis et al., 2008; Saltham- environments. The respective rate of deposition of an oxidant indoors,
mer, 2019; Destaillats et al., 2008), alkanes and alkenes (Hodgson et al., such as ozone, depends on the type of surface and how that affects
1993), aromatics and esters (Xiong et al., 2019), and secondary organic the transportation and uptake of the oxidant (Reiss et al., 1994).
aerosols (SOA) (Waring and Siegel, 2013). Wang and Morrison (2006) For example, fleecy surfaces, such as carpets, have a higher oxidant
found that indoor surfaces continue to produce secondary pollutants deposition velocity (Morrison and Nazaroff, 2000; Abbass et al., 2017)
over a long period of time, with 14-year old surfaces in a house still a than smoother surfaces, such as wood or concrete (Schripp et al., 2012;
source of secondary pollution. Poppendieck et al., 2007a; Lin and Hsu, 2015). Deposition velocities
Indoor surfaces can therefore modify indoor air composition. The of ozone onto indoor materials have been previously reviewed (Kruza
composition of emitted species are surface dependent. Short and long- et al., 2017; Shen and Gao, 2018). There is often a wide variation
chain aldehydes are produced following ozone deposition onto soft in these values, where the age, nature of the material surface, ozone
fabrics (Cros et al., 2012; Lamble et al., 2011), whereas concrete concentrations and the measurement technique can all affect the de-
surfaces emit short, straight-chain and aromatic aldehydes and ketones position velocities that are determined through experiments (Lamble
following ozone deposition (Poppendieck et al., 2007b). Although, it et al., 2011; Wang and Morrison, 2006).
should be noted that these were the measured chemicals from the ex- Hydrogen peroxide (H2 O2 ) can also play a role in indoor surface
perimental studies. These surfaces likely emit other chemicals, but these deposition (Zhou et al., 2020; Poppendieck et al., 2021). Often used as
studies were limited by the instrumentation and quantificational meth- a cleaning agent, hydrogen peroxide can photolyse to form hydroxyl
ods. Fig. 1 shows the surface interactions taking place in a standard radicals (OH) (Kahan et al., 2012; Zhou et al., 2020), which drive in-
home setting. door gas-phase chemistry. OH chemistry often dominates the gas-phase
Skin can be an important contributor to indoor gas-phase chem- chemistry of indoor environments due to its high reactivity (Waring and
istry, particularly in crowded spaces. Wang et al. (2022a) undertook Wells, 2015; Carslaw et al., 2017).
a study of VOC emission rates from human skin, measuring a total Poppendieck et al. (2021) determined the surface deposition veloc-
VOC emission rate of 1150 μg hr−1 per person. This experiment was ities of hydrogen peroxide onto a range of common indoor surfaces,

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T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

including carpets and concrete and the consequent emissions of surface- deposition velocity of species i (cm s−1 ), A represents the internal
formed species. Hydrogen peroxide deposition velocities which were surface area (cm2 ) and V is the total volume of the indoor environment
higher (> 200 cm hr−1 ), were found to be more sustained, compared (cm3 ).
to similar ozone deposition velocities, which were found to decay over This study focuses on the final term in Eq. (1), and in particular,
time. However, over a 6-hr period of hydrogen peroxide exposure to incorporates deposition of ozone and hydrogen peroxide onto internal
indoor surfaces, less than 2 mg m−2 of secondary pollutants were surfaces and the resulting emissions of secondary pollutants from those
emitted, lower than for ozone exposure onto similar surfaces, which surfaces. Whilst the ozone deposition and resulting emissions are an
emitted between 1 and 20 mg m−2 for wall coverings and flooring extension of the work by Kruza et al. (2017), the hydrogen peroxide
over 36 h (Poppendieck et al., 2021, 2007b). These hydrogen peroxide treatment is a new addition to INCHEM-Py.
deposition velocities however were determined from extremely high
concentrations that may have different mechanisms than for ambient
2.2. Development of the model
concentrations.
There has, to date, been little focus on how surface deposition
The first order loss rate of ozone (F sO ) and hydrogen peroxide
of hydrogen peroxide and subsequent surface interactions affect the 3
indoor air chemistry. In fact, there is currently little experimental data (F sH O ) to a surface (in s−1 ) can be calculated using Eq. (2) and Eq. (3)
2 2
evaluating the impact of surface deposition on indoor air chemistry respectively (Kruza et al., 2017).
other than ozone. Therefore, this study uses experimental data on sur- 𝐴
𝐹𝑠O = 𝜈𝑑O (2)
face deposition of ozone and hydrogen peroxide, as well as information 3 3 𝑉
relating to the extent and composition of indoor surfaces in three
𝐴
different indoor micro-environments, to improve an existing model for 𝐹𝑠H = 𝜈𝑑H (3)
2 O2 2 O2 𝑉
indoor air chemistry. We use the model to investigate the interaction of
these two oxidants with internal surfaces and in so doing, gain a better 𝜈 dO3 and 𝜈 dH2 O2 represent the surface deposition velocities of ozone
understanding of the consequent impacts on indoor air chemistry. and hydrogen peroxide onto a material respectively (cm s−1 ). Fol-
lowing an interaction at the surface, the emission rate, Ei (molecule
2. Methods cm−3 s−1 ), of a secondary pollutant (species i), can be calculated
using Eq. (4) and Eq. (5) for ozone and hydrogen peroxide deposition
2.1. The INCHEM-Py model respectively (Morrison and Nazaroff, 2002; Kruza et al., 2017).
𝐴𝜈𝑑O 𝑌𝑖 𝐶O3
3
This study has been conducted using the INCHEM-Py model. 𝐸𝑖 = (4)
𝑉
INCHEM-Py is a detailed, chemical box model which predicts temporal
concentrations of indoor air pollutant species (Shaw and Carslaw, 𝐴𝜈𝑑H 𝑌𝑖 𝐶H2 O2
2 O2
𝐸𝑖 = (5)
2021). INCHEM-Py uses the near-explicit Master Chemical Mechanism 𝑉
(MCM) v3.3.1 (http://mcm.york.ac.uk) as a mechanistic and kinetic In Eqs. (4) and (5), Yi is the production yield of species i emitted from
dictionary of the degradation of 143 gas-phase VOCs and contains over a given surface (dimensionless) and will arise from a combination of
20,000 reactions (Jenkin et al., 1997) and approximately 6,000 species. reactions with, or displacement from, the surface. C O3 and C H2 O2 are
Updates to the original MCM include degradation schemes for 𝛼- and 𝛽- the concentrations of indoor ozone and hydrogen peroxide respectively
pinene and non-aromatic VOCs (Saunders et al., 2003), aromatics (Bloss (molecule cm−3 ).
et al., 2005; Jenkin et al., 2003), 𝛽-caryophyllene (Jenkin et al., 2012)
and isoprene (Jenkin et al., 2015).
2.3. Oxidant deposition
The MCM does not consider lumping nor utilise surrogate species.
Degradation mechanisms are initiated by the reaction of a VOC with
ozone (Jenkin et al., 2020), OH (Jenkin et al., 2018), nitrate (NO3 ) For this work, we have considered ozone deposition onto nine
radicals (Jenkin et al., 2019) and photolysis where relevant. These surfaces and hydrogen peroxide deposition onto six surfaces, based on
initial processes produce hydroperoxy (HO2 ), organic peroxy (RO2 ), available literature. The range of deposition velocities of ozone (Saber-
alkoxy (RO) and Criegee (R’R"COO) radicals as intermediate species, sky et al., 1973; Lin and Hsu, 2015; Klenø et al., 2001; Grøntoft, 2002;
which themselves react in a further series of reactions until carbon Abbass et al., 2017; Gall et al., 2013; Tamás et al., 2006; Cros et al.,
dioxide (CO2 ) and water (H2 O) are produced (Jenkin et al., 1997). 2012; Coleman et al., 2008; Ye et al., 2020; Lamble et al., 2011; Rim
INCHEM-Py also includes terms for indoor photolysis (Wang et al., et al., 2016; Poppendieck et al., 2007a; Wang and Morrison, 2010,
2022b), indoor–outdoor air change, chlorine chemistry (Wong et al., 2006; Nicolas et al., 2007; Morrison and Nazaroff, 2000; Fadeyi et al.,
2017) and secondary organic aerosol (SOA) formation for three terpene 2013; Yao et al., 2020; Di et al., 2017; Rai et al., 2014; Fischer et al.,
species (Kruza et al., 2020; Carslaw et al., 2012). The operational 2013; Wisthaler and Weschler, 2010; Schripp et al., 2012; Mueller
working of the INCHEM-Py model is explained in Shaw and Carslaw et al., 1973; Cox and Penkett, 1972; Grøntoft and Raychaudhuri, 2004;
(2021). Simmons and Colbeck, 1990; Cano-Ruiz et al., 1993) and hydrogen
INCHEM-Py assumes a well mixed, spatial environment and predicts peroxide (Poppendieck et al., 2021) are shown in Fig. 2 and Fig. 3
indoor gas-phase species’ concentrations (C𝑖 ) over time by solving a respectively. For the model simulations, the median deposition velocity
series of coupled and stiff ordinary differential equations of the form: value calculated was utilised.
𝑑𝐶𝑖 ∑ ( )
𝐴
= 𝑅𝑖𝑗 + (𝜆𝑟 𝐶𝑖,𝑜𝑢𝑡 − 𝜆𝑟 𝐶𝑖 ) − 𝜈𝑑𝑖 𝐶𝑖 (1)
𝑑𝑡 𝑉 2.4. Production yields of species from surfaces
where the first term on the right represents the sum of the rates of
reaction involving species i with species j in the gas or particle phase. The production yields of species emitted from a range of surfaces as
The second term is the indoor–outdoor change of species i, where 𝜆r is a result of ozone and hydrogen peroxide deposition has been collated
the air change rate (ACR) (s−1 ), Ci,out is the outdoor concentration of from a range of literature (Wang and Morrison, 2010; Weschler et al.,
species i (molecule cm−3 ) and Ci is the indoor concentration of species 2007; Kruza and Carslaw, 2019; Cheng et al., 2015; Poppendieck et al.,
i (molecule cm−3 ). The final term relates to the irreversible surface 2007b, 2021; Coleman et al., 2008), and are incorporated into the
deposition of species onto indoor materials, where, 𝜈 di represents the model (Table S1 and S2 in the Supporting Information).

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T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Fig. 2. The distribution of reported ozone deposition velocities onto a range of indoor surfaces, including the median, the upper (75% percentile) and lower (25% percentile)
quartiles, the upper whisker (Q3 + 1.5*IQR) and the lower whisker (Q1 − 1.5*IQR) in cm s−1 . Values which fell outside the range of the upper and lower whiskers are also
included in the plot as small circles. n denotes the total number of measurements per surface. m denotes the total number of studies consulted.

Fig. 3. The distribution of reported hydrogen peroxide deposition velocities onto a range of indoor surfaces, including the median, the upper (75% percentile) and lower (25%
percentile) quartiles, the upper whisker (Q3 + 1.5*IQR) and the lower whisker (Q1 − 1.5*IQR) in cm s−1 . n denotes the total number of measurements per surface. m denotes
the total number of studies consulted.

2.5. Indoor spatial representation indoor surface deposition. The total surface area of each specific sur-
face is divided by the total volume of the indoor space to yield a
surface-specific surface area-to-volume ratio.
It is important to consider the surface area of a material in the Surface-specific area-to-volume ratios have been defined for a range
indoor environment, to better understand how oxidant sorption onto of common indoor surfaces, using a comprehensive study which desig-
materials and the transformations that subsequently occur impact in- nated spatial representation in the indoor environment by Manuja et al.
door air quality (Manuja et al., 2019; Ye et al., 2020). Recent stud- (2019). The study measured the total surface area of common indoor
ies (Manuja et al., 2019; Hodgson et al., 2004; Morgan and Cruick- materials in bedrooms, kitchens and work offices. The surface areas of
shank, 2014) provide typical room sizes and surface area compositions. each material were then averaged for each room (Table S3, S4 and S5).
These studies provide the basis for predicting how replacing an indoor The total volumes of the bedroom, kitchen and office with their
surface, for example a wooden floor, with an ’emission-free’ or ’VOC specific contents were 29, 25 and 35 m3 respectively based on those
friendly’ alternative, will affect deposition, emissions and subsequently calculated by Manuja et al. (2019). It was assumed that two adults
would be present in the bedroom, one adult would be present in the
the impact on the overall indoor environment (Cheng et al., 2015).
kitchen and three adults present in the office. Adults are assumed
Surfaces have been included in the INCHEM-Py model, and are to have ≈ 2 m2 of skin surface (Fischer et al., 2013). Clothing is
categorised by material. For example, fleecy carpets and cushioned assumed to contribute to the ‘skin’ surface, as fabrics soiled with
sofas are represented under the ’Soft Fabric’ category, whereas wooden secreted skin oils and flakes have a similar ozone deposition velocity
door frames and floors are assumed to be wooden surfaces. Most and retrospective secondary pollutant emission yields to bare skin Rai
household items can then be considered in the model when analysing et al. (2014), Lakey et al. (2017), Kruza and Carslaw (2019).

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T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

2.6. Model parameterisation (2017) also included surface specific deposition rates. This study has
yielded comparable results, with 94, 91 and 94% of ozone deposited
The model was initialised to simulate a typical apartment located in onto indoor surfaces in the bedroom, kitchen and office respectively.
suburban London. The temperature of the apartment was assumed to In addition, 96, 94 and 95% of indoor hydrogen peroxide is deposited
be 19.9 ◦ C and the relative humidity 53.8%, based on the mean values onto indoor surfaces in the bedroom, kitchen and office respectively,
from extensive monitoring of air quality in homes across the United with these model simulations using an air change rate of 0.5 hr−1 . These
Kingdom (Ministry of Housing, Communities & Local Government (UK values reinforce the idea that indoor surfaces provide a key role in the
Government), 2019). removal of ozone and hydrogen peroxide in the indoor environment.
Nazaroff (2021) undertook a comprehensive literature review of air For an air change rate of 2.0 hr−1 , the total deposition of indoor
change rates (ACR) in residential properties in Europe, North America ozone and hydrogen peroxide onto surfaces was 78 and 87% in the
and central Asia, and concluded that an appropriate median value of air bedroom, 78 and 81% in the kitchen, and 86 and 84% in the office
change rates in homes is 0.5 hr−1 , with 95% of residential air change respectively. Under these higher air change rate conditions, more of
rates existing within a 0.125 and 2.0 hr−1 range. These findings were the oxidant migrates to the outdoor environment before reacting with
used to bound the ACR values in the model simulations. an indoor surface. Fig. 4 provides a breakdown of the percentage of the
Indoor photolysis rates are incorporated into the model and include total deposition of ozone and hydrogen peroxide onto different indoor
the impact of indoor artificial light plus attenuated sunlight (Shaw and surfaces in the different study locations. The surface area percentage of
Carslaw, 2021; Wang et al., 2022b). For these simulations, incandescent each material in each room is also given in Fig. 4.
lighting is used and the windows assumed to admit sunlight with The importance of individual surfaces varies between rooms. For
a wavelength down to 308 nm (’Glass C’ in Wang et al. (2022b)). instance, soft fabric materials are responsible for 38% of the total
The indoor lights were turned on at 07:00 GMT and switched off at ozone deposition in the bedroom, yet represents approximately 21%
19:00 GMT. The date was assumed to be the 21st June and the latitude of the total surface area in the bedroom. Meanwhile, painted surfaces,
is set to that of central London, 51.5 ◦ N. which represents >45% of the bedroom surface area only contributes
The outdoor concentrations of key atmospheric species includ- to 17% of the total ozone deposition. In the kitchen and the office, soft
ing OH, HO2 and the methylperoxy radical (CH3 O2 ), are defined in fabrics represents approximately 3% and 8% of the total surface area
the model by diurnal profiles determined by the solar zenith an- respectively. This leads to soft fabric surfaces being accountable for 7%
gle (Carslaw, 2007). The outdoor concentrations of O3 , NO (nitric and 11% of the total ozone deposition in these individual rooms. Plastic
oxide) and NO2 (nitrogen dioxide) were based on measurements in surfaces in the kitchen and the office are the most important ozone
suburban London over the course of three months and follow a diurnal sink in these spaces, whilst metal, concrete, paper and glass surfaces
profile (Shaw and Carslaw, 2021; EEA, 2018). The average outdoor are responsible for < 1% of ozone deposition, owing to small surface
concentrations for these species are provided in Table S6. areas and low ozone deposition velocities. Despite a low overall surface
The MCM is specifically designed to be an outdoor atmospheric area, deposition of ozone onto skin was the second biggest deposition
degradation mechanism. Additional mechanisms for key indoor species sink in all three rooms, indicating the impact of occupants on ozone
not present in the MCM have been developed and incorporated in deposition indoors.
the INCHEM-Py model utilising experimental rate coefficients and The rate of deposition of ozone onto indoor surfaces changes with
oxidation pathways from literature. Additional degradation schemes room type and surface area of a material (Weschler, 2000). For ex-
in the INCHEM-Py model include; chlorine chemistry (Xue et al., ample, the rate of deposition of ozone onto soft fabrics decreases
2015; Wong et al., 2017; Wang et al., 2020) and oxidation schemes by a factor of approximately 6 when moving from the bedroom to
for linalool (Carslaw et al., 2017), 2,5-dimethylbenzaldehyde (Clifford the kitchen, as there are fewer soft surfaces in the latter. For plastic
and Wenger, 2006; Jenkin et al., 1997), 2-nonenal (Gao et al., 2009; surfaces, the rate of ozone deposition in an office is approximately 14
Gaona Colmán et al., 2017; Kerdouci et al., 2012), octanal, nonanal, times more than the deposition rate in the bedroom. Painted surfaces
decanal, 𝛥3-carene, camphene, and lactic acid (Shaw and Carslaw, have a more comparable impact in different rooms, where the total
2021). The model also includes gas-to-particle partitioning for three ozone deposition only fluctuates by approximately 10% between the
monoterpenes; limonene, 𝛼-pinene and 𝛽-pinene (Carslaw et al., 2012). office and the bedroom and kitchen.
For the inclusion of humans in the model, breath emissions have Fig. 4 shows that indoor hydrogen peroxide deposition shows some
also been added, using data from Kruza and Carslaw (2019), tailored similarities to ozone deposition. Soft fabrics are the most important
according to how many adults are assumed to be present in each material in the bedroom, accounting for 44% of the hydrogen peroxide
indoor space. These additional mechanisms have all been developed deposition. However, unlike with ozone, hydrogen peroxide deposits
as ongoing improvements of INCHEM-Py (Shaw and Carslaw, 2021). predominantly onto painted surfaces in the kitchen (40%) and the
The model contains the concentrations of 110 outdoor VOCs and office (32%). There is no data for hydrogen peroxide deposition onto
other atmospheric species which find their way indoors through ven- plastic, glass and skin surfaces. Metallic surfaces have a larger propor-
tilation (Shaw and Carslaw, 2021). The outdoor hydrogen peroxide tion of hydrogen peroxide uptake than ozone in the kitchen and office,
concentration in the model is assumed to be 1.3 ppb, based on He contributing to 15% of hydrogen peroxide uptake in both rooms. In
et al. (2010). The outdoor VOC concentrations were sourced from absolute terms, the rates at which hydrogen peroxide deposits onto
experimental literature (Uchiyama et al., 2015; Baudic et al., 2016; Lü indoor surfaces are lower than for ozone, primarily due to the low
et al., 2006; Mentese and Bas, 2020; Bari and Kindzierski, 2018; Sturaro indoor hydrogen peroxide concentration (averaged at 0.06 ppb over
et al., 2010; Bari et al., 2016; Hakola et al., 2009; Brickus et al., 1998; the three rooms). For hydrogen peroxide, the deposition rates are more
Vichi et al., 2016; Liu et al., 2018; Gallego et al., 2016; Hellén et al., closely aligned to the individual surface areas than ozone, given the
2018; Dlugokencky, 2022; EEA, 2018) and are given in Table S7. deposition velocities vary over a smaller range than for ozone.
The average concentrations of key indoor species during the day
3. Results (7 am–7 pm) are reported in Table 1, for scenarios with no deposition
(baseline) and then also assuming empty or occupied (two people in the
3.1. The uptake of ozone and hydrogen peroxide on indoor surfaces bedroom, one in the kitchen, three in the office) rooms. The occupied
and unoccupied simulations include deposition for both ozone and
Kruza et al. (2017) found that 85% of the ozone present indoors was hydrogen peroxide.
deposited onto indoor surfaces in their simulated apartment, conducted These modelled concentrations (including deposition) can be com-
with an air change rate of 0.76 hr−1 . Similarly to this study, Kruza et al. pared to experimental studies which measured indoor aldehyde species.

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T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Fig. 4. The percentage distribution of ozone and hydrogen peroxide deposition by surface for the studied rooms. The total percentage surface area of each material in each room
are also included.

Table 1
The average indoor concentration for a range of species in a bedroom, kitchen and office during the day, whilst the lights are on (7am to 7pm). The units for the concentration
of OH is molecule cm−3 , the units for the concentration of HO2 and RO2 are ppt and the units for the rest of the species are given in ppb.
Species Baseline Unoccupied Occupied
Bedroom Kitchen Office Bedroom Kitchen Office Bedroom Kitchen Office
OH 1.1 × 106 1.2 × 106 9.9 × 105 8.9 × 105 9.7 × 105 8.6 × 105 7.4 × 105 9.0 × 105 6.1 × 105
HO2 3.6 3.7 3.5 1.0 1.2 0.80 1.3 1.3 1.2
RO2 5.8 5.7 5.9 1.6 1.9 1.2 1.7 1.9 1.5
O3 26.6 27.0 26.1 2.5 3.5 1.5 1.8 2.7 1.2
NO 0.40 0.44 0.36 2.1 1.9 2.5 2.2 2.1 2.4
NO2 0.76 0.88 0.65 0.59 0.70 0.45 0.55 0.66 0.44
Formaldehyde 0.38 0.45 0.31 0.62 0.79 0.47 0.63 0.77 0.53
Acetaldehyde 0.47 0.54 0.41 0.68 0.92 0.58 0.61 0.82 0.53
Propanal 0.13 0.15 0.12 0.25 0.33 0.18 0.21 0.28 0.16
Butanal < 0.01 < 0.01 < 0.01 0.11 0.19 0.09 0.08 0.15 0.07
Pentanal 0.03 0.03 0.03 0.13 0.18 0.10 0.10 0.14 0.08
Hexanal 0.03 0.04 0.03 0.19 0.17 0.11 0.14 0.14 0.09
Heptanal 0.02 0.03 0.02 0.07 0.06 0.06 0.05 0.05 0.05
Octanal 0.08 0.08 0.08 0.24 0.21 0.22 0.20 0.18 0.20
Nonanal 0.47 0.46 0.48 2.0 1.7 1.6 1.8 1.6 1.5
Decanal 0.13 0.13 0.13 0.66 0.73 0.73 0.75 0.77 0.82
4-OPA < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 0.08 0.08 0.06

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T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Fig. 5. The concentrations of straight-chained aldehyde species and 4-oxopentanal (4-OPA) in an office with and without oxidant deposition onto surfaces.

Uchiyama et al. (2015) reported concentrations of 0.16 ppb, 0.25 ppb, lack information on the health effects of some of these species and they
1.4 ppb and 0.40 ppb for heptanal, octanal, nonanal and decanal re- are unlikely to exert an equal influence on human health. However,
spectively in Japanese homes. Our results (see Table 1) are comparable it does provide a guide to the harmful concentrations that could be
to these measured values, although our heptanal concentrations are attained indoors under different conditions.
slightly lower than measured. Indoor formaldehyde (19.2 ppb) and For the three modelled rooms (with both ozone and hydrogen
acetaldehyde (10.8 ppb) measurements from Uchiyama et al. (2015) peroxide deposition included), the SPCPmod values were 5.8, 6.7 and
however, were much higher than our results (factor of > 24 and > 11 4.8 ppb for the bedroom, kitchen and the office respectively, averaged
over a full day. The concentrations of hexanal, octanal and nonanal
higher respectively), although these are more likely to be influenced by
were found to be highest in the bedroom (0.12 ppb, 0.19 ppb and 1.72
human activities (such as cooking and cleaning) that we do not consider
ppb), whereas the concentration of decanal was found to be highest in
here. We acknowledge that, by ignoring these primary emissions for
the office (0.77 ppb). There were assumed to be three people present
this study, our formaldehyde exposure levels are underestimated. These
in the office, giving skin a higher surface to volume ratio (Weschler
measurement studies have been carried out in various homes, each et al., 2007) than the other rooms, resulting in a higher decanal
containing different materials and hence surface properties. concentration. The rest of the species present in Eq. (6) were found
to have the highest concentrations in the kitchen.
3.2. Secondary pollutants from surface interactions
3.3. Monitoring individual exposure to indoor air pollution
Following oxidant deposition onto indoor surfaces in an occupied
office, there was an increase in secondary pollutants, particularly in Using our results, we have considered a typical day spent indoors,
straight-chained aldehyde species compared to simulations with no to determine the exposure to specific indoor air pollutants that might
be experienced (Fig. 6). We assumed that, on a typical day, a person
deposition (Fig. 5). Following ozone deposition (for an average ozone
will spend from: 00:00–07:00 h in the bedroom, 07:00–08:00 h in
concentration of 1.16 ppb), nonanal had the highest concentration
the kitchen, 08:00–08:30 h outdoors (walking to the office), 08:30–
(1.52 ppb), where emissions from plastic surfaces contributed the most.
12:00 h in the office, 12:00–13:00 h outdoors (lunch break outside),
The concentration of decanal increased by ≈500% following ozone de-
13:00–17:00 h in the office, 17:00–17:30 h walking home outdoors,
position onto all available surfaces. However, the percentage change in 17:30–19:00 h in the kitchen, 19:00–22:00 h in the living room, then
most aldehyde concentrations following hydrogen peroxide deposition the rest of the day in the bedroom. It was assumed there were no high
(for an average hydrogen peroxide concentration of 0.06 ppb) was concentration activities such as cooking and cleaning. We assumed that
small (≈2%) and some concentrations even decreased slightly (≈−1% the bedroom was a proxy for the living area given we did not study
change from the baseline). this particular micro-environment, but it is likely to be dominated by
Surface deposition gives rise to numerous secondary pollutants, similar soft furnishings.
some of which are harmful to health. Carslaw and Shaw (2019) defined The concentrations of key indoor radical species varied throughout
a metric for comparing the potential health impacts of the secondary the day, depending on time and location. The highest concentrations
pollutants that arose under different indoor conditions, using the so- for pollutants tend to correspond with time spent outdoors, given
called ’Secondary Product Creation Potential (SPCP)’. This metric has that many of them are predominantly generated outdoors under our
been adapted to consider the different model simulations here and is simulated conditions (no cooking or cleaning). The highest indoor
defined as: concentration of OH was 1.1 × 106 molecule cm−3 at 7:58 am in the
kitchen. The OH concentration is driven by the reaction of NO with
⎛ [𝑇 𝑜𝑡𝑎𝑙 𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝑁𝑖𝑡𝑟𝑎𝑡𝑒𝑠] + [𝑃 𝐴𝑁𝑠] + [O3 ]+ ⎞ HO2 . NO concentrations are higher in the morning as it is generated
⎜ [𝐺𝑙𝑦𝑜𝑥𝑎𝑙] + [𝐹 𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒] + [𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒]+ ⎟ by rush-hour traffic from outdoors, which will ingress inside.
𝑆𝑃 𝐶𝑃mod =𝛴⎜ ⎟ Our results show that of our total pollutant exposure over the course
⎜ [𝑃 𝑟𝑜𝑝𝑎𝑛𝑎𝑙] + [𝐵𝑢𝑡𝑎𝑛𝑎𝑙] + [𝑃 𝑒𝑛𝑡𝑎𝑛𝑎𝑙] + [𝐻𝑒𝑥𝑎𝑛𝑎𝑙]+ ⎟
⎜ ⎟ of the day, 60% of OH, 81% of HO2 , 32% of O3 and 77% of NOx
⎝ [𝐻𝑒𝑝𝑡𝑎𝑛𝑎𝑙] + [𝑂𝑐𝑡𝑎𝑛𝑎𝑙] + [𝑁𝑜𝑛𝑎𝑛𝑎𝑙] + [𝐷𝑒𝑐𝑎𝑛𝑎𝑙] ⎠ happens indoors. Our highest exposure to OH (32%) and NOx (43%)
(6) is found in the office. Whereas, our highest exposure to HO2 (53%) is
found in the bedroom and living room, primarily due to the duration of
SPCPmod therefore provides the sum of the concentrations of potentially time spent in these rooms over the course of a day. The total pollutant
harmful pollutants that are formed under different model scenarios exposure (%) experienced in each micro-environment over the course
with units of ppb. This metric is a guideline value only, as we currently of the day is given in Table S8.

7
T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Fig. 6. The concentrations of OH (molecule cm−3 ), HO2 (ppt), O3 and NOx (ppb) a person may be exposed to throughout the course of a typical day. The red shading on the
graph indicates time spent in the bedroom, blue indicates time spent in the kitchen, green indicates time spent in the office, white indicates time spent outdoors and yellow
indicates time spent in the living room.

3.4. Surfaces for the future ozone nearly doubled under these conditions, owing to the lower ozone
deposition velocity of concrete, therefore, ozone will have a higher
The INCHEM-Py model has been used to explore whether replacing ambient indoor concentration if plastic is replaced by concrete.
individual surfaces can improve the indoor air quality. This is important
as we consider more eco-friendly and sustainable materials to replace
4. Conclusions
older, less environmentally beneficial surfaces in the future. In the past,
we selected environmentally friendly materials based on the primary
This study was undertaken to evaluate how indoor surfaces react
emission to indoor environments. This work shows that we need to
consider the combination of the primary emissions and secondary with oxidants to impact indoor air quality in a kitchen and bedroom
chemistry to evaluate the impact of material interactions on indoor air in a home environment and an office in a work environment. The
quality. Thus, understanding total emissions from all new materials will model results demonstrated that the importance of individual surfaces
help to inform decisions about which are best to use in different indoor varied between different rooms. The dominant surfaces often had a
environments. large product of deposition rate and surface area. Large unreactive
We note that, in our study, in the bedroom and kitchen, wooden surfaces and small reactive surfaces had minimal impact on modelled
surfaces drive emission rates of shorter-chained aldehyde species (C1 - concentrations. Further experiments focussing on surface deposition
C5 ) following oxidant deposition, compared to the other surfaces which of a wider range of oxidants and the respective production yields for
were present. Whereas, we found that soft fabric and plastic surfaces emitted species and for a range of surfaces, would be highly beneficial.
account for the increase in longer-chained aldehyde species (C6 -C10 ). This study has evaluated the exposure of indoor air pollution for a
Concrete surfaces had the lowest rate of production for the majority of person over the course of a day and the respective health implications.
the straight-chain aldehydes, primarily due its low surface-to-volume It was determined that whilst indoors, OH concentration during the
ratio. We also found that occupied rooms yielded an increase in the con- day was highest in the kitchen, whereas the HO2 concentration was
centration of decanal and 4-oxopentanal (4-OPA), which are notably highest early in the morning, in the bedroom. A modified value of
products of skin lipid ozonolysis (Weschler, 2016). the Secondary Product Creation Potential (SPCPmod ) was highest in the
We ran model simulations, replacing wooden surfaces in the bed- kitchen and lowest in the office, indicating greater total exposure to
room and the kitchen with concrete surfaces to determine the impact potentially harmful air pollutants in the kitchen than the bedroom and
on indoor air chemistry. In addition, the plastic surfaces in the office the office. However, in order to make these assessments more accurate,
were replaced with concrete surfaces. The percentage difference of we need more detailed information on the relative health impacts of
the concentration of straight-chained aldehydes and key indoor species the different species we have studied. This would help us to better
were then calculated. understand how changing surfaces impact on health, as changing a
When wooden materials are replaced by concrete equivalents in the surface will inevitably increase some concentrations, but reduce others.
bedroom and the kitchen respectively, most concentrations decreased:
formaldehyde (by −14% and −24%), acetaldehyde (−19% and −28%),
CRediT authorship contribution statement
propanal (−30% and −45%), butanal (−76% and −81%), pentanal
(−45% and −59%) and hexanal (−22% and −46%). Heptanal, octanal,
nonanal and decanal concentrations all increased, but by minimal Toby J. Carter: Methodology, Software, Validation, Formal analy-
amounts (≈1%). This material replacement produced little change in sis, Investigation, Data curation, Writing – original draft, Visualization.
radical concentrations in the bedroom and the kitchen. Dustin G. Poppendieck: Provision of experimental data (hydrogen
In the office, where plastic was replaced by concrete, the con- peroxide deposition velocities and surface emissions), Writing – re-
centration of short-chained aldehydes formaldehyde and propanal in- view & editing. David Shaw: Methodology, Software, Resources, Data
creased by 6% and 28% respectively, whereas octanal and decanal curation, Writing – review & editing. Nicola Carslaw: Conceptualiza-
concentrations decreased by 19% and 10% respectively. However, the tion, Methodology, Software, Validation, Writing – original draft, Writ-
concentrations of HO2 and RO2 both increased by ≈37%, indicating ing – review & editing, Supervision, Project administration, Funding
a wider perturbation to the indoor chemistry. The concentration of acquisition.

8
T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Declaration of competing interest Carslaw, N., 2007. A new detailed chemical model for indoor air pollution. Atmos.
Environ. 41 (6), 1164–1179. http://dx.doi.org/10.1016/j.atmosenv.2006.09.038.
Carslaw, N., Fletcher, L., Heard, D., Ingham, T., Walker, H., 2017. Significant OH
The authors declare that they have no known competing finan-
production under surface cleaning and air cleaning conditions: Impact on indoor
cial interests or personal relationships that could have appeared to air quality. Indoor Air 27 (6), 1091–1100. http://dx.doi.org/10.1111/ina.12394.
influence the work reported in this paper. Carslaw, N., Mota, T., Jenkin, M.E., Barley, M.H., McFiggans, G., 2012. A significant
role for nitrate and peroxide groups on indoor secondary organic aerosol. Environ.
Data availability Sci. Technol. 46 (17), 9290–9298. http://dx.doi.org/10.1021/es301350x.
Carslaw, N., Shaw, D., 2019. Secondary product creation potential (SPCP): A metric for
assessing the potential impact of indoor air pollution on human health. Environ.
Data from this project is available at https://doi.org/10.15124/ Sci. Process. Impacts 21 (8), 1313–1322. http://dx.doi.org/10.1039/c9em00140a.
f62de417-f8e8-4696-823c-fcbddecf150c, an online data repository Carslaw, N., Shaw, D., 2022. Modification of cleaning product formulations could
hosted by the University of York (Carter et al., 2023). improve indoor air quality. Indoor Air 32 (3), 1–13. http://dx.doi.org/10.1111/
ina.13021.
Carter, T.J., Poppendieck, D.G., Shaw, D., Carslaw, N., 2023. Dataset for a modelling
Acknowledgements
study of indoor air chemistry: The surface interactions of Ozone and hydrogen
peroxide. http://dx.doi.org/10.15124/f62de417-f8e8-4696-823c-fcbddecf150c.
This research is part of MOCCIE 3 (MOdelling Consortium for Chem- Cheng, Y.H., Lin, C.C., Hsu, S.C., 2015. Comparison of conventional and green building
istry of Indoor Environments), which has received funding from the materials in respect of VOC emissions and ozone impact on secondary carbonyl
Alfred P. Sloan Foundation to study Chemistry of Indoor Environments emissions. Build. Environ. 87, 274–282. http://dx.doi.org/10.1016/j.buildenv.2014.
12.025.
(CIE) (Grant Number: G-2020-13912). Conclusions reached or positions
Chin, K., Laguerre, A., Ramasubramanian, P., Pleshakov, D., Stephens, B., Gall, E.T.,
taken by researchers or other grantees represent the views of the 2019. Emerging investigator series: Primary emissions, ozone reactivity, and
grantees themselves and not those of the Alfred P. Sloan Foundation byproduct emissions from building insulation materials. Environ. Sci. Process.
or its trustees, officers, or staff. The hydrogen peroxide work was Impacts 21 (8), 1255–1267. http://dx.doi.org/10.1039/c9em00024k.
completed by Dr. Dustin Poppendieck when he was a postdoctoral re- Clifford, G.M., Wenger, J.C., 2006. Rate coefficients for the gas-phase reaction of
hydroxyl radicals with the dimethylbenzaldehydes. Int. J. Chem. Kinet. 38 (9),
searcher whilst at The University of Texas at Austin. Dustin is currently
563–569. http://dx.doi.org/10.1002/kin.20189.
working at the National Institute of Standards and Technology (NIST). Coleman, B.K., Destaillats, H., Hodgson, A.T., Nazaroff, W.W., 2008. Ozone consump-
We would like to acknowledge the assistance of Professor Linsey Marr tion and volatile byproduct formation from surface reactions with aircraft cabin
in providing more detailed information from the Manuja et al. (2019) materials and clothing fabrics. Atmos. Environ. 42 (4), 642–654. http://dx.doi.
paper. org/10.1016/j.atmosenv.2007.10.001.
Cox, R.A., Penkett, S.A., 1972. Effect of relative humidity on the disappearance of ozone
and sulphur dioxide in contained systems. Atmos. Environ. (1967) 6 (5), 365–368.
Appendix A. Supplementary data http://dx.doi.org/10.1016/0004-6981(72)90203-X.
Cros, C.J., Morrison, G.C., Siegel, J.A., Corsi, R.L., 2012. Long-term performance of
Supplementary material related to this article can be found online passive materials for removal of ozone from indoor air. Indoor Air 22 (1), 43–53.
at https://doi.org/10.1016/j.atmosenv.2023.119598. http://dx.doi.org/10.1111/j.1600-0668.2011.00734.x.
Destaillats, H., Maddalena, R.L., Singer, B.C., Hodgson, A.T., McKone, T.E., 2008. Indoor
pollutants emitted by office equipment: A review of reported data and information
References needs. Atmos. Environ. 42 (7), 1371–1388. http://dx.doi.org/10.1016/j.atmosenv.
2007.10.080.
Abbass, O.A., Sailor, D.J., Gall, E.T., 2017. Effect of fiber material on ozone removal Di, Y., Mo, J., Zhang, Y., Deng, J., 2017. Ozone deposition velocities on cotton clothing
and carbonyl production from carpets. Atmos. Environ. 148, 42–48. http://dx.doi. surface determined by the field and laboratory emission cell. Indoor Built Environ.
org/10.1016/j.atmosenv.2016.10.034. 26 (5), 631–641. http://dx.doi.org/10.1177/1420326X16628315.
Ault, A.P., Grassian, V.H., Carslaw, N., Collins, D.B., Destaillats, H., Don- Dlugokencky, E., 2022. NOAA/GML CH4 trends. URL https://gml.noaa.gov/webdata/
aldson, D.J., Farmer, D.K., Jimenez, J.L., McNeill, V.F., Morrison, G.C., ccgg/trends/ch4/ch4_mm_gl.txt (Date Accessed: March 2022).
O’Brien, R.E., Shiraiwa, M., Vance, M.E., Wells, J., Xiong, W., 2020. Indoor EEA, 2018. European Air Quality Portal. European Environment Agency, URL https:
surface chemistry: Developing a molecular picture of reactions on indoor in- //eeadmz1-cws-wp-air02.azurewebsites.net/ (Date Accessed: December 2021).
terfaces. Chem 6 (12), 3203–3218. http://dx.doi.org/10.1016/j.chempr.2020.08. Fadeyi, M.O., Weschler, C.J., Tham, K.W., Wu, W.Y., Sultan, Z.M., 2013. Impact
023, 10.1016/j.chempr.2020.08.023 https://linkinghub.elsevier.com/retrieve/pii/ of human presence on secondary organic aerosols derived from ozone-initiated
S2451929420304332. chemistry in a simulated office environment. Environ. Sci. Technol. 47 (8),
Bari, M.A., Kindzierski, W.B., 2018. Ambient volatile organic compounds (VOCs) in 3933–3941. http://dx.doi.org/10.1021/es3050828.
Calgary, Alberta: Sources and screening health risk assessment. Sci. Total Environ. Fischer, A., Ljungström, E., Langer, S., 2013. Ozone removal by occupants in a
631–632, 627–640. http://dx.doi.org/10.1016/j.scitotenv.2018.03.023. classroom. Atmos. Environ. 81, 11–17. http://dx.doi.org/10.1016/j.atmosenv.2013.
Bari, M.A., Kindzierski, W.B., Spink, D., 2016. Twelve-year trends in ambient concen- 08.054.
trations of volatile organic compounds in a community of the Alberta Oil Sands Gall, E., Darling, E., Siegel, J.A., Morrison, G.C., Corsi, R.L., 2013. Evaluation of three
Region, Canada. Environ. Int. 91, 40–50. http://dx.doi.org/10.1016/j.envint.2016. common green building materials for ozone removal, and primary and secondary
02.015. emissions of aldehydes. Atmos. Environ. 77, 910–918. http://dx.doi.org/10.1016/
Baudic, A., Gros, V., Sauvage, S., Locoge, N., Sanchez, O., Sarda-Estève, R., Kalo- j.atmosenv.2013.06.014.
gridis, C., Petit, J.E., Bonnaire, N., Baisnée, D., Favez, O., Albinet, A., Sciare, J., Gallego, E., Roca, F.J., Perales, J.F., Guardino, X., Gadea, E., Garrote, P., 2016. Impact
Bonsang, B., 2016. Seasonal variability and source apportionment of volatile of formaldehyde and VOCs from waste treatment plants upon the ambient air
organic compounds (VOCs) in the Paris megacity (France). Atmos. Chem. Phys. nearby an urban area (Spain). Sci. Total Environ. 568, 369–380. http://dx.doi.
16 (18), 11961–11989. http://dx.doi.org/10.5194/acp-16-11961-2016. org/10.1016/j.scitotenv.2016.06.007.
Bekö, G., Weschler, C.J., Wierzbicka, A., Karottki, D.G., Toftum, J., Loft, S., Clausen, G., Gao, T., Andino, J.M., Rivera, C.C., Márquez, M.F., 2009. Rate constants of the gas-
2013. Ultrafine particles: Exposure and source apportionment in 56 Danish phase reactions of OH radicals with trans -2-hexenal, trans -2-octenal, and trans
homes. Environ. Sci. Technol. 47 (18), 10240–10248. http://dx.doi.org/10.1021/ -2-nonenal. Int. J. Chem. Kinet. 41 (7), 483–489. http://dx.doi.org/10.1002/kin.
es402429h. 20424.
Bloss, C., Wagner, V., Jenkin, M.E., Volkamer, R., Bloss, W.J., Lee, J.D., Heard, D.E., Gaona Colmán, E., Blanco, M.B., Barnes, I., Wiesen, P., Teruel, M.A., 2017. Mechanism
Wirtz, K., Martin-Reviejo, M., Rea, G., Wenger, J.C., Pilling, M.J., 2005. Develop- and product distribution of the O3-initiated degradation of (E)-2-Heptenal, (E)-2-
ment of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation Octenal, and (E)-2-nonenal. J. Phys. Chem. A 121 (27), 5147–5155. http://dx.doi.
of aromatic hydrocarbons. Atmos. Chem. Phys. 5 (3), 641–664. http://dx.doi.org/ org/10.1021/acs.jpca.7b01857.
10.5194/acp-5-641-2005. Grøntoft, T., 2002. Dry deposition of ozone on building materials. Chamber measure-
Brickus, L.S., Cardoso, J.N., De Aquino Neto, F.R., 1998. Distributions of indoor and ments and modelling of the time-dependent deposition. Atmos. Environ. 36 (36–37),
outdoor air pollutants in Rio de Janeiro, Brazil: Implications to indoor air quality 5661–5670. http://dx.doi.org/10.1016/S1352-2310(02)00701-X.
in bayside offices. Environ. Sci. Technol. 32 (22), 3485–3490. http://dx.doi.org/ Grøntoft, T., Raychaudhuri, M.R., 2004. Compilation of tables of surface deposition
10.1021/es980336x. velocities for O3, NO2 and SO2 to a range of indoor surfaces. Atmos. Environ. 38
Cano-Ruiz, J., Kong, D., Balas, R., Nazaroff, W.W., 1993. Removal of reactive gases (4), 533–544. http://dx.doi.org/10.1016/j.atmosenv.2003.10.010.
at indoor surfaces: Combining mass transport and surface kinetics. Atmos. Envi- Hakola, H., Hellén, H., Tarvainen, V., Bäck, J., Patokoski, J., Rinne, J., 2009. Annual
ron. Part A. General Top. 27 (13), 2039–2050. http://dx.doi.org/10.1016/0960- variations of atmospheric VOC concentrations in a boreal forest. Boreal Environ.
1686(93)90276-5. Res. 14 (4), 722–730.

9
T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

He, S.Z., Chen, Z.M., Zhang, X., Zhao, Y., Huang, D.M., Zhao, J.N., Zhu, T., Hu, M., Lin, C.C., Hsu, S.C., 2015. Deposition velocities and impact of physical properties
Zeng, L.M., 2010. Measurement of atmospheric hydrogen peroxide and organic on ozone removal for building materials. Atmos. Environ. 101, 194–199. http:
peroxides in Beijing before and during the 2008 Olympic games: Chemical and //dx.doi.org/10.1016/j.atmosenv.2014.11.029.
physical factors influencing their concentrations. J. Geophys. Res. 115 (D17), Liu, Y., Misztal, P.K., Arata, C., Weschler, C.J., Nazaroff, W.W., Goldstein, A.H., 2021.
D17307. http://dx.doi.org/10.1029/2009JD013544. Observing ozone chemistry in an occupied residence. Proc. Natl. Acad. Sci. 118
Hellén, H., Praplan, A.P., Tykkä, T., Ylivinkka, I., Vakkari, V., Bäck, J., Petäjä, T., (6), e2018140118. http://dx.doi.org/10.1073/pnas.2018140118.
Kulmala, M., Hakola, H., 2018. Long-term measurements of volatile organic com- Liu, L., Wang, X., Chen, J., Xue, L., Wang, W., Wen, L., Li, D., Chen, T., 2018.
pounds highlight the importance of sesquiterpenes for the atmospheric chemistry Understanding unusually high levels of peroxyacetyl nitrate (PAN) in winter in
of a boreal forest. Atmos. Chem. Phys. 18 (19), 13839–13863. http://dx.doi.org/ Urban Jinan, China. J. Environ. Sci. (China) 71, 249–260. http://dx.doi.org/10.
10.5194/acp-18-13839-2018. 1016/j.jes.2018.05.015.
Hodgson, A.T., Ming, K.Y., Singer, B.C., 2004. Quantifying Object and Material Surface Lü, H., Wen, S., Feng, Y., Wang, X., Bi, X., Sheng, G., Fu, J., 2006. Indoor and outdoor
Areas in Residences. Lawrence Berkeley National Laboratory, pp. LBNL–56786. carbonyl compounds and BTEX in the hospitals of Guangzhou, China. Sci. Total
Hodgson, A.T., Wooley, J.D., Daisey, J.M., 1993. Emissions of volatile organic com- Environ. 368 (2–3), 574–584. http://dx.doi.org/10.1016/j.scitotenv.2006.03.044.
pounds from new carpets measured in a large-scale environmental chamber. Air Manuja, A., Ritchie, J., Buch, K., Wu, Y., Eichler, C.M., Little, J.C., Marr, L.C., 2019.
Waste 43 (3), 316–324. http://dx.doi.org/10.1080/1073161X.1993.10467136. Total surface area in indoor environments. Environ. Sci. Process. Impacts 21 (8),
Jenkin, M.E., Saunders, S.M., Pilling, M.J., 1997. The tropospheric degradation of 1384–1392. http://dx.doi.org/10.1039/c9em00157c.
volatile organic compounds: A protocol for mechanism development. Atmos. Mentese, S., Bas, B., 2020. A year-round motoring of ambient volatile organic
Environ. 31 (1), 81–104. http://dx.doi.org/10.1016/S1352-2310(96)00105-7. compounds across Dardanelles strait. J. Chem. Metrol. 14 (2), 177–189. http:
Jenkin, M.E., Saunders, S.M., Wagner, V., Pilling, M.J., 2003. Protocol for the //dx.doi.org/10.25135/jcm.51.20.09.1816.
development of the master chemical mechanism, MCM v3 (Part B): Tropospheric Ministry of Housing, Communities & Local Government (UK Government), 2019.
degradation of aromatic volatile organic compounds. Atmos. Chem. Phys. 3 (1), Ventilation and Indoor Air Quality in New Homes . Ministry of Housing,
181–193. http://dx.doi.org/10.5194/acp-3-181-2003. Communities and Local Government (United Kingdom), pp. 1–87, URL
Jenkin, M.E., Valorso, R., Aumont, B., Newland, M.J., Rickard, A.R., 2020. Estimation of https://assets.publishing.service.gov.uk/government/uploads/system/uploads/
rate coefficients for the reactions of O3 with unsaturated organic compounds for use attachment_data/file/835208/Research_-_ventilation_and_indoor_air_quality.pdf
in automated mechanism construction. Atmos. Chem. Phys. 20 (21), 12921–12937. (Date Accessed: October 2021).
http://dx.doi.org/10.5194/acp-20-12921-2020. Morgan, M., Cruickshank, H., 2014. Quantifying the extent of space shortages: En-
Jenkin, M.E., Valorso, R., Aumont, B., Rickard, A.R., 2019. Estimation of rate co- glish dwellings. Buil. Res. Inform. 42 (6), 710–724. http://dx.doi.org/10.1080/
efficients and branching ratios for reactions of organic peroxy radicals for use 09613218.2014.922271.
in automated mechanism construction. Atmos. Chem. Phys. 19 (11), 7691–7717. Morrison, G.C., Nazaroff, W.W., 2000. The rate of Ozone uptake on carpets: Experi-
http://dx.doi.org/10.5194/acp-19-7691-2019. mental studies. Environ. Sci. Technol. 34 (23), 4963–4968. http://dx.doi.org/10.
Jenkin, M.E., Valorso, R., Aumont, B., Rickard, A.R., Wallington, T.J., 2018. Estimation 1021/es001361h.
of rate coefficients and branching ratios for gas-phase reactions of OH with Morrison, G.C., Nazaroff, W.W., 2002. Ozone interactions with carpet: Secondary
aromatic organic compounds for use in automated mechanism construction. Atmos. emissions of aldehydes. Environ. Sci. Technol. 36 (10), 2185–2192. http://dx.doi.
Chem. Phys. 18 (13), 9329–9349. http://dx.doi.org/10.5194/acp-18-9329-2018. org/10.1021/es0113089.
Jenkin, M.E., Wyche, K.P., Evans, C.J., Carr, T., Monks, P.S., Alfarra, M.R., Barley, M.H., Mueller, F.X., Loeb, L., Mapes, W.H., 1973. Decomposition rates of Ozone in liv-
McFiggans, G.B., Young, J.C., Rickard, A.R., 2012. Development and chamber ing areas. Environ. Sci. Technol. 7 (4), 342–346. http://dx.doi.org/10.1021/
evaluation of the MCM v3.2 degradation scheme for 𝛽-caryophyllene. Atmos. Chem. es60076a003.
Phys. 12 (11), 5275–5308. http://dx.doi.org/10.5194/acp-12-5275-2012. Nazaroff, W.W., 2021. Residential air-change rates: A critical review. Indoor Air 31 (2),
Jenkin, M.E., Young, J.C., Rickard, A.R., 2015. The MCM v3.3.1 degradation scheme for 282–313. http://dx.doi.org/10.1111/ina.12785.
isoprene. Atmos. Chem. Phys. 15 (20), 11433–11459. http://dx.doi.org/10.5194/ Nazaroff, W.W., Weschler, C.J., 2004. Cleaning products and air fresheners: Exposure
acp-15-11433-2015. to primary and secondary air pollutants. Atmos. Environ. 38 (18), 2841–2865.
Kahan, T.F., Washenfelder, R.A., Vaida, V., Brown, S.S., 2012. Cavity-enhanced mea- http://dx.doi.org/10.1016/j.atmosenv.2004.02.040.
surements of hydrogen peroxide absorption cross sections from 353 to 410 nm. J. Nicolas, M., Ramalho, O., Maupetit, F., 2007. Reactions between ozone and building
Phys. Chem. A 116 (24), 5941–5947. http://dx.doi.org/10.1021/jp2104616. products: Impact on primary and secondary emissions. Atmos. Environ. 41 (15),
Kang, K., Kim, H., Kim, D.D., Lee, Y.G., Kim, T., 2019. Characteristics of cooking- 3129–3138. http://dx.doi.org/10.1016/j.atmosenv.2006.06.062.
generated PM 10 and PM 2.5 in residential buildings with different cooking Nørgaard, A.W., Kudal, J.D., Kofoed-Sørensen, V., Koponen, I.K., Wolkoff, P., 2014.
and ventilation types. Sci. Total Environ. 668, 56–66. http://dx.doi.org/10.1016/j. Ozone-initiated VOC and particle emissions from a cleaning agent and an air
scitotenv.2019.02.316. freshener: Risk assessment of acute airway effects. Environ. Int. 68, 209–218.
Katsoyiannis, A., Leva, P., Kotzias, D., 2008. VOC and carbonyl emissions from carpets: http://dx.doi.org/10.1016/j.envint.2014.03.029.
A comparative study using four types of environmental chambers. J. Hard Mater. Poppendieck, D., Hubbard, H., Corsi, R.L., 2021. Hydrogen peroxide vapor as an indoor
152 (2), 669–676. http://dx.doi.org/10.1016/j.jhazmat.2007.07.058. disinfectant: Removal to indoor materials and associated emissions of organic
Kerdouci, J., Picquet-Varrault, B., Durand-Jolibois, R., Gaimoz, C., Doussin, J.F., 2012. compounds. Environ. Sci. Technol. Lett. 8 (4), 320–325. http://dx.doi.org/10.1021/
An experimental study of the gas-phase reactions of no3 radicals with a series of acs.estlett.0c00948.
unsaturated aldehydes: Trans -2-hexenal, trans -2-heptenal, and trans -2-octenal. J. Poppendieck, D., Hubbard, H., Ward, M., Weschler, C., Corsi, R.L., 2007a. Ozone
Phys. Chem. A 116 (41), 10135–10142. http://dx.doi.org/10.1021/jp3071234. reactions with indoor materials during building disinfection. Atmos. Environ. 41
Klenø, J.G., Clausen, P.A., Weschler, C.J., Wolkoff, P., 2001. Determination of ozone (15), 3166–3176. http://dx.doi.org/10.1016/j.atmosenv.2006.06.060.
removal rates by selected building products using the FLEC emission cell. Environ. Poppendieck, D.G., Hubbard, H.F., Weschler, C.J., Corsi, R.L., 2007b. Formation and
Sci. Technol. 35 (12), 2548–2553. http://dx.doi.org/10.1021/es000284n. emissions of carbonyls during and following gas-phase ozonation of indoor mate-
Klepeis, N.E., Nelson, W.C., Ott, W.R., Robinson, J.P., Tsang, A.M., Switzer, P., rials. Atmos. Environ. 41 (35), 7614–7626. http://dx.doi.org/10.1016/j.atmosenv.
Behar, J.V., Hern, S.C., Engelmann, W.H., 2001. The national human activity 2007.05.049.
pattern survey (NHAPS): A resource for assessing exposure to environmental Rai, A.C., Guo, B., Lin, C.H., Zhang, J., Pei, J., Chen, Q., 2014. Ozone reaction with
pollutants. J. Exposure Anal. Environ. Epidemiol. 11 (3), 231–252. http://dx.doi. clothing and its initiated VOC emissions in an environmental chamber. Indoor Air
org/10.1038/sj.jea.7500165. 24 (1), 49–58. http://dx.doi.org/10.1111/ina.12058.
Kruza, M., Carslaw, N., 2019. How do breath and skin emissions impact indoor air Reiss, R., Ryan, P.B., Koutrakis, P., 1994. Modeling Ozone deposition onto indoor
chemistry? Indoor Air 29 (3), 369–379. http://dx.doi.org/10.1111/ina.12539. residential surfaces. Environ. Sci. Technol. 28 (3), 504–513. http://dx.doi.org/10.
Kruza, M., Lewis, A.C., Morrison, G.C., Carslaw, N., 2017. Impact of surface ozone 1021/es00052a025.
interactions on indoor air chemistry: A modeling study. Indoor Air 27 (5), Rim, D., Gall, E.T., Maddalena, R.L., Nazaroff, W.W., 2016. Ozone reaction with interior
1001–1011. http://dx.doi.org/10.1111/ina.12381. building materials: Influence of diurnal ozone variation, temperature and humidity.
Kruza, M., McFiggans, G., Waring, M.S., Wells, J.R., Carslaw, N., 2020. Indoor Atmos. Environ. 125, 15–23. http://dx.doi.org/10.1016/j.atmosenv.2015.10.093.
secondary organic aerosols: Towards an improved representation of their formation Ruiz-Jimenez, J., Heiskanen, I., Tanskanen, V., Hartonen, K., Riekkola, M.-L., 2022.
and composition in models. Atmos. Environ. 240 (August), 117784. http://dx.doi. Analysis of indoor air emissions: From building materials to biogenic and anthro-
org/10.1016/j.atmosenv.2020.117784. pogenic activities. J. Chromatogr. Open 2 (March), 100041. http://dx.doi.org/10.
Lakey, P.S., Wisthaler, A., Berkemeier, T., Mikoviny, T., Pöschl, U., Shiraiwa, M., 2017. 1016/j.jcoa.2022.100041.
Chemical kinetics of multiphase reactions between ozone and human skin lipids: Sabersky, R.H., Sinema, D.A., Shair, F.H., 1973. Concentrations, decay rates, and
Implications for indoor air quality and health effects. Indoor Air 27 (4), 816–828. removal of Ozone and their relation to establishing clean indoor air. Environ. Sci.
http://dx.doi.org/10.1111/ina.12360. Technol. 7 (4), 347–353. http://dx.doi.org/10.1021/es60076a001.
Lamble, S.P., Corsi, R.L., Morrison, G.C., 2011. Ozone deposition velocities, reaction Salthammer, T., 2019. Formaldehyde sources, formaldehyde concentrations and air
probabilities and product yields for green building materials. Atmos. Environ. 45 exchange rates in European housings. Build. Environ. 150 (October 2018), 219–232.
(38), 6965–6972. http://dx.doi.org/10.1016/j.atmosenv.2011.09.025. http://dx.doi.org/10.1016/j.buildenv.2018.12.042.

10
T.J. Carter et al. Atmospheric Environment 297 (2023) 119598

Saunders, S.M., Jenkin, M.E., Derwent, R.G., Pilling, M.J., 2003. Protocol for the Wang, Z., Shaw, D., Kahan, T., Schoemaecker, C., Carslaw, N., 2022b. A modeling
development of the master chemical mechanism, MCM v3 (part A): Tropospheric study of the impact of photolysis on indoor air quality. Indoor Air 32 (6), http:
degradation of non-aromatic volatile organic compounds. Atmos. Chem. Phys. 3 //dx.doi.org/10.1111/ina.13054.
(1), 161–180. http://dx.doi.org/10.5194/acp-3-161-2003. Waring, M.S., Siegel, J.A., 2013. Indoor secondary organic aerosol formation initi-
Schripp, T., Langer, S., Salthammer, T., 2012. Interaction of ozone with wooden ated from reactions between Ozone and surface-sorbed d-Limonene. Environ. Sci.
building products, treated wood samples and exotic wood species. Atmos. Environ. Technol. 47 (12), 6341–6348. http://dx.doi.org/10.1021/es400846d.
54, 365–372. http://dx.doi.org/10.1016/j.atmosenv.2012.02.064. Waring, M.S., Wells, J.R., 2015. Volatile organic compound conversion by ozone,
Shaw, D., Carslaw, N., 2021. INCHEM-Py: An open source Python box model for indoor hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and
air chemistry. J. Open Source Softw. 6 (63), 3224. http://dx.doi.org/10.21105/joss. impacts of oxidant sources. Atmos. Environ. 106 (3), 382–391. http://dx.doi.org/
03224. 10.1016/j.atmosenv.2014.06.062.
Shen, J., Gao, Z., 2018. Ozone removal on building material surface: A literature review. Weschler, C.J., 2000. Ozone in indoor environments: Concentration and chem-
Build. Environ. 134 (March), 205–217. http://dx.doi.org/10.1016/j.buildenv.2018. istry. Indoor Air 10 (4), 269–288. http://dx.doi.org/10.1034/j.1600-0668.2000.
02.046. 010004269.x.
Shin, S.H., Jo, W.K., 2013. Temporal characteristics of volatile organic compounds in Weschler, C.J., 2016. Roles of the human occupant in indoor chemistry. Indoor Air 26
newly-constructed residential buildings: Concentration and source. Environ. Eng. (1), 6–24. http://dx.doi.org/10.1111/ina.12185.
Res. 18 (3), 169–176. http://dx.doi.org/10.4491/eer.2013.18.3.169. Weschler, C.J., Wisthaler, A., Cowlin, S., Tamás, G., Strøm-Tejsen, P., Hodgson, A.T.,
Simmons, A., Colbeck, I., 1990. Resistance of various building materials to ozone Destaillats, H., Herrington, J., Zhang, J., Nazaroff, W.W., 2007. Ozone-initiated
deposition. Environ. Technol. (United Kingdom) 11 (10), 973–978. http://dx.doi. chemistry in an occupied simulated aircraft cabin. Environ. Sci. Technol. 41 (17),
org/10.1080/09593339009384949. 6177–6184. http://dx.doi.org/10.1021/es0708520.
Sturaro, A., Rella, R., Parvoli, G., Ferrara, D., 2010. Long-term phenol, cresols and Wisthaler, A., Weschler, C.J., 2010. Reactions of ozone with human skin lipids: Sources
BTEX monitoring in urban air. Environ. Monit. Assess. 164 (1–4), 93–100. http: of carbonyls, dicarbonyls, and hydroxycarbonyls in indoor air. Proc. Natl. Acad. Sci.
//dx.doi.org/10.1007/s10661-009-0877-x. USA 107 (15), 6568–6575. http://dx.doi.org/10.1073/pnas.0904498106.
Tamás, G., Weschler, C.J., Bakó-Biró, Z., Wyon, D.P., Strøm-Tejsen, P., 2006. Factors Wong, J.P., Carslaw, N., Zhao, R., Zhou, S., Abbatt, J.P., 2017. Observations and
affecting ozone removal rates in a simulated aircraft cabin environment. Atmos. impacts of bleach washing on indoor chlorine chemistry. Indoor Air 27 (6),
Environ. 40 (32), 6122–6133. http://dx.doi.org/10.1016/j.atmosenv.2006.05.034. 1082–1090. http://dx.doi.org/10.1111/ina.12402.
Uchiyama, S., Tomizawa, T., Tokoro, A., Aoki, M., Hishiki, M., Yamada, T., Tanaka, R., Xiong, J., Chen, F., Sun, L., Yu, X., Zhao, J., Hu, Y., Wang, Y., 2019. Characterization
Sakamoto, H., Yoshida, T., Bekki, K., Inaba, Y., Nakagome, H., Kunugita, N., 2015. of VOC emissions from composite wood furniture: Parameter determination and
Gaseous chemical compounds in indoor and outdoor air of 602 houses throughout simplified model. Build. Environ. 161 (April), 106237. http://dx.doi.org/10.1016/
Japan in winter and summer. Environ. Res. 137, 364–372. http://dx.doi.org/10. j.buildenv.2019.106237.
1016/j.envres.2014.12.005. Xue, L.K., Saunders, S.M., Wang, T., Gao, R., Wang, X.F., Zhang, Q.Z., Wang, W.X.,
Vichi, F., Mašková, L., Frattoni, M., Imperiali, A., Smolík, J., 2016. Simultaneous 2015. Development of a chlorine chemistry module for the master chemical
measurement of nitrous acid, nitric acid, and nitrogen dioxide by means of a novel mechanism. Geosci. Model Dev. 8 (10), 3151–3162. http://dx.doi.org/10.5194/
multipollutant diffusive sampler in libraries and archives. Heritage Sci. 4 (1), 1–8. gmd-8-3151-2015.
http://dx.doi.org/10.1186/s40494-016-0074-5. Yao, M., Ke, L., Liu, Y., Luo, Z., Zhao, B., 2020. Measurement of ozone deposition
Wang, N., Ernle, L., Bekö, G., Wargocki, P., Williams, J., 2022a. Emission rates of velocity onto human surfaces of Chinese residents and estimation of corresponding
volatile organic compounds from humans. Environ. Sci. Technol. 56, 4838–4848. production of oxidation products. Environ. Pollut. 266, 115215. http://dx.doi.org/
http://dx.doi.org/10.1021/acs.est.1c08764. 10.1016/j.envpol.2020.115215.
Wang, Z., Kowal, S.F., Carslaw, N., Kahan, T.F., 2020. Photolysis-driven indoor air Ye, W., Wang, H., Chen, Z., Zhang, X., 2020. Ozone deposition on free-running indoor
chemistry following cleaning of hospital wards. Indoor Air 30 (6), 1241–1255. materials and the corresponding volatile organic compound emissions: Implications
http://dx.doi.org/10.1111/ina.12702. for ventilation requirements. Appl. Sci. 10 (12), 4146. http://dx.doi.org/10.3390/
Wang, H., Morrison, G.C., 2006. Ozone-initiated secondary emission rates of aldehydes app10124146.
from indoor surfaces in four homes. Environ. Sci. Technol. 40 (17), 5263–5268. Zhou, S., Liu, Z., Wang, Z., Young, C.J., Vandenboer, T.C., Guo, B.B., Zhang, J.,
http://dx.doi.org/10.1021/es060080s. Carslaw, N., Kahan, T.F., 2020. Hydrogen peroxide emission and fate indoors during
Wang, H., Morrison, G., 2010. Ozone-surface reactions in five homes: Surface reaction non-bleach cleaning: A chamber and modeling study. Environ. Sci. Technol. 54 (24),
probabilities, aldehyde yields, and trends. Indoor Air 20 (3), 224–234. http://dx. 15643–15651. http://dx.doi.org/10.1021/acs.est.0c04702.
doi.org/10.1111/j.1600-0668.2010.00648.x.

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