Atmospheric Environment 80 (2013) 507e513

Contents lists available at ScienceDirect

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

A mechanistic study of limonene oxidation products and pathways

following cleaning activities
Nicola Carslaw*
Environment Department, University of York, York YO10 5DD, UK

h i g h l i g h t s

Indoor air composition following cleaning investigated with a detailed chemical model.

Multi-functional carbonyl compounds found to be key components of the gas-phase.

Composition depends critically on outdoor concentrations.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 9 May 2013
Received in revised form
16 August 2013
Accepted 20 August 2013

Indoor air pollution has caused increasing concern since the 1970s, when the advent of stricter energy
efciency measures lead to increased reports of building related symptoms. Cleaning activities have been
linked to adverse health effects indoors, although it is unclear which of the components of cleaning
products cause these reported health effects. This paper uses a detailed chemical model for indoor air
chemistry, to identify the species formed at the highest concentrations following use of a limonenebased cleaning product. The explicit nature of the chemical mechanism also permits the key pathways
to their formation to be identied. The results show that the key species in terms of gas-phase concentration are multi-functional carbonyl species including limonaldehyde, 4-acetyl-1-methyl-1cyclohexene and other dicarbonyl species. The particle-phase was dominated by peroxide species. The
predicted gas-phase concentrations for three limonene-oxidation products were compared to recently
published human reference values, but found not to be high enough to cause concern for typical indoor
conditions, or under high indoor ozone conditions. However, cleaning products contain a range of terpenes other than limonene, which could also produce some of the secondary products identied here, as
well as more common species such as formaldehyde, glyoxal and hydrogen peroxide. A mechanistic
pathway analysis shows that the secondary products formed through limonene oxidation indoors
depend critically on the competition between ozone and hydroxyl radicals, such that indoor pollutant
concentrations and composition could vary widely in different locations for a nominally similar residence
and indoor activities. Future studies should focus on aiming to measure multi-functional carbonyl species
indoors to help validate models, whilst human reference values are needed for many more relevant
species indoors.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Indoor air pollution
Limonene
Ozone
Multi-functional carbonyl groups
Cleaning
Detailed chemical model

1. Introduction
Since the introduction of improved energy efciency measures
in the 1970s, adverse health effects have been frequently reported
indoors (Ashmore and Dimitroulopoulou, 2009). These health effects include a range of building-related symptoms (BRS) such as
eye, nose, throat and airway irritation, as well as headaches and
fatigue, which have unknown etiology, but typically improve away

* Tel.: 44 1904 324777; fax: 44 1904 322998.

E-mail addresses: nc12@york.ac.uk, nicola.carslaw@york.ac.uk.
1352-2310/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2013.08.034

from the workplace (Buchanan et al., 2008). It has been estimated

that of the 89 million people working in ofces in the US, between
35 and 60 million have one or more BRS weekly (Mendell et al.,
2002) and that such symptoms are responsible for a 2% reduction
in productivity, leading to signicant economic loss (Buchanan
et al., 2008).
People in developed countries are estimated to spend 90% of
their time indoors whether through being at home, at work, or
commuting between the two: our exposure to air pollutants happens mainly indoors despite regulations focussing on the outdoor
environment. Many pollutants enter the indoor environment
through a variety of indoor emissions linked to activities such as

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N. Carslaw / Atmospheric Environment 80 (2013) 507e513

cooking, cleaning and home improvements. In addition, outdoor

pollutants make their way indoors through open windows and
doors, as well as through the building fabric. Consequently, concentrations of air pollutants indoors can often be higher than
outdoors.
In recent years, evidence has begun to suggest that secondary
rather than primary pollutants cause the reported ill-health effects
and that ozone may be responsible for creating these pollutants
(Buchanan et al., 2008). Wolkoff et al. (2000) found that reaction
mixtures of terpenes (a-pinene or limonene) and ozone resulted in
signicant upper airway irritation, at concentrations well below the
no-observed-effect-levels (NOELs) of the parent compounds.
Furthermore, exposure to the individual compounds had no effect
at all, only to mixtures.
Apte et al. (2008) found an association between ambient ozone
concentrations and BRS prevalence from the BASE (Building
Assessment Survey Evaluation) study in the US. In addition, they
found that the ambient ozone concentrations correlated with indoor concentrations of some aldehydes, strongly suggesting that
indoor ozone chemistry was taking place, as the main source of
indoor ozone is from outdoors. The European Commission Scientic Committee on Health and Environmental Risks (SCHER)
recently highlighted the lack of knowledge concerning combined
and mixture effects of indoor air pollutants, and in particular, the
need for further research on ozone-initiated reaction products
(SCHER, 2007).
Indoors, terpene species, which are common components of
cleaning uids, fragrances etc., can form a range of secondary
products when oxidised. Monoterpenes (such as limonene and aand b-pinene) have 10 carbon and 16 hydrogen atoms. Consequently, their gas- and particle-phase oxidation (predominantly by
ozone or hydroxyl radicals) products include a variety of polyfunctional species such as alcohols, carbonyls and carboxylic acids,
with an individual product from limonene oxidation containing on
average 3e4 functional groups (Walser et al., 2008).
Cleaning is known to be a source of high indoor air pollutant
levels, and several studies have shown that airway effects in
cleaning personnel can be associated with the use of household and
cleaning products (Wolkoff, 2013). In addition, the most frequent
cause of non-work-related hospital admissions for chemical related
respiratory disease in the US is reported to be from exposure to
household cleaning products (Medina-Ramon et al., 2006). Cleaning products are used for a wide range of applications and are
available in many different formulations that may include terpenes,
bleach (chlorine), amines, quaternary ammonium compounds, aldehydes, hydrochloric acid and sodium hydroxide: many of these
compounds are known to be irritants and/or sensitisers (Quirce and
Barranco, 2010). US adults have been reported to spend on average,
20e30 min a day cleaning their homes, though not necessarily
using cleaning uids all of this time (Moran et al., 2012).
Quirce and Barranco (2010) review the available evidence for
what might be causing the observed high prevalence of asthma
amongst domestic cleaners. They summarise from available evidence that there is a signicant 30e50% increased risk of incident
asthma associated with the at least weekly use of sprays (particularly glass-cleaners, furniture and air-freshener sprays) and that
this risk increases if the frequency of use, or number of products
used increases. Further, they report that non-spray products were
not associated with asthma risk, speculating that spray products
aid inhalation.
Identifying indoor gas- and particle-phase composition is
extremely challenging, given the multi-functionality of many of the
products, and also the fact that concentrations are often at the limit
of experimental detection. This paper aims to identify secondary
indoor air pollutants that attain high concentrations under cleaning

conditions (with a limonene-based cleaner) using a detailed

chemical model and reviews this information in the light of
recently available human reference values.
2. Methods
The basis of the detailed chemical model for indoor air used in
this work has been described in detail by Carslaw (2007) and a
more recent update by Carslaw et al. (2012). Briey, a detailed
chemical box model was constructed based on a comprehensive
chemical mechanism (the Master Chemical Mechanism, MCM v3.2,
http://mcm.leeds.ac.uk/MCM/) and used to investigate indoor air
chemistry in a typical suburban residence in the UK. The MCM is
described in detail elsewhere (Jenkin et al., 1997, 2003; Saunders
et al., 2003; Bloss et al., 2005). Version 3.2 contains a nearexplicit representation of the gas-phase degradation of w143 volatile organic compounds (VOCs), including limonene, the key VOC
in this work. The mechanism is constructed following a dened
protocol, using the latest kinetic and product data where available,
or structure activity relationships in their absence (Jenkin et al.,
1997). It considers chemistry initiated by reaction with O3
(ozone), OH (hydroxyl radicals) and NO3 (nitrate radicals) and formation of all the major rst-generation products as identied in
reported studies. The schemes continue for each individual VOC
until the nal products of carbon dioxide and water are made
(Jenkin et al., 1997).
In addition to the gas-phase chemistry, Carslaw et al. (2012)
added 41 gas-to-particle conversions for limonene chemistry,
given its ubiquity indoors, as well as its propensity for forming
secondary organic aerosol (SOA). Gas-to-particle partitioning was
dened for the 41 species according to the absorptive partitioning
theory of Pankow (1994), whereby the phase-partitioning of a
given species is dened by the thermodynamic equilibrium of that
species between the gas-phase and condensed organic-phase.
Carslaw et al. (2012) assumed that 30% of the outdoor TSP (total
suspended particulate) was organic in nature and provided a surface for indoor SOA to absorb onto once indoors.
The box-model assumes a single well-mixed environment and
the concentration of each species is calculated according to Equation (1):


n
X
dCi
A
Q
Vd i Ci lr fCo  lr Ci i
R
dt
Vi
Vi j 1 ij

(1)

where Ci (Co) is the indoor (outdoor) concentration of a species; Vd

is the deposition velocity of a species; Ai is the surface area of a
room; Vi is the volume of a room; lr is the air exchange rate (AER)
between indoors and outdoors; f is the outdoor-to-indoor penetration factor (assumed to be equal to 1); Qi is the indoor emission
rate and Rij is the reaction rate between species i and j. The model
contains w20,000 reactions describing VOC emissions, gas-phase
chemistry, deposition to surfaces, exchange with outdoors and
gas-to-particle partitioning for limonene. The air exchange rate is
assumed to be 0.76 air changes per hour, A/V ratio is 3 m2 m3, the
temperature is 293 K and a relative humidity of 50% (Carslaw et al.,
2012). Indoor VOC emission rates and outdoor VOC concentrations
are set as described in Sarwar et al. (2002) and outdoor NOx and O3
concentrations are typical for suburban London (Carslaw, 2007):
the outdoor ozone concentration reaches a maximum of w35 ppb
by early afternoon, whereas the NO and NO2 concentrations reach
maximum concentrations during the morning rush-hour of about
12 and 17 ppb respectively. Only one surface production rate is
considered in the model for nitrous acid (HONO), where a heterogeneous production rate of (2.9  1.8)  103 m min1 is used

N. Carslaw / Atmospheric Environment 80 (2013) 507e513

Table 1
Most important gas-phase species that accumulate following cleaning (excluding
limonene): % contribution to overall composition and species classication. These
species represent w90% of the total gas-phase limonene-oxidation products and all
species that contribute more than 1% individually. MCM names are used in the table
(see http://mcm.leeds.ac.uk/MCM/) and structures are shown in Figs. 1 and 2 except
for PAN (peroxyacteylnitrate), GLYOX (glyoxal), HCHO (formaldehyde) and H2O2
(hydrogen peroxide), which are all made via multiple pathways.
Species

% Contribution

Species classication

LIMKET
C729CHO
LIMAL
C622CHO
PAN
C822PAN
GLYOX
HCHO
C923OH
H2O2
LIMALBCO
LIMAOOH
LIMALACO
LIMANO3

23
12
12
10
8
7
6
6
2
1
1
1
1
1

Carbonyl
Carbonyl
Carbonyl
Carbonyl
PAN
PAN
Carbonyl
Carbonyl
Alcohol
Peroxide
Carbonyl
Peroxide
Carbonyl
Organic nitrate

(Carslaw, 2007). The model is run for 3 days to make sure that
steady-state is achieved, with results for the third day being used
for analysis. Further details regarding initial concentrations, emission and deposition rates and treatment of photolysis can be found
in Carslaw (2007) and Carslaw et al. (2012).
3. Results and discussion
Carslaw et al. (2012) used their detailed chemical model to focus
on the SOA composition indoors for a typical suburban residence in
the UK. They also investigated the predicted SOA composition
during cleaning activities. They added 200 ppb of limonene to a
typical residential environment for 30 min between 10:00e10:30 h
to simulate a cleaning event, based on observed concentrations of
limonene during cleaning activities (Singer et al., 2006). Here, the
analysis is extended to study the cleaning episode in more detail. In
particular, analysis of the gas-phase composition following cleaning activities is extended, especially given the ndings of Wolkoff
et al. (2008) that gas-phase rather than particle-phase compounds appear to be responsible for prominent sensory effects.
There are approximately 530 limonene-oxidation products
formed in the gas-phase in the model of Carslaw et al. (2012). The
concentration of each of these species was averaged for the period
from 10:00e14:00 h to represent concentrations during and
immediately after cleaning activities, and for a 4 h period without
cleaning for comparison. The difference in concentration was then
calculated to see which species attained the highest differential
concentrations. Table 1 lists the 14 species that achieved an overall
contribution to the gas-phase concentration of 1% or more
(excluding limonene itself). Note that in the absence of cleaning
activities, the concentration of limonene is assumed to be 4 ppb,
based on Sarwar et al. (2002). The overall composition of the major
gas-phase limonene-oxidation products (excluding limonene) was
72% carbonyls, 16% PAN species, 4% peroxide material, 5% alcoholic
species, 2% organic nitrates and 1% acidic material.
By comparison, Table 2 shows the main contributors to the SOA
composition following limonene oxidation. The SOA material was
composed of 73% peroxide groups, 18% organic nitrates, w3% PANs
and acidic material and w2% both carbonyl and alcoholic material.
As can be seen from Figs. 1 and 2, many of these species contain
more than one functional group. The classications provided in
Tables 1 and 2 are therefore guided by how the species are assumed
to behave in the chemical mechanism following further reaction

509

Table 2
Most important components of the indoor SOA that accumulate following cleaning:
% contribution to overall composition and classication. These species represent 96%
of the total SOA mass and all species greater than 1% individually. MCM names are
used in the table (see http://mcm.leeds.ac.uk/MCM/) and structures are shown in
Figs. 1 and 2.
Species

% Contribution

Species classication

LIMCOOH
LIMALBOOH
LIMALAOOH
LIMAOOH
LIMCNO3
LMKANO3
C924OOH
LIMBOOH
LIMANO3
C817PAN
LIMONONIC
LIMALAOH

20
16
14
13
8
6
4
4
3
3
2
1

Peroxide
Peroxide/carbonyl
Peroxide/carbonyl
Peroxide
Organic nitrate
Organic nitrate
Peroxide
Peroxide
Organic nitrate
PAN
Acid
Carbonyl

(Jenkin et al., 1997). The only species that are assumed to display
features of two functional groups are LIMALAOOH and LIMALBOOH,
which exhibit some peroxide and some carbonyl behaviour
(Table 2).
In order to investigate the key formation routes further, the
average rates of reaction for all of the reactions within the limonene
scheme have been calculated for the 10:00e14:00 h cleaning
period. In this way, the most important reaction routes leading to
the key products identied in Tables 1 and 2 can be dened (Figs. 1
and 2).
The initial oxidation steps of limonene in this system are via
reaction with O3 or OH, the latter of which is formed from
limonene-ozone reactions (such as when the Criegee biradical,
LIMOOB decays to C923O2 in Fig. 2, OH is also formed). Note that
the NO3 concentration is very low in this system (<1 ppt) and
doesnt compete in the initial oxidation of limonene. Oxidation via
OH leads to three possible peroxy radicals (Fig. 1) whilst oxidation
via O3 can produce two Criegee biradical intermediates (Fig. 2). In
terms of competition between these routes, there is a ratio of about
1.3:1 in favour of oxidation via O3 under these conditions.
The major gas-phase species identied in Table 1 apart from
limonene are LIMKET (4-acetyl-1-methyl-1-cyclohexene, or 4AMCH), C729CHO (a dicarbonyl species with 8 carbon atoms),
LIMAL (3-isopropenyl-6-oxo-heptanal, or limonaldehyde, or IPOH)
and C622CHO (a 7 carbon species with both a carbonyl group and a
hydroxyl group). LIMKET is formed from the degradation of an oxy
radical (LIMCO) formed when a limonene-OH peroxy radical
(LIMCO2) reacts with NO and to a lesser extent, RO2 (Fig. 1).
C729CHO and C622CHO both derive from limonene-O3 oxidation
(Fig. 2). For LIMAL, chemical formation routes are from the oxidation of limonene via OH (Fig. 1), but also via O3 (Fig. 2), with the OH
route being 1.4 times more important. These four species undergo
chemical reactions at different rates as shown in Figs. 1 and 2, and
also undergo deposition to surfaces and exchange with outdoors
(Carslaw et al., 2012). LIMAL also partitions onto the condensed
phase to a minor extent. Despite the importance of these carbonyl
species in the gas-phase, they are relatively unimportant in the
particle phase: their high volatility makes them less likely to end up
condensed onto a particle than species containing organic nitrate
or peroxide groups.
The peroxide species are the most important group of compounds for SOA composition under cleaning conditions, and Table 2
shows that LIMCOOH is the most important individual species,
responsible for w20% of the overall total. LIMCOOH is formed when
LIMCO2 reacts with HO2 (Fig. 1). The equivalent peroxides from the
other limonene-OH peroxy radicals (LIMAOOH and LIMBOOH) are

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N. Carslaw / Atmospheric Environment 80 (2013) 507e513

Fig. 1. Major gas-phase production routes of key limonene oxidation products following reaction with OH under cleaning conditions. The rates of reaction are presented in units of
105 molecule cm3 s1. Species shown in bold grey are the key species in the gas-phase. Species shown in bold black are the key species in SOA. Species shown in both bold grey and
black are important in both phases. Note that pathways with reaction rates below 1  105 molecule cm3 s1 are excluded for clarity. Also note that H atoms are not shown in these
structures to avoid overcrowding particularly around the carbon rings, but that all single bonded oxygen atoms (not radicals) are also bound to a H atom.

also important, as are LIMALAOOH and LIMALBOOH from the ozone

oxidation route (Fig. 2). For LIMCO2 and LIMAO2, reaction with HO2
to form the peroxide is the most important sink under these
conditions.
Fig. 1 also shows how the species containing organic nitrate
functionality are formed (LIMANO3, LMKANO3, LIMCNO3,
LIMBNO3). The organic nitrate species is the minor product formed
when NO reacts with a peroxy radical (such as LIMAO2, LIMBO2,
LIMCO2, LMKAO2), typically, around 20e25% of the overall reaction
route. Collectively they can become signicant: their strong tendency to condense onto the particle phase means they have a much
bigger impact on the SOA composition compared to that of the gasphase.
Table 1 ranked gas-phase species according to the highest
concentrations formed during cleaning activities. However, in
terms of exposure and potential health effects, total concentration
is more relevant. Therefore, Table 3 shows the differential, as well
as the overall concentration of the most important species for the
4 h during and immediately after cleaning activities. Where the
gures in the two columns are similar, cleaning has a large impact
on the overall concentration of that compound (e.g. C923OH,
LIMALBCO, LIMAOOH, LIMALACO). Where the concentrations are
quite different, cleaning activities contribute towards the overall
concentration, but do not necessarily control it (e.g. HCHO) under
typical indoor residential conditions.
Wolkoff (2013) reviewed available data to suggest No Observed
Adverse Effect Level (NOAEL) values for sensory irritation of

213 ppb for H2O2 and 1. 6 ppm for limonene. In addition, human
data for sensory eye irritation for PAN suggested a Lowest Observed
Adverse Effect Level (LOAEL) of 125 ppb. Clearly, the predicted
values during cleaning activities fall way below these thresholds.
Wolkoff et al. (2013) recently provided human reference values
(RFs) for acute airway effects from ve common ozone-terpene
reaction products in indoor air. Their study used inhalation exposure over 60 min to determine acute upper and lower respiratory
tract effects, which is recognised as an established method for risk
assessment of indoor air pollutants. Three of the ve compounds
are included in the MCM limonene scheme: LIMAL, LIMKET (or
IPOH and 4-AMOH respectively in Wolkoff et al. (2013)) and 4-OPA
(4-oxo-pentanal). The human reference values for sensory irritation
are estimated to be 160 ppb, 1.3 ppm and 1.3 ppm for LIMAL,
LIMKET and 4-OPA respectively and 450 and 30 ppb for LIMKET and
4-OPA respectively for airow irritation (Wolkoff et al., 2013).
The predicted concentrations of LIMAL and LIMKET in Table 3
fall a long way short of those needed to produce sensory or
airow effects. Table 3 does not report the concentration of 4-OPA
as it is predicted to be very low under these conditions e less than
1 ppt. This study only considers the degradation of limonene as a
source for these compounds and cleaning uids contain a range of
terpenoid species (Forester and Wells, 2009): geraniol is a source of
4-OPA for instance, although LIMAL and LIMKET are likely to be
specic to limonene degradation (Forester et al., 2007). Wisthaler
and Weschler (2010) highlight the importance of surfaces for production of 4-OPA. In their study, surface reactions were responsible

N. Carslaw / Atmospheric Environment 80 (2013) 507e513

511

Fig. 2. Major gas-phase production routes of key limonene oxidation products following reaction with O3 under cleaning conditions. The rates of reaction are presented in units of
105 molecule cm3 s1. Species shown in bold grey are the key species in the gas-phase. Species shown in bold black are the key species in SOA. Note that pathways with reaction
rates below 1  105 molecule cm3 s1 are excluded for clarity. Also note that H atoms are not shown in these structures to avoid overcrowding particularly around the carbon rings,
but that all single bonded oxygen atoms (not radicals) are also bound to a H atom.

for 90% of the gas-phase 4-OPA, with gas-phase production playing

a minor role. Concentrations of a few ppb of 4-OPA have been
measured in aircraft cabins and ofce air (Wisthaler and Weschler,
2010; Wolkoff et al., 2013), with squalene, a major component of
skin lipids, believed to be an important source in such
environments.
Table 3
Average concentrations from 10:00e14:00 h for baseline cleaning simulation: differential (difference between cleaning and non-cleaning periods) and total concentrations in parts per trillion (ppt). Species are ranked according to largest
differential concentration.
Species

Differential
concentration/ppt

Total concentration/
ppt

LIMONENE
LIMKET
C729CHO
LIMAL
C622CHO
PAN
C822PAN
GLYOX
HCHO
C923OH
H2O2
LIMALBCO
LIMAOOH
LIMALACO
LIMANO3

67,432
1744
898
888
740
567
547
479
426
169
107
90
68
65
56

70,976
2876
1007
1173
1251
700
597
1382
30,462
169
394
90
70
65
93

O3 concentrations during cleaning activities in this study are

suppressed to only w5 ppb, as the indoor concentrations are
determined largely by those typically experienced outdoors in
residential UK areas, around 35 ppb maximum concentration by
late afternoon (Carslaw, 2007; Apte et al., 2008). Should outdoor
and hence indoor O3 concentrations be higher, there will be
increased concentrations of the secondary products. Ozone concentrations indoors range typically from 28 to 60 ppb and a high
value of 247 ppb was reported in Mexico City (Rohr et al., 2003).
Therefore, the cleaning simulation was repeated, with outdoor
concentrations multiplied by 10, and consequent indoor ozone
concentrations closer to 50 ppb. Note that the maximum limonene
concentration under these conditions was around 160 ppb,
compared to 200 ppb for the baseline cleaning run. Table 4 shows
the results for the high ozone simulation in a similar format to
Table 3, except peak concentrations are also included for this more
extreme scenario.
The overall composition of the major gas-phase limoneneoxidation products (excluding limonene) was 65% carbonyls, 9%
PAN species, 3% peroxide material, 14% alcoholic species, <1%
organic nitrates and 3% acidic material. Therefore, under these high
O3 conditions, carbonyls, PANs, peroxides and organic nitrates
became less important whilst alcoholic and acidic species become
more important. This change in ordering relates to the shift between limonene-ozone oxidation versus limonene-OH oxidation.
For the baseline cleaning conditions, oxidation via O3 was 1.3 times
more important than via OH. For the high ozone conditions, this

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N. Carslaw / Atmospheric Environment 80 (2013) 507e513

Table 4
Average concentrations from 10:00e14:00 h for high ozone cleaning simulation:
differential (difference between cleaning and non-cleaning periods) and total concentrations in ppb. Also included is the maximum predicted concentration during
the cleaning activities in ppb. Species are ranked according to largest differential
concentration.
Species

Differential
concentration/ppb

Total concentration/
ppb

Maximum
concentration/ppb

LIMONENE
C729CHO
C622CHO
LIMAL
HCHO
LIMKET
C923OH
PAN
C822PAN
GLYOX
LIMALBCO
LIMALACO
H2O2
LIMAOOH
LIMANO3

32.3
3.4
3.3
2.9
2.5
2.2
1.5
1.2
0.9
0.8
0.8
0.6
0.5
0.1
0.01

34.1
3.8
4.1
3.3
32.7
2.3
1.6
1.6
1.1
2.2
0.9
0.6
0.8
0.1
0.04

161
7.7
5.1
8.6
38.4
4.6
1.9
2.6
1.8
2.4
1.1
1.4
2.0
0.2
0.06

shifts to 1.6 times more important. Consequently, C729CHO becomes more important than LIMKET for the high ozone run, as the
latter is formed via ozone oxidation (Fig. 2), whilst LIMKET derives
from OH oxidation (Fig. 1). Further, both of these species react with
O3, but LIMKET does so with a rate coefcient that is 10 faster than
that for C729CHO. Given that indoor O3 concentration is much
higher for this run, more LIMKET will be lost through reaction with
O3 than C729CHO.
LIMANO3 actually decreases in concentration for the high ozone
run. Again, it is formed through the OH oxidation route (Fig. 1), but
also requires the presence of NO. The much higher ozone suppresses NO concentrations, so the organic nitrates are much less
favoured when ozone is higher. Some species such as C923OH are
actually formed at almost 10 higher concentrations for 10 more
ozone, suggesting a very efcient production route. The only loss
route for this compound in the chemical mechanism employed in
this work is through reaction with OH. Although the OH concentration is 5 higher during the high O3 cleaning conditions
compared to baseline cleaning conditions, it only removes the
C923OH relatively slowly compared to the fast production rate
through ozone oxidation of limonene under these conditions.
These subtle changes in composition are interesting, but also
illustrate an important point. Gas (and particle) phase composition
could be very different for a cleaning activity (or anything else that
releases pollutants indoors) in a similar building but in different
locations with different outdoor concentrations. Consequently,
resulting health effects could also vary depending on the location.
Table 4 shows that the predicted concentrations of LIMAL and
LIMKET do not exceed the human reference values from Wolkoff
et al. (2013), even when higher concentrations of O3 are considered. The reference values measured by Wolkoff et al. (2013) suggest that LIMAL and LIMKET would not contribute substantially to
sensory irritation in the eyes and upper airways for ofce environments. For the conditions selected for this study, such effects are
also unlikely as a result of exposure to these limonene oxidation
products during cleaning.
The study of Wolkoff et al. (2008) suggests that gas-phase
products following limonene oxidation are responsible for
observed sensory effects, specically unreacted limonene and
formaldehyde, which accounted for w75% of the effects. Unreacted
limonene and formaldehyde attain the highest concentrations for
the model conditions investigated here. Although the differential
concentration of HCHO formed through cleaning is only a few ppb,

note that cleaning products contain a range of terpenoid species

(such as a- and b-pinene, a-terpineol, citronellol, geraniol and birisone (Anderson et al., 2007)), which will also produce HCHO (and
other secondary species) when they degrade. The concentrations of
many of the secondary species predicted here (HCHO, glyoxal, PAN
and H2O2) are lower limits for actual cleaning activities. However,
Wolkoff and Nielsen (2010) suggested than concentrations of HCHO
below 80 ppb should not lead to either chronic or acute sensory
irritation in the airways amongst the general population and it
appears unlikely that concentrations of PAN, H2O2 or limonene
attained during cleaning activities can reach levels required to
cause sensory irritation (Wolkoff, 2013).
Wolkoff et al. (2013) suggested that terpene reaction products
with multiple oxygen groups (e.g. dicarbonyls) may exhibit inammatory and respiratory sensitising properties. In this study,
carbonyl compounds (often multi- or bi-functional species) are
predicted to dominate the gas-phase limonene-oxidation products
following cleaning, such as LIMAL and LIMKET. However, at present,
such products are challenging to measure, so there is no way of
checking that the model results are valid. Clearly, such measurements would be of value in the future, along with human reference
values for more of these multi-functional species.
In terms of the predicted SOA composition, peroxide species
dominate, followed by nitrated material, both of which have a high
propensity to condense onto existing particles (Table 2). Rohr et al.
(2003) note that carbonyl, carboxyl and hydroxyl functional groups
on condensed phase products are hydrophilic, so able to dissolve in
mucous in the respiratory tract and cause irritation. If such species
do have potential health effects, partitioning onto SOA could be
more important indoors compared to outdoors, as photolysis rates
are much lower indoors and so higher concentrations can be
reached (Fan et al., 2005). The condensed phase may provide an
effective means of harmful material penetrating to the lower respiratory tract: inhaled H2O2 gas by contrast, is effectively removed
in the nasal region (Li et al., 2002).
4. Conclusions
This study has aimed to identify the major species that form
during cleaning activities in a typical residence. The gas-phase
composition is dominated by carbonyl species, whilst the particle
phase contains a high proportion of peroxide and organic nitrate
species. However, both in the gas- and particle-phases, the species
produced are often bi- or multi-functional.
There are currently few health benchmark data for limoneneoxidation products, such as the study by Wolkoff et al. (2013). In
addition, there are few measurements of the secondary species
identied in this work that attain relatively high concentrations.
Logue et al. (2010) in their hazard assessment of indoor air contaminants note that the SVOCs (semi-volatile organic compounds
such as those in this study) are under-sampled indoors. Clearly, in
the future, there is a need for experimental studies where key
secondary species (particularly those containing carbonyl groups)
are measured indoors as well as more studies such as those by
Wolkoff et al. (2013) that determine reference values for such
species.
Whilst the concentrations predicted from this cleaning event
(even at high O3) did not exceed the reference values reported by
Wolkoff et al. (2013), this study only considers the degradation of
limonene and its consequent oxidation. Cleaning uids contain a
range of other terpene species, which would also be oxidised to
secondary products. Some of the predicted cleaning concentrations are likely to be lower limits, particularly those for 4-OPA,
glyoxal, formaldehyde, PAN and H2O2 as discussed earlier. There
may also be other species of relevance not currently represented in

N. Carslaw / Atmospheric Environment 80 (2013) 507e513

the MCM. For instance, Nrgaard et al. (2006) suggest that secondary ozonides from limonene degradation could be a stable and
hence important species at ambient temperature, but these are
currently not included in the MCM degradation chemistry. Finally,
ozone concentrations (outdoor conditions) can profoundly affect
the predicted composition and are key to the balance between the
oxidation of limonene by OH and ozone, and the consequential
oxidation routes and secondary products.
References
Anderson, S.E., Wells, J.R., Fedorowicz, A., Butterworth, L.F., Meade, B.J.,
Munson, A.E., 2007. Evaluation of the contact and respiratory sensitization
potential of volatile organic compounds generated by simulated indoor air
chemistry. Toxicol. Sci. 97, 355e363.
Apte, M.G., Buchanan, I.S.H., Mendell, M.J., 2008. Outdoor ozone and buildingrelated symptoms in the BASE study. Indoor Air 18, 156e170.
Ashmore, M.R., Dimitroulopoulou, C., 2009. Personal exposure of children to air
pollution. Atmos. Environ. 43, 128e141.
Bloss, C., Wagner, V., Jenkin, M.E., Volkamer, R., Bloss, W.J., Lee, J.D., Heard, D.E.,
Wirtz, K., Martin-Reviejo, M., Rea, G., Wenger, J.C., Pilling, M.J., 2005. Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric
oxidation of aromatic hydrocarbons. Atmos. Chem. Phys. 5, 641e664.
Buchanan, I.S.H., Mendell, M.J., Mirer, A.G., Apte, M.G., 2008. Air lter materials,
outdoor ozone and building-related symptoms in the BASE study. Indoor Air 18,
144e155.
Carslaw, N., 2007. A new detailed chemical model for indoor air pollution. Atmos.
Environ. 41, 1164e1179.
Carslaw, N., Mota, T., Jenkin, M.E., Barley, M.H., McFiggans, G., 2012. A signicant
role for nitrate and peroxide groups on indoor secondary organic aerosol. Environ. Sci. Technol. 46, 9290e9298.
Fan, Z., Weschler, C.J., Han, I.-K., Zhang, J., 2005. Co-formation of hydroperoxides
and ultra-ne particles during the reactions of ozone with a complex VOC
mixture under simulated indoor conditions. Atmos. Environ. 39, 5171e5182.
Forester, C.D., Ham, J.E., Wells, J.R., 2007. Geraniol (2,6-dimethyl-2,6-2,6-diene-8-Ol)
reactions with ozone and OH radical: rate constants and gas-phase products.
Atmos. Environ. 41, 1188e1199.
Forester, C.D., Wells, J.R., 2009. Yields of carbonyl products from gas-phase reactions
of fragrance compounds with OH radical and ozone. Environ. Sci. Technol. 43,
3561e3568.
Jenkin, M.E., Saunders, S.M., Pilling, M.J., 1997. The tropospheric degradation of
volatile organic compounds: a protocol for mechanism development. Atmos.
Environ. 31, 81e104.
Jenkin, M.E., Saunders, S.M., Wagner, V., Pilling, M.J., 2003. Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds. Atmos. Chem. Phys. 3, 181e193.
Li, T.-H., Turpin, B.J., Shields, H.C., Weschler, C.J., 2002. Indoor hydrogen peroxide
derived from ozone/d-limonene reactions. Environ. Sci. Technol. 36, 3295e
3302.
Logue, J.M., McKone, T.E., Sherman, M.H., Singer, B.C., 2010. Hazard assessment of
chemical air contaminants measured in residences. Indoor Air 21, 92e109.

513

Medina-Ramon, M., Zock, J.-P., Kogevinas, M., Sunyer, J., Torralba, Y., Borrell, A.,
Burgos, F., Ant, J.M., 2006. Asthma, chronic bronchitis, and exposure to irritant
agents in occupational domestic cleaning: a nested case-control study. Occup.
Environ. Med. 62 (9), 598e606.
Mendell, M.J., Fisk, W.J., Kreiss, K., Levin, H., Alexander, D., Cain, W.S., Girman, J.R.,
Hines, C.J., Jensen, P.A., Milton, D.K., Rexroat, L.P., Wallingford, K.M., 2002.
Improving the health of workers in indoor environments: priority research
needs for a national occupational research agenda. Am. J. Public Health 92,
1430e1440.
Moran, R.E., Bennett, D.H., Tancredi, D.J., Wu, X., Ritz, B., Herz-Picciotto, I., 2012.
Frequency and longitudinal trends of household care product use. Atmos. Environ. 55, 417e424.
Nrgaard, A.W., Njgaard, J.K., Larsen, K., Sporring, S., Wilkins, C.K., Clausen, P.A.,
Wolkoff, P., 2006. Secondary limonene endo-ozonide: a major product from
gas-phase ozonolysis of R-()-limonene at ambient temperature. Atmos. Environ. 40, 3460e3466.
Pankow, J.F., 1994. An absorption model of the gas/aerosol partitioning involved in
the formation of secondary organic aerosol. Atmos. Environ. 28, 189e193.
Quirce, S., Barranco, P., 2010. Cleaning agents and asthma. J. Investig. Allergol. Clin.
Immunol. 20, 542e550.
Rohr, A.C., Weschler, C.J., Koutrakis, P., Spengler, J.D., 2003. Generation and quantication of ultrane particles through terpene/ozone reaction in a chamber
setting. Aerosol Sci. Technol. 37, 65e78.
Sarwar, G., Corsi, R., Kimura, Y., Allen, D., Weschler, C., 2002. Hydroxyl radicals in
indoor environments. Atmos. Environ. 36, 3973e3988.
Saunders, S.M., Jenkin, M.E., Derwent, R.G., Pilling, M.J., 2003. Protocol for the
development of the Master Chemical Mechanism, MCM v3 (part A): tropospheric degradation of non-aromatic volatile organic compounds. Atmos.
Chem. Phys. 3, 161e180.
Scientic Committee on Health and Environmental Risks (SCHER), 2007. Opinion on
Risk Assessment on Indoor Air Quality. European Commission: Health and
Consumer Protection Directorate-General, Brussels.
Singer, B.C., Destaillats, H., Hodgson, A.T., Nazaroff, W.W., 2006. Cleaning products
and air fresheners: emissions and resulting concentrations of glycol ethers and
terpenoids. Indoor Air 16, 179e191.
Walser, M.L., Desyaterik, Y., Laskin, J., Laskin, A., Nizkorodov, S.A., 2008. High-resolution mass spectrometric analysis of secondary organic aerosol produced by
ozonation of limonene. Phys. Chem. Chem. Phys. 10 (7), 1009e1022.
Wisthaler, A., Weschler, C.J., 2010. Reactions of ozone with human skin lipids:
sources of carbonyls, dicarbonyls, and hydroxycarbonyls in indoor air. Proc.
Natl. Acad. Sci. 107, 6568e6575.
Wolkoff, P., Clausen, P.A., Wilkins, C.K., Nielsen, G.D., 2000. Formation of strong
airway irritants in terpene/ozone mixtures. Indoor Air 10, 82e91.
Wolkoff, P., Clausen, P.A., Larsen, K., Hammer, M., Larsen, S.T., Nielsen, G.D., 2008.
Acute airway effects of ozone-initiated d-limonene chemistry: importance of
gaseous products. Toxicol. Lett. 181, 171e176.
Wolkoff, P., Nielsen, G.D., 2010. Non-cancer effects of formaldehyde and relevance
for setting an indoor air guideline. Environ. Int. 36, 788e799.
Wolkoff, P., Larsen, S.T., Hammer, M., Kofoed-Srensen, V., Clausen, P.A.,
Nielsen, G.D., 2013. Human reference values for acute airway effects of ve
common ozone-initiated terpene reaction products in indoor air. Toxicol. Lett.
216, 54e64.
Wolkoff, P., 2013. Indoor air pollutants in ofce environments: assessment of
comfort, health, and performance. Int. J. Hyg. Environ. Health 216 (4), 371e394.