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Atmospheric Environment 45 (2011) 3676e3684

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

The AIRMEX study - VOC measurements in public buildings and schools/


kindergartens in eleven European cities: Statistical analysis of the data
Otmar Geiss, Georgios Giannopoulos*, Salvatore Tirendi, Josefa Barrero-Moreno, Bo R. Larsen,
Dimitrios Kotzias
European Commission, Joint Research Centre, Institute for Health and Consumer Protection, Chemical Assessment and Testing Unit, Via E. Fermi 2749, Ispra 21027 (VA), Italy

a r t i c l e i n f o a b s t r a c t

Article history: Indoor and outdoor air concentrations as well as personal exposure concentrations of volatile organic
Received 7 December 2010 compounds (VOCs) have been measured during 2003e2008 in public buildings, schools, kindergartens
Received in revised form and private homes in eleven cities over Europe covering geographic areas in north, central and south
8 April 2011
Europe during different seasons within the frame of the AIRMEX (European Indoor Air Monitoring and
Accepted 15 April 2011
Exposure assessment) study. A database is presented containing the results for 23 VOCs based upon
approximately 1000 samples taken from 182 different working environments (offices, classrooms,
Keywords:
waiting halls) in public buildings, schools and kindergartens, from 103 private homeplaces and from
VOCs
Database
adult volunteers (148 samples). The statistical analysis of the data demonstrated that sources in the
Indoor air quality indoor environment are prevailing for most of the investigated VOCs with indoor/outdoor (I/O)
Geographical variation concentration ratios following the order: hexanal z D-limonene [ formaldehyde > acetone > 1-
Seasonal variation butoxy-2-propanol > acetaldehyde > propanal > 1-butanol > n-undecane > methylcyclohexane > n-
dodecane. For aromatic hydrocarbons the main impact was shown to be penetration from outdoor air as
indicated by I/O ratios near one and is characterised by significantly higher indoor as well as outdoor
concentrations in the south of Europe with respect to the north. For the terpenes, the lowest indoor
concentrations were measured during the warm season, which may be explained by higher ventilation
rates and reactions with ozone penetrated from outdoor air.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction (Cocheo et al., 2000) and the PEOPLE project (Ballesta et al., 2000)
the focus was exclusively on benzene. In the former project, carried
Studies have shown that indoor exposure to volatile organic out in six European cities from 1996 to 1998, the exposure of 50
compounds (VOCs) can significantly contribute to adverse health volunteers was studied by monitoring the concentrations in homes
effects (Dockery et al., 1993; Pope et al., 1995; Laden et al., 2001). over a time range of 108 h. In the latter project a shorter sampling
The vast majority of human activities take place in indoor areas period (12 h) was used for personal exposure measurements in
such as private homes, offices, shops and cars. Thorough investi- combination with a high number of samples for each city.
gations of the VOC pollution levels in such micro-environments are Measurements were made during 2002e2003 outdoors, indoors
essential for the understanding of population exposure to harmful and close to the breathing zone of volunteers.
substances, for epidemiological work and the eventual ameliora- The AIRMEX study (Kotzias et al., 2009) aims at the identifica-
tion of the indoor air quality. During the last decade three major tion and quantification of main indoor air pollutants in European
VOC exposure studies have assessed European indoor micro- public buildings - including schools and kindergartens - and at the
environments. In the frame of the EXPOLIS study, which took estimation of human exposure to these pollutants while working
place in several European cities a wide range of VOCs were and/or residing in these areas for a certain period of time. The study
measured over 48 h in private homes, on the workplace, outdoors, focuses on 14 VOCs (hydrocarbons, aromatic compounds, alcohols
and near to the breathing zone of volunteers (Edwards and and carbonyls). Some of them have been identified in the INDEX
Jantunen, 2001; Edwards et al., 2001a,b). In the MACBETH study project as priority compounds in indoor environments (Kotzias
et al., 2005). VOCs were monitored in eleven European cities over
a five years period and in dedicated campaigns with a 7 days
* Corresponding author. duration outdoors, in public buildings and schools/kindergartens,
E-mail address: georgios.giannopoulos@jrc.ec.europa.eu (G. Giannopoulos). in private homes and with personal sampling devices near the

1352-2310/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2011.04.037
O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684 3677

breathing zone of volunteers. Schools and kindergartens have been methylcyclohexane, 2-butoxyethanol, butanol, n-decane, n-
included in the present study since children spend a large amount undecane and n-dodecane).
of time in this type of public buildings and since children’s health is
particularly susceptible to hazardous pollutants (Guzelian et al., 2.1. Sampling
1992; Aprea et al., 2000; Commission, 2004).
Studies done in the past in Munich, Hannover, Cologne and Simultaneous sampling of indoor/outdoor concentrations and
Leipzig have indicated that indoor concentrations for most VOCs exposure concentrations was carried out by diffusive sampling in
are highest during winter and lowest during summer (Schlink et al., campaigns with the duration of a full 7-day week including week-
2004; Ilgen et al., 2001). Schlink et al. (2004) concluded from their ends. For exposure-concentration sampling devices were placed on
study on seasonal VOC concentration variations that a correct the body of volunteers nearby the breathing zone during daytime
assessment of indoor air quality must take into account the season and close to bed during night-time. For convenience, volunteers
when the sampling takes place. For this reason the AIRMEX project were asked to wear the exposures samplers for only three days. Only
included two campaigns in each city; one in the cold and one in the in a few cases did volunteers agree to wear two passive personal-
warm period of the year. A first analysis of the AIRMEX data with samplers (one for VOC and one for carbonyls). For this reason the
focus on the potential health effects of formaldehyde and benzene data coverage for personal exposure concentrations to carbonyls is
(Kotzias et al., 2009) indicated that air pollution concentrations are lower than for the other VOCs. Indoor concentration samplers were
consistently higher indoors than outdoors for formaldehyde (and to distributed inside the buildings at a height of 2e2.5 m in order to
a lesser extent for benzene) and that personal exposure concen- cover the areas of main access by the occupants. In public buildings
trations are higher or similar to indoor concentrations and that in the samplers were placed in the entrance halls and offices. In
some cases, indoor concentrations in homes by far exceed those of kindergartens and schools the samplers were mounted in class-
public buildings and school/kindergartens, thus dominating rooms. In the homes of the volunteers the samplers were placed in
personal exposures. Moreover it was indicated that non- the living room during the daytime and in the bedroom at night.
carcinogenic responses from formaldehyde and benzene like Outdoor concentration samplers were placed at rain-protected
inflammation may be enhanced by the presence of toluene in the positions in close vicinity to the studied buildings. For all
indoor air VOC mixtures (Kotzias et al., 2009). measurements radial type diffusion samplers were used. Hydro-
In the current paper we provide detailed information on all carbon and alcohol sampling was carried out with charcoal based
measured concentrations of the compounds investigated within cartridges (Radiello code 130, Supelco 3050 Spruce Str., St. Louis,
the AIRMEX study, which is intended to serve as a reference for MO, USA) whereas carbonyl sampling was done by 2,4-dini-
future indoor air investigations and exposure studies. The statistical trophenyl-hydrazine based cartridges (Radiello code 165, Supelco,
analysis of the dataset demonstrates the influence of geographical St. Louis, MO, USA). The precision and accuracy of diffusive sampling
and seasonal variations on the indoor air concentrations of VOCs in of VOCs in air have been studied in detail (Ballesta et al., 2000;
public buildings, school/kindergartens and homes. Strandberg et al., 2006; Meininghaus et al., 2003; Clarisse et al.,
2003). For the utilised Radiello diffusive samplers the total
2. Materials and methods measurement uncertainty has been found to be in the order of about
16% for a measuring time period of 7 days (Plaisance et al., 2008).
A detailed description of sampling and measurement tech-
niques has been presented elsewhere (Kotzias et al., 2009). A short 2.2. Sample preparation and analysis
overview of the analytical procedures and the sampling strategy is
given below. 2.2.1. Analysis of hydrocarbons and alcohols
Measuring campaigns were carried out in public buildings Samples were prepared and analysed following the ISO/FDIS
located in urban areas with high traffic density, and in kindergar- 16200-2 method (ISO/FDIS 16200-2). The gas chromatographic
tens/schools mostly situated in suburbs with reduced (medium) system used was the Agilent 6890 (Agilent Technologies, Santa
traffic impact. The characteristics of the studied indoor micro-
environments were similar for all cities (for example buildings Table 1
with public access). However, no attention was paid to the age of Airmex locations and dates where measurement campaigns took place.

the buildings. In a very few exceptional cases samples were taken in City Country Campaign North South Warm Cold Comments
single offices or entrance halls where smoking was allowed Arnhem/ NL March 2004  
(Greece, Catania). Volunteers were identified among the employees Nijmegen August 2006  
and/or teachers working in the selected indoor environments for Athens GR December 2003  
October 2005  
personal exposure monitoring. The cities included in this project
Brussels BE September 2004   Only public
were selected to give a good representation of typical European March 2007   buildings,
indoor environments. The cities are listed in Table 1. Measurements no schools
were done twice in each city: in the warm and in the cold season of Budapest HU May 2007  
the year and on average three public buildings and two schools January 2008  
Catania IT October 2003  
were monitored in each city. May 2004  
The list of priority substances to be measured was defined Dublin IE May 2007  
following the selection criteria of the INDEX project (Kotzias et al., February 2008  
2005), namely that the compounds had to be present in the indoor Helsinki FI August 2007  
April 2008  
air and that they have shown adverse health effects being hence
Leipzig DE April 2005  
a potential hazard to European populations. Benzene, toluene, July 2006  
ethylbenzene, m/p-xylene, o-xylene, 1,2,4-trimethylbenzene, Nicosia CY July 2004   In 2004 only
n-hexane, a-pinene, D-limonene, formaldehyde, acetaldehyde, schools
propanal and hexanal were always measured in every campaign. January 2007  
Thessaloniki GR November 2004  
Additionally a set of other chemicals were measured as well based May 2006  
on the characteristics of the area under evaluation (i.e. styrene,
3678 O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684

Table 2
Statistical information for each compound for all measurements done in the frame of the AIRMEX project.

Values Min Max Arith. Mean 5th Percentile 25th Percentile Median 75th Percentile 95th Percentile

[n] [mg m 3
] [mg m 3
] [mg m 3
] [mg m 3
] [mg m 3
] [mg m 3
] [mg m 3
] [mg m 3
]
Acetaldehyde Outdoor (Ambient) 105 0.1 5.1 1.8 0.3 1.0 1.8 2.4 4.2
Public Buildings/Schools 186 1.4 29.1 8.5 2.5 5.0 7.2 10.1 18.8
Private houses 96 3.7 41.3 12.8 4.9 7.6 11.2 15.9 24.8
Personal Inhalation 58 5.1 29.1 13.7 6.1 9.4 12.4 15.6 23.7

Acetone Outdoor (Ambient) 66 0.3 12.8 0.3 1.7 4.5 6.2 9.3 4.5
Public Buildings/Schools 129 1.4 336.8 5.7 11.9 19.5 29.6 59.6 30.6
Private houses 88 10.4 165.1 11.6 22.7 31.0 47.4 94.2 38.6
Personal Inhalation 45 11.8 225.9 16.4 30.1 31.0 51.6 66.7 44.5

Benzene Outdoor (Ambient) 108 0.4 15.2 3.2 0.6 1.2 2.1 4.6 8.0
Public Buildings/Schools 188 0.5 63.7 4.4 0.8 1.6 2.6 4.9 11.9
Private houses 96 0.4 32.1 2.8 0.7 1.2 1.9 3.3 4.9
Personal Inhalation 146 0.7 26.4 4.7 1.2 2.2 3.5 6.0 13.6

2-Butoxyethanol Outdoor (Ambient) 41 0 0 0 0 0 0 0 0


Public Buildings/Schools 74 0 136.5 4.5 0 0 0.25 1.3 8.3
Private houses 50 0 11.0 0.6 0 0 0 0 2.7
Personal Inhalation 53 0 7.9 0.5 0 0 0 0.25 2.4

1-Butoxy-2-propanol Outdoor (Ambient) 12 0 1.6 0.4 e e e e e


Public Buildings/Schools 21 0.5 33.9 4.7 0.5 0.9 4.7 3.0 18.6
Private houses 8 1.9 39.6 12.5 e e e e e
Personal Inhalation e e e e e e e e e

1-Butanol Outdoor (Ambient) 46 0 10.9 1.5 0 0.2 0.6 1.7 5.0


Public Buildings/Schools 82 0.3 41.4 3.7 0.5 1.1 1.8 3.7 11.2
Private houses 46 0.4 9.8 2.5 0.6 1.0 1.8 3.5 7.5
Personal Inhalation 40 0.4 8.2 2.8 0.5 1.4 2.3 3.5 6.8

n-Decane Outdoor (Ambient) 22 3.0 9.9 6.2 3.0 4.3 5.7 7.7 9.4
Public Buildings/Schools 46 7.7 32.8 14.4 8.8 11.4 13.1 16.2 22.4
Private houses 40 8.8 32.7 17.3 9.8 13.1 15.6 20.9 30.5
Personal Inhalation 37 11.6 47.6 24.5 15.5 20.7 22.7 27.0 35.2

n-Dodecane Outdoor (Ambient) 22 3.0 9.9 6.2 3.0 4.3 5.7 7.7 9.4
Public Buildings/Schools 46 7.7 32.8 14.4 8.8 11.4 13.1 16.2 22.4
Private houses 40 8.8 32.7 17.3 9.8 13.1 15.6 20.9 30.5
Personal Inhalation 37 11.6 47.6 24.5 15.5 20.7 22.7 27.0 35.2

Ethylbenzene Outdoor (Ambient) 108 0.2 17.9 2.2 0.3 0.6 1.1 2.6 6.1
Public Buildings/Schools 178 0.2 26.9 2.4 0.5 0.7 1.3 3.0 7.4
Private houses 88 0.2 12.8 1.5 0.4 0.6 1.1 1.7 3.8
Personal Inhalation 146 0.4 44.7 3.2 0.5 1.1 1.8 3.8 8.2

Formaldehyde Outdoor (Ambient) 105 0.3 7.3 2.6 0.6 1.7 2.4 3.2 4.9
Public Buildings/Schools 185 1.5 49.7 16.7 4.5 10.4 14.1 22.7 31.5
Private houses 97 3.9 57.2 21.5 7.9 13.6 19.7 25.3 44.2
Personal Inhalation 58 7.4 29.9 16.6 8.3 12.7 15.3 19.7 25.7

n-Hexane Outdoor (Ambient) 73 0.3 6.0 1.6 0.4 0.8 1.1 2.2 3.6
Public Buildings/Schools 134 0.3 33.3 3.0 0.5 1.0 1.7 3.1 7.6
Private houses 84 0.2 78.4 2.5 0.5 0.9 1.4 2.1 3.5
Personal Inhalation 92 0.6 50.8 4.0 0.9 1.5 2.4 4.2 9.7

n-Heptane Outdoor (Ambient) 22 0 0.7 0.4 0 0.3 0.4 0.6 0.7


Public Buildings/Schools 46 0.2 9.7 1.0 0.3 0.5 0.6 1.0 3.1
Private houses 40 0.2 8.9 1.2 0.3 0.5 0.7 1.2 2.4
Personal Inhalation 37 0.5 10.5 1.4 0.5 0.8 0.9 1.2 3.8

Hexanal Outdoor (Ambient) 102 0.2 3.3 0.9 0.3 0.5 0.8 1.4 2.1
Public Buildings/Schools 185 1.2 159.6 16.4 3.0 6.8 11.4 21.6 39.6
Private houses 96 6.2 198.1 32.3 8.5 14.8 24.4 39.4 82.0
Personal Inhalation 66 1.0 68.0 22.2 1.8 14.0 20.2 28.3 44.1

D-Limonene Outdoor (Ambient) 102 0 2.4 0.3 0 0 0.2 0.3 1.2


Public Buildings/Schools 179 0 175.7 9.4 0.3 1.2 2.6 9.1 33.0
Private houses 96 0 492.9 29.2 1.6 4.9 9.5 31.0 87.6
Personal Inhalation 146 0.4 276.9 26.1 1.4 4.3 10.4 32.1 88.4

Methylcyclohexane Outdoor (Ambient) 44 0 2.0 0.4 0 0.1 0.3 0.5 1.2


Public Buildings/Schools 86 0.1 36.6 2.9 0.1 0.4 0.7 1.2 14.1
Private houses 68 0 6.2 0.9 0.1 0.3 0.5 0.9 3.7
Personal Inhalation 67 0 23.0 2.2 0.3 0.5 0.8 1.6 9.2

Propanal Outdoor (Ambient) 104 0 1.9 0.7 0.1 0.3 0.6 0.9 1.4
Public Buildings/Schools 185 0.5 26.0 3.0 0.8 1.4 2.3 3.0 9.1
Private houses 96 0.4 12.7 3.0 0.9 1.8 2.7 3.3 5.9
Personal Inhalation 58 1.5 28.0 4.5 1.5 2.3 2.6 3.7 18.0
O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684 3679

Table 2 (continued )

Values Min Max Arith. Mean 5th Percentile 25th Percentile Median 75th Percentile 95th Percentile

[n] [mg m ] [mg m


3 3
] [mg m 3
] [mg m 3
] [ mg m 3
] [ mg m 3
] [mg m 3
] [mg m 3
]
a-Pinene Outdoor (Ambient) 89 0 1.5 0.1 0 0 0 0.2 0.6
Public Buildings/Schools 160 0 47.3 3.2 0 0.6 1.5 3.1 12.3
Private houses 97 0.2 214.1 14.5 0.6 2.6 6.1 16.9 47.3
Personal Inhalation 129 0 58.9 8.3 0.5 2.3 4.5 9.2 32.2

Styrene Outdoor (Ambient) 66 0 2.0 0.1 0 0 0 0 1.1


Public Buildings/Schools 128 0 3.2 0.2 0 0 0 0 2.4
Private houses 88 0 22.1 0.4 0 0 0 0 1.0
Personal Inhalation 83 0 5.4 6.4 0 0 0 0.1 2.5

Toluene Outdoor (Ambient) 108 0.8 207.8 11.5 1.2 2.3 4.8 12.9 33.2
Public Buildings/Schools 188 1.0 103.8 12.6 1.7 3.3 7.1 15.5 47.6
Private houses 96 1.3 160.6 11.7 2.5 4.5 6.5 11.1 28.4
Personal Inhalation 146 1.4 291.0 22.4 3.4 6.7 11.7 27.5 55.3

1,2,4-Trimethylbenzene Outdoor (Ambient) 105 0.2 16.3 2.2 0.2 0.4 0.9 2.0 8.2
Public Buildings/Schools 185 0.2 44.3 3.3 0.3 0.6 1.2 3.1 13.6
Private houses 96 0.3 58.9 2.7 0.3 0.6 1.1 2.9 6.6
Personal Inhalation 143 0 35.1 3.1 0.5 0.8 1.6 3.0 8.8

n-Undecane Outdoor (Ambient) 22 0 2.7 0.6 0 0 0.5 0.8 1.9


Public Buildings/Schools 46 0 19.5 2.2 0 0.9 1.4 2.1 6.3
Private houses 40 0 113 7.2 0.8 1.2 2.3 5.0 20.0
Personal Inhalation 37 0 11.1 3.0 0 1.6 2.4 3.2 8.4

m/p-Xylene Outdoor (Ambient) 108 0.5 36.5 5.7 0.6 1.4 2.5 7.2 16.2
Public Buildings/Schools 188 0.7 75.1 6.2 1.1 1.8 2.9 7.1 21.5
Private houses 96 0.5 28.1 3.8 0.9 1.7 2.8 4.6 9.3
Personal Inhalation 146 0.8 144.2 10.5 1.3 2.8 4.7 12.2 31.0

o-Xylene Outdoor (Ambient) 108 0.2 12.3 2.0 0.3 0.5 0.9 2.6 5.5
Public Buildings/Schools 188 0.2 22.2 2.2 0.6 0.9 1.2 2.4 7.1
Private houses 96 0.2 20.5 1.8 0.5 0.9 1.2 2.0 3.7
Personal Inhalation 146 0.4 61.6 4.2 0.6 1.4 2.0 5.0 11.3

Clara, CA, USA) equipped with a flame ionisation detector. Chro- arithmetical averages and percentiles of concentrations observed in
matographic separation was achieved using a J&W Scientific all eleven cities for each compound and in each micro-environment
capillary column (DB-5, 60 m, 0.25 mm i.d., 1 mm film thickness, (outdoors, indoors, personal). The information contained in the
Agilent J&W columns, Santa Clara, CA, USA). The detection limit for table may serve as reference for typical European exposure
all compounds ranges from 0.2 to 0.3 mg m 3. scenarios and is essential for probabilistic exposure assessment
through timeeactivity analysis. The data are not claimed to be
2.2.2. Analysis of carbonyls exhaustive and representative for all European possible situations.
Samples were prepared and analysed following the ISO/FDIS However, it can be used for exposure assessment in the investi-
16000-4 method (ISO/FDIS 16000-4, 2004). Analysis of carbonyl gated areas and may also give a good indication for the average
compounds was conducted using the Agilent Series 1100 liquid European exposure to VOCs.
chromatographic system (Agilent Technologies, Santa Clara, CA, VOCs with the highest absolute concentrations include acetone
USA) coupled to a diode array detector (DAD) set at 360 nm. (median concentration in private houses 47.4 mg m 3 and
Chromatographic separation was achieved using a Waters Nova- 51.6 mg m 3 in personal samples), n-decane (median concentration
Pak C18, 60 Å. 4 mm (3.9  300) mm column (Waters Corpora- in personal inhalation samples 22.7 mg m 3), n-dodecane (median
tion, 34 Maple Street, Milford, MA, USA). The detection limit for all concentration in personal samples 22.7 mg m 3), formaldehyde
carbonyls ranges from 0.2 to 0.3 mg m 3. (median concentration in private houses 19.7 mg m 3) and hexanal
(median concentration in private houses 24.4 mg m 3 and 20.2 in
2.2.3. Fitting of the experimental data personal samples).
Experimental data obtained through the measurement In Table 3 the levels of selected VOCs measured in AIRMEX study
campaigns are plotted using cumulative probability plots. Addi- are compared with a similar study (Expolis-Helsinki).
tionally, fitted plots have been also elaborated using the mean and First of all, it is clear that concentrations measured in the two
standard deviation values calculated from the measured data. The studies are on a similar level. However, some minor differences are
data follow a log-normal distribution. The fitting has been worth noting, namely that the outdoor concentrations in the AIR-
produced using MS-ExcelÒ. Using the random number generator MEX study tend to be higher for the aromatic compounds than in
function with a defined number of data and providing the type of the Expolis-Helsinki study, and vice-versa for the residential,
distribution (log-normal) and the corresponding standard devia- workplaces and personal exposure concentrations. This can be
tion and mean values, it has been possible to reproduce the theo- explained by differences in the traffic fleet as discussed later in the
retical form of these distributions. paper and by differences in ventilation rates. Furthermore differ-
ences of only minor nature can be observed for terpenes. This is
3. Results and discussion confirmed by the cumulative probability plots discussed in Section
4.2.
Table 2 summarises all data collected within the frame of the The data obtained in the AIRMEX study are comparable to the
AIRMEX project. The table contains minimum, maximum, indoor data from similar studies in Oxford (Lai et al., 2004) and
3680 O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684

Table 3
Comparison of mean VOC concentrations (mg m 3
) from the AIRMEX study and the Expolis-Helsinki study.

Airmex (Arithmetic Mean) Expolis-Helsinki (Arithmetic Mean)


(Edwards et al., 2001a; Jantunen et al., 1999)

Outdoor Residential Workplace Personal Outdoor Residential Workplace Personal


Benzene 3.2 4.4 2.8 4.7 1.7 2.2 3.9 3.4
Toluene 11.5 11.7 12.6 22.4 5.6 20.4 32.3 25.3
Ethylbenzene 2.2 1.5 2.4 3.2 1.0 2.9 16.1 7.7
m/p-Xylene 5.7 3.8 6.2 10.5 3.1 7.8 38.8 25.0
Hexanal 0.9 32.3 16.4 22.2 2.1 11.6 5.0 8.2
n-Decane 6.2 17.3 14.4 24.5 1.1 5.3 13.9 16.5
n-Undecane 0.6 7.2 2.2 3.0 0.7 5.1 13.0 14.3
2-Butoxyethanol n.d. n.d 4.5 n.d e 2.5 e e
a-Pinene 0.1 14.5 3.2 8.3 2.1 16.1 5.5 10.2
D-Limonene 0.3 29.2 9.4 26.1 e 31.6 14.2 18.7

a number of German cities (Schlink et al., 2004). The biggest identified formaldehyde and hexanal as being among the main
differences found from these studies are the somewhat higher aldehydes detected in indoor air.
concentrations in the German study for toluene and lower Formaldehyde has recently been identified as carcinogenic to
concentrations for n-decane and n-dodecane, which might be humans (IARC, 1982, 2006), and its median I/O ratio of approxi-
attributed to local sources but needs to be further studied. mately 6 underlines the need to minimize emissions from building
Using the data provided in the Table 2, indoor/outdoor (I/O) and products, household products and furnishings inside closed envi-
private house/office (Ho/Of) ratios were calculated with the aim to ronments. Other compounds of concern are 2-butoxyethanol and D-
identify compounds that are typical for these micro-environments. limonene that are skin contact allergens (class III and IIB, respec-
tively NKB, 1994). 2-butoxyethanol is used as a solvent in spray
3.1. Indoor/Outdoor (I/O) ratios and home to office ratios lacquers, enamels, varnishes, and latex paints and as an ingredient
in paint thinners, paint strippers, and varnish removers (ATSDR,
The I/O ratio shown in Fig. 1 was calculated by dividing the 1999), whereas D-limonene is widely used in cleaning products
median indoor concentrations (offices and classroom) by the (Steinemann, 2009; Rodrigues et al., 2009). Besides its contact-
median outdoor concentrations for each location and compound. allergenic properties, D-limonene has been proven to add ultra-
The data are extracted from Table 2. fine particles to indoor environments through formation of ozone
A practical implication of the findings shown in Fig. 1 and mediated secondary aerosol (Weschler and Shields, 1999), which
Table 4 may be that when investigating indoor pollutants the has also been connected with sensory irritation in office environ-
sampling strategy should especially focus on those compounds ments (Wolkoff et al., 2006). In the category of compounds with
which have an I/O ratio of >2. However, from the I/O ratio values a ratio of almost 1 we find benzene, toluene, the xylenes and the
the compounds can also be divided into categories ranging from trimethylbenzenes. The levels found for these compounds indoors
being predominantly indoor pollutants (ratio > 6) to being originate predominantly from the polluted outdoor air penetrating
pollutants not deriving from indoor sources (ratio approaching 1). into the indoor environment and they are associated with auto-
In Table 4 these ratios are listed. In the first category we find mobile emissions (Chan et al., 1991; Barrefors and Petersson, 1993;
formaldehyde, D-limonene and hexanal, which are mainly origi- Lawryk et al., 1995). Benzene is of concern as known human
nating from indoor sources. The findings for formaldehyde and carcinogen, and the common practice of improving indoor air
hexanal are in agreement with Barguil et al. (1990) who confirmed quality by opening windows is not applicable for this pollutant. The
the existence of indoor aldehyde sources in residential homes and only practical way to abate this category of compounds in the

Fig. 1. Ratio median concentration indoor working/school environment against median concentration outdoors for all data collected in the frame of the AIRMEX project.
O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684 3681

Table 4 Table 5
Ratio-categories obtained by dividing median indoor concentration of offices/ Ratio-categories obtained by dividing median indoor concentrations in private
classrooms by median outdoor concentrations. houses by median indoor concentrations in offices/classrooms (Ho/Of ratios).

Category Compounds Category Compounds


Ratio > 6a Formaldehyde, hexanal, D-limonene, a-pinene, Ratio > 2 Hexanal, D-limonene, a-pinene
2-butoxyethanol Ratio 2 > x < 1 n-Decane, n-undecane, acetone, acetaldehyde,
Ratio 6 > x < 4 Acetaldehyde, acetone, 1-butoxy-2-propanol formaldehyde, propanal, n-heptane, n-dodecane
Ratio 4 > x < 2 n-Undecane, propanal, methylcyclohexane, n-dodecane, Ratio  1 Benzene, methylcyclohexane, ethylbenzene,
1-butanol n-hexane, toluene, 1,2,4-trimethylbenzne, 1-butanol,
Ratio < 2 Benzene, ethylbenzene, n-hexane, n-heptane, toluene, m/p-xylene, o-xylene
1,2,4-trimethylbenzene, m/p-xylene, o-xylene
a
Ratio > 6 or ambient air concentration close to zero.

in Europe (EXPOFACTS) is important together with timeeactivity


indoor environment is through forced ventilation with filtering of patterns and may differ between geographical locations and
the air. between seasons of the year. However, also potential geographical
Analogue to the I/O ratio, a home to office ratio (Ho/Of) is ob- and seasonal variations in indoor concentrations must be consid-
tained by dividing the median concentrations calculated for each ered. The degree of scattering in the present indoor air concen-
compound in the private homes by the median concentration tration dataset for individual compounds and for individual indoor
calculated for offices/classrooms. micro-environments can mask geographical and seasonal trends.
The Ho/Of ratio is displayed for all compounds in Fig. 2 and Thus data were pooled for public buildings, private homes, schools
Table 5. It is evident that the two most abundant compounds in the and kindergartens assuming that any geographical and seasonal
private-house micro-environment are the terpenes a-pinene and variation would equally affect concentrations in these indoor
D-limonene. Apparently such uses are more common in private
environments. Furthermore, three groups of individual compounds
homes than in offices/classrooms. a-Pinene is frequently used in were examined as the sum of the individual concentrations, namely
perfumes, cleaning products and fragrances (Steinemann, 2009; aromatic hydrocarbons, terpenes and aldehydes (Table 6).
Rodrigues et al., 2009) and just as D-limonene it may cause skin
and eye irritation and contributes to the formation of strong airway
irritants in terpene/ozone reaction mixtures (Wolkoff et al., 2006). 4.2. Geographical variation
Although a large number of terpene ozonolysis products have been
identified (Calogirou et al., 1999; Glasius et al., 2000) it is not The geographical variation was analysed by dividing the data
known, which are responsible for the irritation of skin, eye, and into two groups (Central-North and South Europe) and visualized in
airway. However, the present findings of high Ho/Of as well as I/O the form of cumulative probability plots of observed concentrations
ratios for terpenes may be of relevance for future indoor air quality and fitted curves assuming log-normal distributions. In Table 7 the
guidelines (Kephalopoulos et al., 2007). utilised parameters are presented.
A clear difference between north and south was evident for the
4. Geographical and seasonal variations in indoor indoor concentrations of aromatic hydrocarbons (Fig. 3). In absence
concentrations of the measured compounds of indoor sources for this group of compounds (Table 4) the
northesouth difference is attributed to a similar trend for outdoor
4.1. Introduction concentrations. In fact the ambient air pollution levels around the
investigated public buildings were notably higher in the southern
A number of variables must be taken into account when setting European cities of Athens, Thessaloniki and Catania. Higher
up probabilistic European exposure scenarios. Data on different concentration of aromatic hydrocarbons in outdoor environments
body characteristics (e.g. bodyweight) for the various populations in the south of Europe may be explained by different traffic patterns
fi

Fig. 2. Distribution of home/office ratios.


3682 O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684

Table 6
Groups of substances evaluated for geographical and seasonal variations.

Group Compounds
Aldehydes Formaldehyde, acetaldehyde, hexanal, propionaldehyde
Aromatic HC Benzene, toluene, 1,2,4-trimethylbenzne, ethylbenzene,
m/p-xylene, o-xylene
Terpenes a-pinene, D-limonene

Table 7
Parameters used for data fitting: Log-Normal distribution (mg m 3
).

Substance group Geographical Mean Median SD 95% confidence interval


seasonal
Aldehydes Warm 58.869 52.000 30.793 5.138
Cold 47.400 41.400 31.669 5.173
North 56.307 49.400 32.606 4.508
South 44.837 43.200 27.921 6.080

Aromatic HC Warm 24.613 15.900 22.723 3.764 Fig. 4. Geographical variation of terpenes.
Cold 31.863 18.500 36.126 5.963
North 15.559 13.300 9.051 1.258 There is a difference in the aldehydes concentrations between
South 59.051 49.650 40.385 8.741
north and south of Europe (Fig. 5), which fits well with the
Terpenes Warm 13.357 6.300 16.358 2.823 extended use of wood products in north Europe. Aldehydes sources
Cold 35.975 18.450 60.669 10.510
are predominantly pressed wood products and furniture made
North 23.994 11.350 47.338 6.696
South 26.478 12.000 40.749 9.906 with pressed wood products, ureaeformaldehyde foam insulation
(UFFI), combustion and environmental tobacco smoke, durable
press drapes, other textiles, and glues (WHO, 1989; Health Canada,
2005). In particular for hexanal a major source has been demon-
and a significant amount of passenger vehicles not equipped with strated to be the chemical reaction of oxidants in the air with
a catalytic converter (Karakitsios et al., 2006, 2007). The observed linoleic acid (Svedberg et al., 2004) deriving from wood products.
trend for aromatic hydrocarbons is in agreement with recent
studies on benzene, which investigated the relation between
pollution levels and the latitude of the place the samples were 4.3. Seasonal variations
taken from (Ballesta et al., 2000; Cocheo et al., 2000). In the latter,
the observed increase in annual average benzene concentrations In the work of Diez et al. (2003) a general increase of VOC
from north to south was explained with the difference in prevailing concentrations in the cold season is reported, mainly due to lower
meteorological conditions, such as local wind speeds. However, the ventilation and air exchange rates. However, this effect depends on
Cocheo study was conducted in Copenhagen, Antwerp, Padua, the specific VOC, of the emission sources, the building type, the
Murcia and Athens and did not include cities from eastern Europe, geographic location, the outdoor air quality and other factors
what makes a direct comparison difficult. (Schlink et al., 2004).
For the group of terpenes there was no substantial difference To identify a possible seasonal variation of the indoor air
between north and south (Fig. 4), which may be due to the fact that concentrations the division of the data into two groups was
their indoor sources are related to modern lifestyle which clearly complicated by the fact that the measurement campaigns for each
does not differ substantially between the various areas of Europe city did not take place simultaneously but they were spanned over
that have been included in the present study (terpenes sources: a period of several years. Thus, as criterion for the categorisation of
fragrances, cleaning products). the data, the ambient temperature of the city during the campaigns
was utilised. For each geographical location data were pooled
together for the warmest of the two campaigns and classified as the

Fig. 3. Geographical variation of aromatic HC. Fig. 5. Geographical variation of aldehydes.


O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684 3683

Fig. 6. Seasonal variation of terpenes. Fig. 8. Seasonal variation of aldehydes.

warm period, whereas the rest of the data have been used to form 5. Conclusions
the so called cold period. In Table 1 the geographical and seasonal
division is presented. The AIRMEX project is the most recent of a series of pan-
For terpenes the analysis shows a clear difference between European projects aiming to assess personal exposure and taking
warmer and colder seasons (Fig. 6) with indoor concentrations an inventory of VOC levels in indoor environments in several
being lower during the warm season. Terpenes react rapidly with European cities. Results presented in this work represent an elab-
oxidants in the air such as ozone, which is much more abundant in oration of the whole set of raw-data and are hereby made publicly
the warm season due to the higher photochemical activity and accessible via a database (http://web.jrc.ec.europa.eu/airmex/).
penetrates from the outdoor air. This finding provides a good Moreover, the statistical analysis of the data in the present paper
indication of the importance of indoor air chemistry for the provides a good indication of a possible influence of indoor air
concentration levels of various substances. An additional explana- chemistry on the concentration levels of reactive substances, which
tion could be the increased ventilation rates during the warm should be taken into consideration in future indoor air quality
season. No difference between the warm and the cold season was guidelines. Attention should be taken in indoor air quality moni-
evident for the aromatic hydrocarbons (Fig. 7), which is expected toring campaigns to pollutants with an indoor/outdoor ratio higher
from the fact that they do not have significant indoor sources and than 2. A clear difference between north and south was evident for
therefore an increased ventilation rate does not really influence the indoor concentrations of aromatic hydrocarbons which can be
their indoor concentration. attributed to the different kinds of vehicle fleet in the studied cities.
During the warm season the indoor concentration of alde- For terpenes no similar trend was revealed for geographical varia-
hydes appeared to be slightly higher than during the cold season tion but there was a significant difference between the values ob-
(Fig. 8), which may support the hypothesis of ozone penetration tained for the warm and the cold period with concentrations being
(formaldehyde is an oxidation product in the terpene/ozone lower during the warm period. Besides potentially increased
reaction (Calogirou et al., 1999) and hexanal is an oxidation ventilation rates in the warm period, this can be attributed to the
product of ozone with linoleic acid). However, also increased reactivity of terpenes with ozone penetrating from outdoor air,
emission/evaporation/desorption rates from their indoor sources which is more abundant during warm periods. Our findings of
may play a role. higher concentration of aldehydes (ozone oxidation reaction
products) during the warm period support this hypothesis.

Acknowledgements

The authors wish to acknowledge all participants at this project.


Without the on-site local coordination this project could not have
been realized. Namely the coordinators are: Dr. Cuccia and Dr.
Nastri from the Regione Siciliana, Azienda Unita Sanitaria Locale
N.3 in Catania, Italy; Dr. Bloemen and his collaborators from the
RIVM in Bilthoven, Netherlands; Prof. Herbarth and his collabora-
tors from the Umweltforschungszentrum in Leizpig, Germany; Dr.
Kalabokas from the Research Centre for Atmospheric Physics and
Climatology Acacedmy of Athens in Greece; Dr. Nikolaou from the
Organisation for the Masterplan & Environment in Thessalonica,
Greece; Dr. Michael and his collaborators from the Ministry of
Health in Nicosia, Cyprus; Dr. Kauppi and her collaborators from the
Finnish Environment Institute, Dr. Putus from the Ministry of Social
Affairs and Health, Dr. Säteri and her collaborators from the
Ministry of Environment; Dr. Nurminnen and Dr. Jylkkä from the
Fig. 7. Seasonal variation of aromatic HC. City of Helsinki in Finland; Dr. McLaughlin and his collaborators
3684 O. Geiss et al. / Atmospheric Environment 45 (2011) 3676e3684

from the University College Dublin, Dr. Fitzpatrick, Dr. Healy and Jantunen, M.J., Katsouyanni, K., Knoppel, H., Kuenzli, N., Lebret, E., Maroni, M.,
Saarela, K., Sram, R., Zmirou, D., 1999. Final Report: Air Pollution Exposure in
Dr. McCartan from the Dublin City Council in Dublin, Ireland; Prof.
European Cities: The Expolis Study. Kuopion Yliopiston Painatuskeskus, Kuopio.
Zaray and Dr. Mihucz from the Eötvös Lorand University in Buda- Karakitsios, S., Papaloukas, C., Kassomenos, P., Pilidis, G., 2006. Assessment and
pest, Hungary. prediction of benzene concentrations in a street canyon using artificial neural
networks and deterministic models. Their response to what if scenarios.
Ecological Modelling 193, 253e270.
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