Building and Environment 66 (2013) 173e180

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Building and Environment

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Inltration or indoor sources as determinants of the elemental

composition of particulate matter inside a school in Wroc1aw, Poland?
Anna Zwo

ska b, Jerzy Zwo

zdziak a, *, Izabela Swka a, Barbara Krupin zdziak a, Alicja Nych a
a
Environmental Protection Engineering Institute, Wroclaw University of Technology, Wyb. Wyspianskiego 27, 50 370 Wroclaw, Poland
b
Department of Chemistry, University of Antwerp, Belgium

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

Article history: Childrens exposure to air pollution requires a focus on air quality in places where they spend most time,
Received 11 February 2013 e.g. in schools. Therefore, understanding how indoor elemental concentrations relate the outdoor ones is
Received in revised form necessary to create healthy indoor school environment. The aims of this study were to examine the
25 April 2013
elemental composition of particulate matter (PM1, PM2.5, PM10) in the school and also to investigate to
Accepted 25 April 2013
what degree indoor elemental concentrations are affected by outdoor air or generated inside the school.
The measurements were performed inside and outside the public school building in the centre of the
Keywords:
city. It was observed that concentrations of most elements were higher at school than outside. The
PM1
PM2.5
dominant elements in PM1 both indoors and outdoors were S, Cl, K, and Zn. PM2.5 and PM10 fractions
PM10 inside the school were clearly enriched in elements of mineral origin, additionally S, Zn, K and Cl were
School also present in high concentrations both indoors and outdoors. Results suggested that a signicant
I/O ratio contribution to indoor Zn, Pb and S concentrations in the PM2.5 fraction was from penetration of outdoor
Elemental analysis air. 88%, 80% and 90% of the observed total variations in indoor concentrations of Zn, Pb, and S were
explained by the linear relationship between indoor and outdoor concentrations. The lack of correlation
between indoor and outdoor concentrations obtained for Si, Ca, Ti, Sr indicated that these metals were
more likely to originate from indoor sources.
2013 Elsevier Ltd. All rights reserved.

1. Introduction Recent most intensive studies are now focusing on source

There is great interest recently in investigating health effects
related to ambient particulate matter (PM) [1e10]. According to a
study of Tzivian [11], air pollutants can be ranked in decreasing
order of their impact on the respiratory system, namely PM2.5 >
PM10 > SO2 > O3 > NO2. In addition, the airborne concentration of
toxic substances, such as lead, zinc, chromium, copper, sulfur in-
creases with decreasing particle size [12]. Grahame and Schlesinger
[3] in a review paper concluded that there is strong evidence
supporting the negative health effects of suspended particles,
however, the specic properties of PM are still unknown.
High concentrations of PM2.5 and PM10 in cities, often exceeding
air quality standards, have also raised concerns about the indoor
environment, especially in schools in city centers [13e19]. Children
spend up to 8 h per day in school and were found to be very sus-
ceptible to effects of PM on lung functions [16,17,20].
* Corresponding author. Tel.: 48 713202500.
E-mail address: anna.zwozdziak@pwr.wroc.pl (A. Zwo

zdziak).
identication of PM in ambient air to assess likely health outcomes
of specic sources, such as trafc, fuel combustion, crustal sources,
etc. In this paper we take an approach to the source apportionment
of trace metals and crustal elements, that are components of PM1,
PM2.5 and PM10, in indoor school environments. We attempt to
determine whether there is a coherence between outdoor and in-
door air related to the contribution of different elements in PM.
Identication of the main PM indoor sources would help their
mitigation and consequently minimize adverse health effects
of PM.
2. Materials and methods
2.1. Sampling sites
Simultaneous indoor (in the school patio) and outdoor (on the
school roof) PM10, PM2.5 and PM1 concentration measurements
were conducted in a secondary school located in the centre of
Wroclaw (ca. 7,00,000 inhabitants) in south-western Poland. This
four-storey school building was chosen as the measurement site.
Inside the building there is a huge patio (ca. 30 m long, 15 m wide,

0360-1323/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.buildenv.2013.04.023
174 A. Zwo
zdziak et al. / Building and Environment 66 (2013) 173e180
10 m high) covered with a glass roof. Corridors and classrooms
doors run around the perimeter of patio on each oor. Fig. 1 de-
scribes the sampling sites.
The classrooms are naturally ventilated most often through
doors which are opened to the corridors during breaks. Thus,
airing the classroom during breaks makes exchanging the air
between the patio and classroom possible, particularly in winter-
time. Therefore, the indoor air quality in the school patio can be
representative for classrooms. In addition, spirometric measure-
ments were carried out in the hall, having the direct contact with
patios air. The measurements of PM concentrations in outdoor air
were performed at one height within the roof boundary layer,
extending from the ground to the roof with the roof being the same
height as the tree tops. This is the level where air is exchanged
between the street and the boundary layer. Pollutants from auto-
mobiles and home furnaces are mainly emitted to this layer. The air
from this layer then inltrates into the school building.
2.2. Sampling of suspended particulate matter
The measurements were performed on a daily basis: 24 h during
weekends or 8 h (teaching hours, 08:00 ame4:00 pm) and 16 h
(4:00 pme08:00 am) during workdays, for one week per month
from December 2009 to October, 2010 (no measurements in July &
August due to school holidays) with the use of Harvard cascade
impactors (MS&T Area Samplers, Air Diagnostics and Engineering,
Inc., Harrison, ME, USA). The pumps (Air Diagnostics and Engi-
neering, model SP-280E) were set at an airow of 23 dm3/min for
PM1, and 10 dm3/min for PM2.5 and PM10. The particles were
collected onto 37 mm diameter Teon membrane lters (PALLFLEX,
TK15-G3M). All lters were pre- and post-conditioned in a clean
room with environmentally controlled temperature and humidity
prior to weighing. Weighing was carried out with an electronic
microbalance (Santorius 000 V001). Elemental concentrations in
different PM fractions were analyzed using energy-dispersive X-ray
uorescence (EDXRF- Epsilon-5, PANalytical, The Netherlands)
spectroscopy in the Micro and Trace Analysis Centre of the Uni-
versity of Antwerp, Belgium. Data quantications are described
elsewhere [21,22]. In total, 20 elements were determined (Al, Si, S,
Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Sr, Cd, Sb and Pb).
Samples of particulate matter were divided into two periods:
winter (December, January, February, March) and summer (April,
May, June, September). The outdoor meteorological parameters like
temperature, humidity, wind speed and direction were collected
from the nearest air monitoring station. The weather was cold
(daily mean temperature ranged from -8  C to 3  C) and more
Fig. 1. Inside view of school building and location of sampling sites: 1 e a hall with classrooms and a platform with the sampling equipment (the arrow indicates location of 2nd
sampling site on the school roof), 2 - sampling instruments.
humid (daily mean relative humidity ranged from 88% to 92%)
during the winter sampling periods when compared to the summer
periods (5  C to 15  C; 60%e90%). The prevailing wind directions
were predominantly from the south west, west and north west for
both periods. During winter, the wind speed was in the range 0.9e
3.6 m/s, while in summer it was 0.3e3.6 m/s. In the indoor site, air
temperature, humidity and air velocity were checked using Mini
HydroThermo-Anemometer (Extech Instruments) four times a day
throughout the sampling durations. The indoor temperature varied
slightly from 18  C to 21  C, regardless of the season; relative hu-
midity ranged between 31% and 54%; air velocity was below the
detection limit (0.5 m/s).
3. Results and discussion
3.1. Mass concentrations of PM1, PM2.5 and PM10
Seasonal mass concentrations (24 h average values) of PM1,
PM2.5 and PM10 inside and outside the school are summarized in
Table 1. From the point of view of childrens health, the more
relevant time e averaging period should be teaching hours (from
8:00 am to 4:00 pm) than the 24 h averaged value. However, to
facilitate comparisons with recognized air quality guidelines and
standards it is important to know 24 h means. The World Health
Organization (WHO) Air Quality Guidelines (AQG) [5] are stricter
than the EU Air Quality Standards (AQS) [23]. The short-term WHO
AQG for PM10 is 50 mg/m3 (24 h mean). The EU AQS 24 h mean for
PM10 is the same value but can be exceeded 35 days a year. The
short term (24 h mean) WHO AQG for PM2.5 is 25 mg/m3. There is no
corresponding short term (24 h mean) limit in the EU AQS. How-
ever, there is currently an EU AQS target annual concentration of
PM2.5 of 25 mg/m3 which will become a concentration limit in
January 2015.
Before comparing the measured PM values to their respective
guidelines, the different PM1/PM2.5/PM10 fractions indoors and
out during winter and summertime conditions were analyzed. The
PM1/PM2.5 and PM2.5/PM10 ratios exhibited a seasonal behavior.
Higher PM2.5/PM10 ratios (mean values) were recorded in winter:
0.87 for indoors and 0.86 for outdoors, whereas in the summer
months this ratio fell to around 0.31 for indoors and 0.65 for out-
doors. In winter, the ratio exceeded WHOs normal range of 0.5e0.8
for developed countries [5], however, was comparable to values of
0.8e0.9 observed in German monitoring stations inuenced by
trafc [24]. The seasonal changes seem to be predominantly due to
different contribution of dust emission sources, both indoors and
outdoors. Firstly, the higher outdoor PM2.5/PM10 ratio in winter was
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zdziak et al. / Building and Environment 66 (2013) 173e180 175

Table 1 PM2.5 concentrations in classrooms exceeded WHO limits

Overview of the indoor and outdoor 24 h mean concentrations of PM1, PM2.5 and [14,19,25,26]. It is also important to realize that children usually
PM10 in a study school for both sampling periods (values in mg/m3).
spend more time in school than outside and therefore are subjected
Indoor Outdoor to greater exposure to PM concentrations inside school than in the
Mean S.D. Min Max Mean S.D. Min Max ambient air, so the indoor limits should be stricter.
The discussion above concerned 24 h averages but more
Winter
PM1 21.2 5.3 12.8 33.4 25.5 7.8 16.4 40.7 attention should be focused on the period that children are
PM2.5 59.8 21.6 18.2 86.6 49.1 15.6 24.4 67.7 attending school. To compare our results to some other studies we
PM10 68.5 21.8 21.6 93.1 56.8 17.3 26.2 88.5 calculated both 8-h median and mean concentrations and the re-
Summer
sults are shown in Table 2. It is worth drawing attention rst to
PM1 8.5 3.6 4.2 11.6 8.9 3.4 3.7 13.2
PM2.5 13.5 4.1 8.9 18.8 16.0 9.1 8.0 21.6 median PM10 values which are very similar in winter (110 mg/m3)
PM10 43.1 17.9 12.6 68.4 24.7 10.5 11.6 46.6 and summer (108 mg/m3) which suggest the indoor PM10 con-
centrations is activity related. Secondly, the similarity in winter and
summer results differs from study [25] where are seasonal varia-
presumably a consequence of higher particulate emission from tions (Table 2).
combustion sources than in summer. Secondly, in summer in- To express the relationship between indoor and outdoor particle
creases the contribution of coarse fraction, i.e. from road re- concentrations, the indoor-to-outdoor (I/O) ratio was calculated for
suspension, and hence decreases the PM2.5/PM10 ratio. In summer each sampling day (day time corresponds to teaching hours and
there was also a great difference between the PM2.5/PM10 ratios for night time corresponds to non-teaching hours) and each period
indoors and outdoors (0.31 versus 0.65). It is sufcient to compare (Table 3). For day time samples, the average I/O ratios varied from
the average daily concentration of PM1, PM2.5 and PM10 indoors and 1.3 to 5.6 in the summer, and from 0.8 to 2.5 in the winter. The high
outdoors (Table 1) and it becomes clear that inside the school was I/O ratio for PM10 and PM2.5 suggests, that a substantial fraction of
mainly generated aerosol with diameters in the range 1 mme2.5 mm both ne and coarse particles was generated by indoor sources i.a.
in winter, and in summer in the range of 2.5 mme10 mm. In other dust re-suspension due to children activities. This was conrmed
words, the analysis of differences in concentrations of PM10ePM2. 5, by the lower ratio of the concentrations at night (I/O < 1.0).
and PM2,5ePM1 showed that the indoor air was enriched in the Combining the results in Tables 1 and 2 can be concluded that the
PM2,5e1 fraction as compared to the air outside in winter, whereas dust sources inside the school inuence PM concentrations indoors
in summer was enriched in the PM10e2. 5 fraction. Thus, there were both in winter and in summer. This is particular evident during
strong sources of PM inside the school mostly affecting the ner teaching hours when children stay at school. Particulate matter
fraction in winter, and the coarser fraction in summer. indoors is mainly allocated to the PM2.5e1.0 fraction in winter,
In winter, the local outdoor PM10 and PM2.5 concentrations whereas in summer to the coarse fraction (PM10e2.5).
exceeded the short-term WHO guidelines quite often, as evidenced Assessing childrens exposure to aerosols present in the school
by the 24 h means and the concentration ranges shown In Table 1. air is important to characterize the chemical composition of
PM concentrations were distinctly lower in the summer. As shown particles for its potential to cause adverse health effects. It is
by this data, the concentrations of PM2.5 and PM10 were higher widely believed that substances of crustal origin cause less health
inside than outside the school in wintertime, whereas in sum- problems than those resulting from combustion processes
mertime only PM10 concentrations were higher inside. PM1 con- [30,31]. However, crustal-associated ne PM may interact with
centrations reached comparable levels indoors and outdoors for other types of particles in producing adverse health outcomes
both seasons with the outdoor concentrations being higher than [32]. Some studies showed the association between Si and other
the indoor concentrations by 20% and 5% for winter and summer crustal elements in PM2.5 and some irregularities in the func-
periods, respectively. tioning animal organisms [32e34]. However, it was not clear if
The mean indoor concentrations of PM1, PM2.5, PM10 were in effect was solely due to crustal elements or whether some other
winter: 21.2; 59.8 and 68.5 mg/m3 whereas at the same time out- components of PM2.5, whose concentrations correlated with that
door were: 25.5; 49.1 and 56.8 mg/m3, respectively. This is consis- of crustal elements, were more toxic. This is a very difcult issue
tent with several other studies that have shown that PM10 and to resolve.

Table 2
Indoor and outdoor concentrations (minemax) of PM2.5 and PM10 for various schools in Europe (w- winter samples; s e summer samples).

References City, country PM fraction Concentration, mg/m3 Comments

Outdoor Indoor

[28] Mnchen, Germany PM10 24.4 (4.7e127) 118.2 (57.8e209.9) 2 classrooms, teaching hours, 2005,
PM2.5 17.0 (5.1e64) 37.4 (19.3e105.9) median (minemax)
[14] Mnchen, Germany PM10 21 (11e52) 117 (71e172) 6 schools, teaching hours, mean (minemax)
[29] Antwerp, Belgium PM2.5 61 (11e166) 27 schools, 12 h (day), 2002e2003
Mean(minemax)
[27] Mnchen, Germany PM10 92 (16e313)w Winter 79, summer 74, classrooms
65 (18e178)s 2004/2005; teaching hours
Median(minemax)
PM2.5 20 (3e81)w
13 (5e35)s
This study Wroc1aw, Poland PM10 67 (30e78)w 110 (94e190)w School hall, teaching hours
30 (9e35)s 108 (60e154)s 2009e2010
Median(minemax)
PM2.5 55 (20e67)w 107 (44e143)w
11 ( 3e15)s 25 (12e40)s
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Table 3 Table 5
Overview of the indoor/outdoor mass concentration ratios (I/O) for PM1, PM2.5 and 24 h elemental concentrations (standard deviation) of indoor (I) and outdoor (O)
PM10. PM2.5 for both periods (values in ng/m3).

Winter Summer Element PM2.5(I) winter PM2.5(O) winter PM2.5(I) summer PM2.5(O) summer

PM1 PM2.5 PM10 PM1 PM2.5 PM10 Si 1963(1507) 259(240) 292(155) 193(89)
K 830(330) 528(157) 144(56) 110(40)
Day time
Ca 2227(1476) 159(57) 259(176) 89(49)
0.8  0.2 2.0  0.8 2.5  1.7 1.3  0.4 4.1  2.9 5.6  2.9
Ti 122(92) 11(10) 14(8) 7(5)
Night time
Fe 525(412) 215(158) 126(127) 78(31)
0.9  0.1 0.8  0.1 0.8  0.0 0.8  0.1 0.7  0.1 1  0.3
Sr 7.3(3.8) 2.2(0.7) 1.5(0.7) 0.7(0.6)
Cr 6.6(3.1) 4.3(2.2) 2.5(0.9) 1.6(0.8)
Ni 2.4(1.2) 4.0(1.4) 1.3(1.6) 0.7(0.4)
Mn 46(48) 23(11) 14(7) 9(5)
3.2. Element concentrations in PM1, PM2.5 and PM10 Cu 50(12) 40(16) 36(23) 20(15)
Zn 267(116) 227(102) 46(19) 43(20)
In total, 20 elements were determined (Al, Si, S, Cl, K, Ca, Ti, V, Cr, As 4.0(3.0) 4.9(3.4) 2.0(2.0) 1.2(1.3)
Mn, Fe, Ni, Cu, Zn, As, Se, Sr, Cd, Sb and Pb). Almost all elements Pb 85(23) 81(27) 34(10) 27(13)
Al 561(456) 48(49) 68(47) 32(25)
were detected in each sample [16], except for Se, Cd which were not
S 1720(770) 1946(971) 768(211) 727(292)
detected in 72% and 50% of the samples, respectively. Sb was not Cl 804(629) 1589(845) 65(60) 118(250)
detected at all, and the concentrations of V were at the detection Al 561(456) 48(49) 68(47) 32(25)
limit. Al was detected only in 52% of PM1 samples, and hence Al was
not included in PM1 analyses (see Table 4).
In Tables from 4 to 6 elemental concentrations of suspended concentrations. Stranger et al. [30] reported similar concentrations
particulate matter PM1, PM2.5 and PM10 collected indoors and of PM2.5 for most elements in 27 classrooms in Antwerp. In that
outdoors during the winter and summer periods are listed. The study, however, Zn and Cu concentrations were much lower,
dominant trace elements by mass in PM1 both indoors and out- probably because of the lower outdoor concentrations.
doors were S, Cl, K, and Zn in wintertime, suggesting a signicant Only selected elements are discussed at policy level in the Eu-
contribution of combustion processes to PM1 concentrations ropean Union. Currently, there are only annual target values for Ni,
[35,36]. For PM1, (Table 4) the wintertime indoor concentrations of As, Cd (they enter into force from 2013) and a limit value for Pb.
Si, K, Ca, Ti, Fe, Mn, Cu, Zn, Pb and S were higher than outdoors. The These elements should not exceed the annual standard of 20 ng/m3,
summertime indoor elemental concentrations were lower than 6 ng/m3, 5 ng/m3 and 0.5 mg/m3, respectively [23]. For these ele-
wintertime. Indoor and outdoor Sr, Cr, Ni, Zn, As, Pb and S con- ments the standards were much higher than the observed concen-
centrations demonstrated rather small differences both in winter trations. Cadmium was below the detection limit for most samples
and summer. The PM2.5 fraction inside the school (Table 5) was and has not been reported in Tables 4e6. Ni had a maximum con-
clearly enriched in elements of mineral origin (Si, Ca, Ti, Fe, Sr, Al). centration value of 4 ng/m3 and maximum Pb concentration was
Indoor concentrations of K, Zn, Cr, Ni, Mn and Pb were higher in- 85 ng/m3. However, the reported levels for As in some samples
doors and indoor Cl concentrations were lower indoors for both reached 6 ng/m3 but the extreme concentrations days are not
summer and winter whereas indoor S and As concentrations were representative of the true annual average. Nevertheless, there is an
higher indoors only in summer. Similar behavior was observed for urgent need to control both indoor and outdoor As concentrations.
PM10 fractions (Table 6) except for indoor concentrations of S and Cl Much higher day time (teaching hours) indoor concentrations
in summer which were higher than outdoors. On contrary, the in- than outdoor ones were observed for crustal elements: Si, Ca, Ti, Sr,
door As concentration was higher in winter. It should be noted that Fe, Mn, particularly in the winter (Fig. 2). As pointed out in several
elemental composition of PM2.5 was very close to the composition other studies [13,19,27,28], the reason for the high I/O ratio was
of PM10, which suggests that elements in particles from PM2.5 probably re-suspension of settled mineral dust during cleaning
fraction contributed signicantly to PM10 fraction. In summer, both (sweeping) and children movement. Human activity contributes
indoor and outdoor concentrations of most elements in all fractions mainly to re-suspension of larger particles but that was not
were considerably lower than observed in winter. Elements of conrmed in our study for PM10. However, for PM2.5, the highest I/O
mineral origin, sulfur and chlorine occurred in the highest

Table 6
Table 4 24 h elemental concentrations (standard deviation) of indoor (I) and outdoor (O)
24 h elemental concentrations (standard deviation) of indoor (I) and outdoor (O) PM10 for both periods (values in ng/m3).
PM1 for both periods (values in ng/m3).
Element PM10(I) winter PM10(O) winter PM10(I) summer PM10(O) summer
Element PM1(I) winter PM1(O) winter PM1(I) summer PM1(O) summer
Si 2529(1387) 793(534) 2639(1519) 1746(1016)
Si 104(81) 29(17) 40(17) 28(12) K 928(282) 600(157) 492(218) 297(162)
K 390(148) 308(97) 84(32) 77(29) Ca 3415(1253) 578(307) 2467(1477) 837(735)
Ca 35(13) 6(2) 27(16) 18(15) Ti 172(86) 37(20) 131(84) 61(42)
Ti 3.4(5.0) 0.7(0.6) 1.5(0.9) 0.8(0.6) Fe 655(402) 422(186) 570(234) 604(368)
Fe 92(64) 35(16) 41(74) 18(5) Sr 11(4) 3.9(1.3) 8.0(4.9) 3.4(2.4)
Sr 0.7(0.3) 0.6(0.3) 0.5(0.3) 0.5(0.2) Cr 6.8(2.4) 4.5(1.1) 6.1(2.5) 4.2(3.4)
Cr 1.5(0.5) 1.4(0.5) 0.8(0.5) 0.8(0.4) Ni 2.9(1.0) 2.2(0.7) 2.3(1.0) 2.2(2.4)
Ni 1.0(0.3) 0.8(0.2) 0.7(0.7) 0.3(0.2) Mn 45(51) 28(8) 28(11) 23(10)
Mn 18(28) 7.2(3.4) 5.7(2.5) 5.0(2.6) Cu 58(11) 48(9) 41(15) 36(18)
Cu 17(6) 13(6.0) 18(16) 13(7) Zn 276(102) 235(102) 104(36) 74(43)
Zn 146(62) 127(60) 28(12) 26(11) As 5.8(2.6) 4.9(3.2) 2.3(2.2) 3.2(2.7)
As 3.0(1.5) 3.0(1.8) 1.7(2.2) 1.2(0.9) Pb 87(18) 83(22) 44(12) 38(9)
Pb 47(12) 41(13) 18(5) 18(6) S 1744(843) 2040(1037) 892(213) 767(353)
S 920(373) 808(396) 557(211) 551(172) Cl 1141(645) 1636(688) 463(325) 317(387)
Cl 236(234) 856(279) 39(79) 89(23) Al 772(407) 195(121) 787(469) 445(287)
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zdziak et al. / Building and Environment 66 (2013) 173e180 177

Table 7
Spearman correlation between indoor and outdoor 24 h element concentrations in
PM1, PM2.5 and PM10 for both seasons (p < 0.01).

Element Winter Summer

PM1 PM2.5 PM10 PM1 PM2.5 PM10

Si
K 0.92 0.81
Ca
Ti
Fe 0.83 0.85 0.71 0.68
Sr
Cr
Ni 0.93
Mn 0.89 0.84 0.68 0.55
Cu
Zn 0.97 0.93 0.98 0.82 0.69
As 0.81 0.75 0.86
Pb 0.97 0.92 0.94 0.72
S 0.93 0.97 0.98 0.84 0.61 0.62
Cl 0.75 0.78 0.85 0.57

Fig. 2. Mean ratio between indoor and outdoor day time element concentrations in
PM1, PM2.5 i PM10 for both seasons.
ratio was observed for Ca [14], Ti (11.6), Si (7.6), Sr (3.4), Fe (2.4). The
high I/O ratio was also found for crustal elements in the PM1 frac-
tion. Fine particles could remain suspended in air for a relatively
long time and due to poor ventilation during the winter, this pro-
cess could lead to their accumulation and high levels being main-
tained all day. The I/O concentration ratios for other elements,
except for Cl, were at comparable levels but the values were mostly
above 1.0. Nevertheless, these increases in values for indoor air
were small compared with the ones for Si, Ca and Ti. This is in
accordance with the results obtained previously by Janssen et al.
[13] that showed the highest I/O ratios were for elements from
soils, namely Si, Ca and Ti. The elements that were not increased
inside schools were S, Br, Pb and Cl, which were considered as
originated from non-crustal sources.
Spearman correlations between 24 h indoor and outdoor
elemental concentrations are presented in Table 7 but only for cases
of elemental correlations with p-value < 0.01. It is interesting that
in winter the elements that were strongly correlated could be
attributed to combustion sources of: coal (S, Fe, K, Cl), waste (Mn,
Pb, Zn, Cl, As [37,38]), biomass (K, S [36]) and vehicular emissions (S,
Zn, Pb [39,40]). The existence of strong correlations for Fe, Zn, As, Pb
and S in all factions was not surprising, because these elements
were mainly concentrated in ne particles (PM2.5), and the
contribution of PM2.5 in PM10 was very high in wintertime (Tables 5
and 6). These results clearly indicate that children in the school are
exposed to a number of elements associated with the nest frac-
tion, originated from outside. The lack of correlation between in-
door and outdoor concentrations obtained for Si, Ca, Ti, Sr indicate
that these metals are more likely to originate from indoor sources.
It is consistent with their high I/O ratios, particularly in winter for
PM2.5: up to 7.6; 14, 11.6 and 3.5 for Si, Ca, Ti and Sr, respectively.
In Fig. 3 indoor day time and night time concentrations of As, Zn,
Pb and S for the PM2.5 fraction (considered the most dangerous to
health) were plotted against their respective outdoor concentra-
tions. In this linear regression function the constant which de-
termines the slope of that line is often considered as the inltration
factor and the constant term is the average indoor elemental con-
centration [41e45] An important measure in determining the de-
gree of linear-correlation of variables (goodness of t) in
regression analysis is the coefcient of determination (R2). For the
winter measurements, the coefcient of determination for Zn, Pb,
As and S were 0.88, 0.80, 0, 41 and 0.90, respectively. It means that
88%, 80%, 41% and 90% of the observed total variation in indoor
concentrations of Zn, Pb, As and S can be explained by the linear
relationship between indoor and outdoor concentrations. The other
12%, 20%, 51% and 10% of the total variation in Zn, Pn, As and S
remain unexplained. With a decrease in the R2 value, the strength
of the linear association between variables is weaker. The smallest
R2 value obtained was for As which may be interpreted as being
some independent As sources within the school of As in addition to
inltration. Table 8 presents a summary of the regression analysis
for all fractions of Zn, Pb, As and S. The highest inltration factors
were found for S, Pb and Zn both in PM1 and PM2.5. The data
indicate that the inltration of outdoor particles containing S, Pb
and Zn is the main source of indoor concentrations. It means that
from 80% (Pb, Zn) to nearly 90% (S) of ambient particles, that
penetrate indoors remains suspended. These results conrm pre-
vious analyses of the I/O ratio for Pb, Zn and S. This ratio was at 0.9e
1.2 in winter. The value close to 1.0 indicates a more efcient pro-
cess of penetration of particles containing these elements. Sulfur is
a classic marker of aerosol which penetrates from the outside,
because its indoor sources are unknown [41,46]. This explains the
highest penetration factor (0.86). Sulfur in atmospheric particulate
matter is mainly in the form of sulfates that are produced from the
oxidation of SO2. However, sulfates are also considered as primary
pollutants from the combustion of solid fuels, vehicular emissions
or biomass burning. In the global scale, the contribution of primary
sulphates to the total sulphur emissions is about 3% [47], however,
in the vicinity of combustion sources its contribution may increase
to 20e30% [48,49]. It is known that sulfates cannot form in high
temperature processes as they are not stable, but they are produced
when the temperature lowers to 430 K [50]. SO2 can also react in
the air with alkali metal oxides to form sulfates. Guo et al. [51]
comparing the SEM image of coal y ash particles and the atmo-
spheric aerosol suggested that emission from coal combustion is a
substantial source of primary sulfates in the form of CaSO4,
although airborne gypsum particles are more often attributed to
eolian particles or secondary sulfates. According to data reported by
Guo et al. [51], the fraction of sulfur emitted as primary sulfates
during coal combustion varied from 10 to 45%. We believe that high
concentrations of sulfur both outdoors and indoors were primary
178 A. Zwo
zdziak et al. / Building and Environment 66 (2013) 173e180

Table 9
Spearman correlation (p < 0.01) between As concentrations and remaining ele-
ments in PM1 and PM10 in the indoor air (in winter).

Si K Ca Ti Fe Zn Pb Al S

PM1 0.45 0.50

PM10 0.69 0.68 0.67 0.50 0.68 0.59 0.70 0.72

Similarly, the results shown in Table 8 indicate that the indoor

concentrations of Zn and Pb were highly correlated with those
measured outdoors for PM1 and PM2.5. The high inltration factors
suggest that indoor particle-bound Zn and Pb were mainly origi-
nated from outdoor emission sources, probably anthropogenic
sources such as coal combustion or vehicular emission.
In the case of arsenic, this study found a weaker correlation
between indoor and outdoor arsenic concentrations than for Zn, Pb
and S (Table 8), probably because of the existence of some As indoor
sources. Unlike Zn, Pb and S, the highest inltration factor for As
was observed for PM10 which indicated that this metal likely
originated outdoors; however, only the smaller fraction inltrated
indoors (PM1). This probably explains the I/O ratio equals 1.0 for As
in PM1 and 1.2 for PM10. Arsenic is emitted as an air pollutant
mainly from coal-fuelled power plants and copper and lead
smelters. Also, the burning of treated wood in domestic furnaces is
of particular concern, as the smoke may contain dangerous
amounts of arsenic compounds used to treat the wood. Arsenic
from combustion sources in air primarily exists in the form of
particulate matter, mostly in particles less than 2 mm in diameter
[52]. Children in schools may also be exposed to arsenic compounds
when using school equipment made from treated wood. Abrasion
of the wooden surfaces or even ceramic or wall surfaces (arsenic is
used in paints and dyes) may also be the indoor sources of As and
then it occurs in coarse fractions. The conrmation can be found in
Spearman correlations between indoor concentrations of As and
the remaining elements in PM1 and PM10 fractions (Table 9).
Arsenic was moderately correlated only with Pb and S in PM1
fraction, however, a signicant correlation was found between As
and all other elements, except for S, in PM10 fraction. The most
probable cause of the strong correlations in PM10 was the same
origin, namely the re-suspension of settled dust containing
different materials.

4. Conclusions

The results clearly indicate the existing problem of high ne

dust concentrations inside the school often exceeding the WHO
short-term guideline value for the ambient air e 25 mg/m3. In
winter, the indoor concentrations of particulate matter during
Fig. 3. PM2.5 arsenic, zinc, lead and sulfur concentrations inside (I) and outside (O) the teaching hours were several times the outdoor concentrations. This
school in wintertime.
means that children are subjected to much higher exposure to
particulate matter in school than staying outside.
sulfate particles from direct emissions during combustion pro-
The PM2.5 concentration inside the school was partly deter-
cesses. Cold weather in winter and weak solar radiations created
mined by inltration from the outside air, (mainly the fraction
unfavorable conditions for strong SO2 oxidation reactions and
PM1), and partly due to the existence of sources within the school. It
producing secondary sulfates.
was found that the aerosol formed in the school in winter was
dominated by particles with diameters in the range of 1e2.5 mm
Table 8
(the average concentration inside the school was about 39 mg/m3,
Determination coefcients R2 and inltration factors b1 (in parentheses) for Zn, Pb,
As and S in PM1, PM2.5 and PM10 (in winter). outside concentrations were about 13 mg/m3). However, in summer
the aerosol inside the school was dominated by particles in the
Zn Pb As S
range 2.5 mme10 mm, (the average indoor concentration was about
R2 (b1) 20 mg/m3 and the outdoors concentration about 9 mg/m3). Much of
PM1 0.92 (0.74) 0.85 (0,79) 0.65 (0.65) 0.75 (0.84) the variability in concentrations of Zn, Pb, S, in PM2.5 inside the
PM2.5 0.88(0.81) 0.80 (0.77) 0.41 (0.68) 0.90 (0.86)
PM10 0.22 (0.26) 0.38 (0.56) 0.66 (0.73) 0.59 (0.53)
school has been explained by the concentration from outside,
suggesting that particles containing these elements inltrated to a
 A. Zwo
zdziak et al. / Building and Environment 66 (2013) 173e180
large degree from the outdoor air. The lack of correlation between
the indoor and outdoor concentrations of the mineral elements,
indicated the existence of their sources inside the school (when I/
O > 1.0). The weaker correlation between the concentration of
arsenic in PM2.5 inside the school and outside was probably due to
the fact that arsenic came from indoor sources (most likely from the
abrasion of the treated wood surface and the glass ceramic surface)
and only partly from the outdoor air (combustion processes). The
problem of high arsenic concentrations both indoors and outdoors
requires further research. Our results show the urgent need to
continue this type of research, both in the aspect of monitoring the
elemental concentration in ne dust in the schools and outside, as
well as of the risk of respiratory dysfunction in children due to high
concentrations of toxic elements in school.
Acknowledgement
This work was supported by the National Science Centre under
project No. N304 067937 Effects of air pollution on short-term
pulmonary function changes in schoolchildren. Special thanks
are due to the school manager and teachers of Secondary School No.
13 in Wroclaw for their interest in this work and valuable support.
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