Atmospheric Environment 44 (2010) 4954e4963

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

Time-resolved measurements of aerosol elemental concentrations in indoor working environments

 M. Zitnik a, *, A. Kastelic a, Z. Rupnik a, P. Pelicon a, P. Vaupeti a, K. Buar a, S. Novak a, Z. Samardija a, c c z S. Matsuyama b, G. Catella b, K. Ishii b
a b

Joef Stefan Institute, P.O. Box 3000, SI-1001 Ljubljana, Slovenia z Department of Quantum Science and Energy Engineering, Tohoku University, Aramaki-Aza-Aoba 6-6-01-2, Aoba-ku, Sendai 980-8579, Japan

a r t i c l e i n f o
Article history: Received 3 August 2009 Received in revised form 5 August 2010 Accepted 9 August 2010 Keywords: Aerosols Indoor air pollution Element sensitive Time resolution Machine workshop PIXE SEM EDX

a b s t r a c t
We have measured the elemental concentrations in aerosols with a 2-h time resolution in two different types of working environment: a chemistry laboratory dealing with the processing of advanced nanoparticulate materials and a medium-sized machine workshop. Non-stop 10-day and 12-day samplings were performed at each location in order to determine the concentration trends during the nonworking/working and weekday/weekend periods. Supplementary measurements of PM10 aerosols with a 2-day sample collection time were performed with a standard Gent PM10 sampler to compare the elemental concentrations with the time-averaged concentrations detected by the 2D step-sampler. The concentrations were determined a posteriori by analyzing the x-ray spectra of aerosol samples emitted after 3-MeV proton bombardment. The PM10 samples collected in the chemistry laboratory were additionally inspected by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) to determine the chemical compositions of the individual particles. In the workshop, a total PM10 mass sampling was performed simultaneously with a minute resolution to compare the signal with typical outdoor PM10 concentration levels. A factor analysis of the time-resolved dataset points to six and eight factors in the chemistry laboratory and the machine workshop, respectively. These factors describe most of the data variance, and their composition in terms of different elements can be related to specic indoor activities and conditions. We were able to demonstrate that the elemental concentration sampling with hourly resolution is an excellent tool for studying the indoor air pollution. While sampling the total PM10 mass concentration with a minute resolution may lack the potential to identify the emission sources in a noisy environment, the time averaging on a day time scale is too coarse to cope with the working dynamics, even if elemental sensitivity is an option. 2010 Elsevier Ltd. All rights reserved.

1. Introduction A wealth of epidemiological data support the hypothesis that, on average, for every 10 mg m3 rise in the total mass concentration of inhalable particles (PM10) in the air, there is an increase of about 1% in cardiovascular mortality on a day-to-day basis (Routledge and Ayers, 2006). To isolate the agents and mechanisms that exert harmful effects on human health, to identify and characterize the emission sources and, not least, to estimate the effect of aerosols on the global climate and pollution, it is necessary to study the composition of the aerosol particles. Here, one of the most important pieces of information is the mass concentrations of the

* Corresponding author.  E-mail address: matjaz.zitnik@ijs.si (M. Zitnik). 1352-2310/$ e see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2010.08.017

different elements in the aerosols. In addition to the emission activity, the concentration levels are governed by complex meteorological conditions, chemical reactions in the atmosphere, deposition dynamics, and the processes, the importance of which may override the local character (long-range transport) and which occur with various strengths and on different time scales, ranging from minutes to years. Generally, it is more difcult to understand the observed concentration trends when the sampling time is long. For outdoor sampling this implies a large area of potential emission sources, and without any knowledge of the wind eld the source assignment relies solely on receptor modelling e the statistical procedures to identify and quantify the sources at a receptor location. The difculties in source appointment can, to a large extent, be overcome when studying aerosols in the indoor environment by a restricted air streaming, short sampling times and specic site activities (Baldwin and Maynard, 1998).

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The signicance of indoor particulate matter, which may differ substantially in terms of composition from outdoor particulates, has yet to be fully explored (Mitchell et al., 2007). However, the fact that humans spend a substantial amount of time inside buildings has triggered many eld studies. Some recent examples include an examination of a specic aerosol composition due to train and passenger movements in underground railway stations (Salma et al., 2007; Kang et al., 2008; Raut et al., 2009), the release of aerosols due to various cooking methods in a kitchen (See and Balasubramanian, 2008), the particle emission rate in domestic environments when typical activities such as vacuum cleaning are undertaken (Gehin et al., 2008), as well as the study of air quality in residential houses located near major highways (Martuzevicius et al., 2008). Aerosols were investigated in dental ofces (Sotiriou et al., 2008), in highway tollbooths (Shih et al., 2008), and school classrooms (Fromme et al., 2008). Many studies focused on dust problems at different workplaces, which occur, for example, when dealing with metallic materials (Kuo et al., 2007; Nygren and Aspman 2004), spray painting (Wilms et al., 2006), and exposure to sulfuric acid in zinc production (Bratveit et al., 2004). A clinical study of the largest reported alveolitis and asthma breakout in a car-engine manufacturing plant was recently reported by Robertson et al. (2007). On the one hand, we are faced with automatic devices that can easily run for long periods of time and are able to determine the total PM10 mass concentration (Teom, Patashnick and Rupprecht, 1991), the black carbon concentration (Aethalometer, Hansen et al., 1984) or the size-sorted particle concentration (using either light-scattering or condensation methods) in real time with a resolution of the order of 1 min or even less. On the other hand, the time-resolved information about the chemical state of a single aerosol particle can be extracted from the mass spectrum of a particle taken from an airow (Hellen et al., 2008). However, the AMS technique is not practical for monitoring purposes, because this would imply the need to sustain sensitive and complicated equipment for a long period of time. An excellent time and also spatial resolution is offered by lidars detecting the backscattered light; when they are not tuned to a specic resonance frequency of, for example, water vapor (Gerding et al., 2004), they measure only the optical properties of aerosol particles (Pavese et al., 2009). In many cases the temporal resolution requirements can be relaxed to an hour or so and no prompt response is required. When combined with an efcient element-selective analytical approach that does not require an elaborate sample preparation, simple and standalone sampling devices offer an excellent alternative for studying aerosol concentration dynamics. While Proton Induced X-ray Emission (PIXE) is characterized by a low background due to small proton bremsstrahlung, X-Ray Fluorescence (XRF) can take the advantage of modern and intense synchrotron sources to collect a single aerosol sample spectrum in a few seconds (Bukowiecki et al., 2005). More elaborate versions of these techniques with micro-focused projectile beams provide the elemental composition of single aerosol particles (Toyoda et al., 2004) and even their  spatial distribution inside the lter material (Zitnik et al., 2008). As for the sampling techniques able to keep track of collected particular matter over time, a well-known example is given by the streaker (Mazzei et al., 2007; Vechii et al., 2008), where the circular lter substrate rotates below a xed air inlet with an angular velocity of about 2 deg h1 allowing an approximately one-weeklong non-stop sampling period with a time resolution of about 1 h. Another is a DRUM multi-stage impactor, which offers 6 weeks of continuous deposition of PM, separated into up to eight different size intervals and a 3-h time resolution (Per-Trepat et al., 2007). Here we report on a sample-and-analysis approach somewhere between the two: we have combined a simple sampling device (2D

step-sampler) with PIXE analysis to measure the indoor elemental concentration trends with a 2-h time resolution over a period of about three weeks. Aided by a statistical factor analysis of the element-specic dataset acquired and using auxiliary information extracted from a single-particle analysis and Logbook entries, we identify typical air-pollution levels and potentially risky activities for two types of indoor spaces: a chemistry laboratory (CL) and a machine workshop (MW). A supplementary measurement with a standard time-averaged PM10 Nuclepore sampling was performed to calibrate the 2D step-sampler. In addition, the 2D stepsampler data are compared with the total PM10 concentration trend recorded with a commercial Teom instrument. 2. Sampling and analysis In the rst sampling period the aerosols were collected in the CL. This particular laboratory deals with the synthesis and processing of nanostructured inter-metallic alloys and ceramics. In several rooms of the CL there are the pieces of equipment for the synthesis of ceramics and inter-metallic alloys: high-temperature ovens, a spray-dryer, an arc-melter, a melt-spinner, etc. Sensitive metallic powders are stored in pressurized glove boxes to prevent their oxidation, while ne ceramic powders are stored at reduced pressure to avoid contamination of the room. Small whetting and milling machines are used occasionally in the course of the material-preparation procedures. The sampling with the 2D stepsampler started on January 13, 2008, 12 AM in the central room of the CL and continued without interruption until January 25, 2008, 8 AM. During this time 143 aerosol samples were taken, each with a 2-h sampling time. A period of low working activity with restricted use of the machines in the CL (the so-called nowork in Fig. 1) lasted until January 16, 2008, 12:00 AM, when the working mode returned to normal (denoted by work in Fig. 1). To compare the concentration levels and to estimate the outdoor aerosol signal, the time-integrated sampling was conducted from January 16, 2008, 12 AM until January 18, 2008, 12 AM. A pair of PM10 Gent samplers (Maenhaut et al., 1994) was employed for this purpose: one was placed indoors, close to the 2D step-sampler and the other was placed just outside the CL. The particles were collected on a 47-mm-diameter Nuclepore lter (0.4-mm pore size) with an airow of 15 L min1. The sampling was quasi simultaneous, since each of the samplers was collecting particles for only 15 min during each hour. Apart from the PIXE analysis, these time-integrated Nuclepore samples were also investigated using scanning electron microscopy (SEM) and electron-probe microanalysis with energydispersive X-ray spectroscopy (EDX). The EDX analysis of the individual micro-particles on the lter substrate was employed to determine their chemical compositions. The second part of the sampling, from February 12, 2008, 8 AM, until February 22, 2008, 8 AM, was conducted in one of the MW rooms, where materials such as iron, stainless steel, aluminum and plastic are machined with lathes and CNC milling machines. During the working hours (7e15 h, MondayeFriday) about ve of the machines are running routinely. Besides taking 120 samples, each with a 2-h collection time, two pairs of time-integrated PM10 samples (indoor-outdoor) were taken by two Gent samplers. As in the case of the CL, each sampler was collecting particles for only 15 min during each hour. The rst pair was sampled during the weekend (February 15e17) and the second pair during the following working days (February 18e20). In addition, we have simultaneously measured the indoor PM10 mass concentration with a 10-s time resolution using a commercial Teom 1400A instrument. A total of 263 aerosol samples were taken with the 2D stepsampler developed at Tohoku University (Matsuyama et al., 2003).

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nowork weekend

work weekend

1/13

1/14

1/15

1/16

1/17
np

1/18

1/19

1/20

1/21

1/22

1/23

1/24 2000

Concentration [ng/m ]

Ca 0 Fe

S 2 Cu Zn 2 4

5 g/cm2
Cl K Ti x 2 V x 10 Cr Mn Ni Pr / 20 Nd / 20 0 20 40 3

1 1 60 80 100 Ar 120 140

Time intervals [2 hours]

Fig. 1. Concentrations of 14 different elements in the CL presented as a function of time for the period January 13e24, 2008. The dates (mm/dd format) and time stamps for noon (vertical dashed bar) and midnight (vertical full line) are added for orientation. The np box indicates the time-integration interval of two extra PM10 samples (indoors and outdoors). Weekends and time intervals with low (nowork) and high working activity (work) are denoted. A vertical bar, the rst on the left in the Ni data row, denotes the standard areal density of Ni foil, which serves to put the data on an absolute scale. Mass concentrations of the elements in the air are calculated from calibrated areal densities by taking into account the known surface of the spot sample and the air volume pumped through it. The last row (light blue) presents the data proportional to the spectral yield of the Ar Ka line, which is used to monitor the spot-to-spot stability of the proton dose. Background concentrations are subtracted from the data. The numbers 1e5 beside the bars refer to different events, as discussed in the text. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article).

In short, when an air pump is switched off, a small, reversible motor moves the suction nozzle, placed just below the lter surface, to a new sample position on a lter, 5 mm apart from the center of the previous spot. The lter, with a 160 160 mm2 surface, is large enough to hold about a thousand aerosol samples. The lter sheet was cut out of the Nuclepore circular substrate with a 293-mm diameter and 1-mm pore size. When in position, the pump is switched on for a preset sampling time (2 h in our case) to push 0.5 L of air per minute through the nozzle with a 2-mm diameter. A needle valve keeps the air mass ow stable and a programmable controller switches between the nozzle movement and the pump operation. The samples were irradiated at the external ion beamline attached to the Tandetron accelerator facility MIC at the Joef Stefan z

Institute in Ljubljana, Slovenia. The 3-MeV proton beam with a 1-mm diameter exits the vacuum through a thin Kapton foil and hits the sample spot, placed 15 mm away from the beamline exit. The x-ray emission from the sample spot is observed with a SiLi xray detector placed at an angle of 45 , backwards with respect to the incoming proton beam and 55 mm away from the target. The proton-beam current was about 15 nA. For each spot, the spectrum was acquired for 15 min and the relative proton dose delivered to different spots was extracted from the yield of the Ar K e L23 emission line (Ka line, for brevity); this signal originates from a constant concentration of Ar in the air, and its time integral is proportional to the acquired proton dose. An absolute calibration of the data was enabled by recording the x-ray spectrum of a thin Ni foil with a known 50 mg cm2 concentration (Micromatter

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standard). The standard foil was attached to the same lter sheet and brought to the central position with respect to the beam. The computer-controlled movements took care of the automatic placement of the table with the lter frame in such a way as to bring the center of the next sample spot into the beam center when the single spectrum acquisition of the previous spot was completed. The concentration levels due to the lter sheet contamination were determined by collecting the spectra from several unexposed spot areas. The corresponding concentration levels were found to be fairly independent of the spot position and their averages were subtracted from the data before the analysis. The PIXE spectra of the time-averaged Gent samples put in a vacuum were recorded simultaneously by two x-ray detectors (low- and high-energy regions) during the target irradiation with the 2.5-MeV proton beam. The dose for each spectrum was 100 mC and the average proton current was 20 nA. Again, the Micromatter standards were used to calibrate the x-ray yield of 15 different elements, ranging from the Na Ka line at 1.040 keV to the Sb Ka line at 26.360 keV. The specic element yields from different spots were extracted from the spectra with the GUPIX code (Maxwell et al., 1995) and converted into the corresponding surface mass densities in the so-called thin-target approximation (neglecting the proton-beam energy loss and the x-ray self-absorption effects) and on the basis of known atomic cross-sections, experimental geometry and spectrometer characteristics. 3. Results 3.1. The chemistry laboratory The elemental concentration trends measured in the CL are presented in Fig. 1. Besides the strong variation of Ca, Fe, S, Cl, and K signals, isolated peaks are also visible: the concentration spikes of Cu, Zn, Ti, V, Cr, Mn, Pr and Nd. The last two elements, which do not belong to the usual set of elements found in the outside air, show only a single prominent peak, detected between 10 and 12 AM on Friday, January 18, 2008 (event No. 1 in Fig. 1). During the same time interval a local maximum of Fe, Cr, and Mn concentrations is observed too. The peak occurrence is related to the preparation of NdeFeeB nanopowder, starting at 10.30 AM on the same day. The traces of this event were also found by an SEM-EDX analysis of the time-averaged indoor PM10 sample, which detected the presence of micro-particles consisting of Pr, Nd, Zr and Fe oxides (Fig. 2a). The origin of the Ca signal is related to the earth dust, the concentration of which in the air indoors is sustained by people moving around the laboratory: during workdays there are broad peaks of the Ca concentration centered around noon. During the weekend the dust had time to settle down and the Ca signal drops almost to the background level. The CaeFe correlation factor (0.30) points, at least in part, to a similar origin of the Fe. On the other hand, the KeS data (correlation factor 0.40) display no weekend/workday contrast, suggesting the observed variation of these two elements may be a consequence of changing outdoor concentrations. For Cl, there is an anti-correlated time trend with respect to S, which might be explained by the substitution of Cl with S in NaCl, leading to volatile HCl, and consequentially to a lower Cl concentration in the particulates when the concentration of S is increased (Seinfeld and Pandis, 1998). An EDX spectrum in Fig. 2c reveals the presence of CaSO4 particles in a time-integrated outdoor sample and shows that Ca is also partially correlated with S. There are a few spikes in the Cu concentration observed (event No. 2 in Fig. 1): the earliest two appear on January 16 (4e6 PM) and on January 17 (8e10 AM). From the Logbook inspection these are associated with whetting of the Cu electrode of the arc-melter on the machine in the same room. The other two Cu spikes observed on January 22 (10e12 AM)

and on January 23 (4e6 PM) very likely have the same origin. An increased concentration of Ti in the air was detected in several time intervals during workdays (events No. 3 in Fig. 1). This could be related to the preparation of SrTiO3 or TiO2 nanopowder for sintering, or to the synthesis of TieZr(Hf)eNi hydrogen-storage alloys. An increase in the Zn concentration is also observed during the working hours (event No. 4 in Fig. 1), but its presence in the air is probably indirect: although in the CL they deal with ZnO powder (Fig. 2b), the trend of Zn resembles the Ca one, so it may well be that Zn (and perhaps also Ti) was previously deposited in the room and enters the air due to the movements of people. The Cr and Mn peaks are strongly correlated to Fe (correlation coefcients 0.74 and 0.68, respectively) and point to another, not evidenced direct cause (events No. 5 in Fig. 1), which was active outside the working hours (4e6 AM on January 16, and late night on January 17e18) and is probably related to the machining of an iron alloy. Except for events No. 1e3 and 5, there is not much change observed for the timesampler data in between the nowork and work regimes, while the difference between the weekdays and the weekend air quality is clear. The statistical analysis of the CL dataset corroborates the above reasoning and offers additional insights. A factor analysis (FA) of the covariance matrix with the Vari-max rotation method identied six factors that explain 60% of the variance (Table 1). In particular, the results conrmed the association of Fe with Pr and Nd (PreNd factor) and show that dust deposited in the CL by previous activities (with Ca as a marker element) contains a considerable share of Ti, Zn and Fe (Indoor dust factor). A factor that is insensitive to the weekend/workday condition is shown to be predominantly composed of S and K (Outdoor dust factor). There is clear evidence of a strongly correlated FeeMneCr concentration (Metal factor) as well as of a factor with a predominant Cu contribution. The FA analysis points to the TieNi factor, so that the observed Ti peaks (events No. 3) most probably originate from activities related to the synthesis of TieZr(Hf)eNi hydrogenstorage alloys. Relatively high communalities (h2 > 0:7) of Ca, Cr, Fe, Ni, Pr, and Nd demonstrate that the six factors presented in Table 1 account quite well for the observed variance of these elements. To estimate the present efciency of the 2D step-sampler we compared the elemental concentrations detected by the standard Gent PM10 sampling with data obtained by averaging the 2D stepsampler concentrations over the corresponding time period (Fig. 3). The inlet of the indoor Gent sampler was positioned 2.5 m away from the 2D step-sampler. It is interesting to note that despite the much shorter sampling time (2 h versus 13.25 h) and the much smaller volume airow (0.5 L min1 versus 15 L min1), the areal density of the dust collected on the 2D step-sampler spot is still about 3-times larger than the areal density of the PM10 sample with its 500-times larger surface. The aerosol collection onto small, uniformly loaded spots is therefore a good option for time-resolved sampling when the analysis is performed by collimated particle or x-ray beams. Most of the relative elemental concentrations for the three cases presented in Fig. 3 are similar. However, a rough agreement between the time-averaged signal of the 2D stepsampler and the signal of the time-integrated indoor sampling (Gent) is achieved only by multiplication of the former by a factor of 5, except for Pr and Nd, which require much smaller correction factors (1.0 and 0.5, respectively). Such a discrepancy can be partly explained by the fact that the indoor and the outdoor PM10 samplers were collecting the dust only for 15 min each hour and could miss concentration episodes with a short duration, for example, the PreNd episode. Another problem may be due to the dust deposition on the exposed lter sheet surface outside the spot area. This is indicated by the nonzero concentrations of the elements found outside the spots, the average of which was

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Fig. 2. a) SEM image of the selected area of the time-integrated indoor Nuclepore sample. An EDX spectrum of the particle shown in the dotted circle reveals that it is composed of a mixture of Pr, Nd, Zr, and Fe oxides. b) SEM image of ZnO agglomerate of nanoparticles captured on the time-integrated indoor Nuclepore sample. The presence of the Cl Ka peak in the EDX spectrum indicates that the agglomerate also contains some Znechloride particles. c) SEM image of time-integrated outdoor Nuclepore sample area. An EDX spectrum of encircled particle shows a composition that corresponds mainly to calcium sulphate (CaSO4) with some other elements (Na, Al, Si, K, Fe) as impurities in the agglomerated complex particle.

subtracted to generate the spot-concentration data. Three other possible reasons for the discrepancy may be the different pore sizes of the lter, 1.0 mm and 0.4 mm for 2D step-sampler and Gent sampler, respectively, the occurrence of partial clogging at the sampling spots, and, nally, the absence of any upper size-preselection of the particles collected by the 2D step-sampler. All these problems can be properly addressed and solved in a further application of the method. Although we cannot directly rely on the absolute concentrations, a similar comparison for the workshop

data leads again to an average correction factor of 5, which may then be taken as an empirical scaling factor for the present setting of the 2D step-sampler. Looking at the PM10 concentrations in Fig. 3, it is interesting to compare the elemental composition of the aerosols detected outside and inside the CL. While the outside Fe, Ca, Cl, Cr, and Mn concentrations are about two-times larger, the averaged concentrations of S, K, Ti, Ni, and Zn show about the same value at both sampling places. Except for the presence of Pr, Nd, and Cu, there

 M. Zitnik et al. / Atmospheric Environment 44 (2010) 4954e4963 Table 1 The factor analysis results for the CL aerosol dataset. Loadings less than 0.2 are omitted and loadings larger than 0.50 are type-set in bold. Reported is the percentage of variance explained by each factor (%). Number 1 % 0.17 Factor composition and description 0.89 Fe D 0.80 Cr 0.76 Mn 0.41 Zn 0.28 K 0.25 Fe 0.27 Ni Metal 0.99 Pr 0.98 Nd 0.24 Fe PreNd: nanopowder preparation 0.90 Ca 0.50 Ti 0.50 Zn 0.25 Fe Indoor dust 0.75 K 0.57 S 0.22 Zn Outdoor dust 0.82 Ni 0.30 Ti 0.29 Cr TieNi: synthesis of TieZr(Hf)eNi alloys 0.59 Cu 0.35 Ti Cu: whetting of arc-melter electrode

4959

2 3 4 5 6

0.15 0.11 0.07 0.06 0.04

does not seem to be much qualitative difference in the elemental aerosol composition between the inside and outside during the time interval of the PM10 sampling.

3.2. The mechanical workshop The concentration trends of 18 different elements that were detected in the MW are presented in Fig. 4. Some concentrations display simultaneous abrupt changes in time, which clearly point to the same source. For example, the PbeBaeZn group is characterized by a pairwise correlation factor larger than 0.88 and obviously has the same origin. The signal of this group is the strongest during the weekend and just after the nominal working hours (events No. 1 in Fig. 4). It was identied as being due to the removal of an old

12 8 4 0

8000

6000

PM10 sampler - outdoor

4000

PM10 sampler - indoor

2000 2D step-sampler x 5

0 Ca Fe S Cu Zn Cl K Ti V Cr Mn Ni Pd Nd

Fig. 3. Comparison of the time-averaged elemental concentrations of the 2D stepsampler with concentrations derived from the Gent samplers placed inside and outside the CL for an active time period denoted by np in Fig. 1. The dashed line indicates an empirical scaling factor of 5, which is adopted for the calibration, as discussed in the text.

layer of white paint from doors in the course of a restoration procedure that consisted of heating up a painted surface and removing the old paint by grinding. The lead in the old paint should probably be in some form of lead carbonate, PbCO3, while the presence of Ba is probably due to BaSO4, which is also a common white-paint agent. Indeed, the concentration of S also displays peaks, time-correlated to these events. They are superimposed onto a smooth background signal that originates from other emission sources. With a lower time resolution the peaks would merge with the background and it would be more difcult to correlate the S with the group. Zn, the third member of the group, could appear either as zinc white (ZnO), or as the white pigment lithopone, a mixture of ZnS (68e70%) and BaSO4(28e30%). Although the restoration procedure was carried out in the nearby carpenters room, the average 2-h concentrations at the sampling point reached alarmingly high levels e on Saturday afternoon, February 16, 2008, the concentrations of Pb, Ba, and Zn were 30 mg m3, 10 mg m3 and 7 mg m3, respectively. These numbers are derived from the measured 2D step-sampler concentrations using an empirical scaling factor of 5, as argued above. The analysis of the time-integrated PM10 sampling, which took place in the carpenters room at that time, indicates that close to the source these concentrations could even be up to 15-times higher. The concentration of Ca shows an expected increase during the workshop working hours (7e15 h), which extends to the late afternoon because of cleaning activities. It is curious that Cl is related to Ca with a correlation factor 0.60 indicating the presence of Cl in the indoor dust. An inspection of the correlation-coefcient values suggests Fe is a member of the metal group, together with Ti, V, Cr, Mn, Ni, Cu and W. The FeeCa correlation coefcient of 0.34 indicates that the metal group may also be related to the indoor dust that is dispersed in the air due to the movement of the workers. A signicant increase of the Si concentration going up to 30 mg m3 was detected on Wednesday morning (February 20), and is attributed to extensive grinding activities in the MW at that time. To rene a simple analysis based on the inspection of correlation factors and concentration time trends of the different elements, a factor analysis was performed on the MW dataset too. A total of eight factors are identied in Table 2, and they explain 73% of the total variance of the dataset. The communalities (h2) for Cl, Ca, Ti, Mn, Fe, Co, Zn, Br, Ba, W and Pb are larger than 0.7, and the variance of these elements is expected to be well represented by the selected factors. The factor number 1 describes the white-paint dust and its composition helps to resolve the dilemma, introduced above: Zn and S contribute with 0.88 and 0.50 loadings, respectively, which translates to a 2:1 mass ratio, approximately, when we consider the ratio of the measured absolute mass concentrations for these two elements. We may conclude that the Zn and most of the S appear in the White paint factor as a sulde ZnS, which points to the white pigment lithopone as a source. While the origin of the four factors (1e3, 8) seems quite clear e the paint removal, the machining of High-Speed-Steel (HSS) alloys, the machining of NieCr alloys and grinding with sandpaper, there remains some ambiguity with the rest. Factors 4 and 6 are related to the machining of AleCu and AleMn alloys, but are also loaded with Cl and Br, respectively. These elements might be present in the cutting-uid additives employed to enable smoother cutting and colling of aluminum objects during the machining. Although the producers of modern additives mostly claim their products are chlorine free, Cl and Br are sometimes used as emulgators to achieve a stable and homogeneous dispersion of the emulsion in the water. The appearance of Fe in factors 4 and 6 indicates that these factors might be of mixed origin, i.e., due to the simultaneous machining of aluminum and iron alloys and perhaps also of machinable plastic. The only reasonable explanation we could nd to explain the presence of a clear KCl signal

Ratio PM10 (indoor) versus 2D step-sampler

Concentration [ng/m ]

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Time intervals - Teom [10 s]

0 20 total PM10 total 2D step-sampler x 3 40 PM10-1 60 PM10-2 80x10
3

PM10 [ g/m ]

600 400 200

2/12

2/13

2/14 work

2/15

2/16

2/17

2/18

2/19

2/20 work

2/21

2/22

nowork

14x10

1
Ba Br Zn Cu Ni Co Mn Cr V Ti W

12

5 g/cm
10

Concentration [ng/m ]

Fe Si

1
Pb

Ca

1
-2

1
S Cl K

-4 Ar signal 160 180 200 220 240 260

Time intervals [2 h]
Fig. 4. PM10 and mass concentrations for 19 elements in the mechanical workshop as a function of time for the period February 12e22, 2008. The dates (mm/dd format) and time stamps for noon (vertical dashed line) and midnight (vertical full line) are added for orientation. The PM10 boxes indicate the time-integration interval for two pairs of extra samples (indoor and outdoor). Horizontal bars denote weekends and working days. A vertical bar, the rst on the left in the Ni data row, denotes the standard areal density of Ni foil, which serves to put the data on an absolute scale. Mass concentrations of elements in the air were obtained from calibrated areal densities by taking into account the known surface of the sample spot and the volume of air pumped through the sample. The last row (violet) presents the data proportional to the spectral yield of the Ar Ka line, which is used to monitor the spot-to-spot stability of the spectral data. For a comparison with the total PM10 mass the empirical scaling factor of 5 is used for the total 2D step-sampler concentration. The number 1 beside the bars refers to events associated with the White paint factor, which is discussed in the text. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article).

(factor 7) is aluminum welding with KCl ux performed occasionally in the MW. Finally, factor 5 is associated with the indoor dust, which is expected to contain a substantial loading of Ca. The

assignment of this factor as an Indoor dust is further encouraged by the presence of Fe in a similar relative amount with respect to Ca (0.22/0.86), as the one found in CL (0.25/0.90), but the origin of the

 M. Zitnik et al. / Atmospheric Environment 44 (2010) 4954e4963 Table 2 The factor analysis results of MW aerosol dataset. Loadings less than 0.2 are omitted and loadings larger than 0.50 are type-set in bold. Reported is the percentage of variance explained by each factor (%). Number 1 % 0.18 Factor composition with description 0.97 Pb 0.98 Ba 0.88 Zn 0.50 S 0.39 V 0.25 Fe 0.22 Ti White paint: removal of an old paint layer 0.96 W 0.87 Co 0.76 Ti 0.38 Mn 0.31Fe 0.25 V 0.20 Ca HSS: machining of High-Speed-Steel alloys, use of tools with TiN coating 0.85 Ni 0.72 Cr 0.49 Fe 0.27 V NieCreFe: machining of NieCr alloys (Inconel) and iron 0.66 Cl 0.64 Cu 0.53 Fe 0.24 Ni AleCueCl: machining of AleCu alloys (Duraluminum), iron and plastic, cutting-uid 0.86 Ca 0.61 Cl 0.38 Mn 0.22 Ti 0.22 Fe Indoor dust 0.83 Br 0.59 Mn 0.32 V 0.21 Fe AleMn: machining of AleMn alloys 0.71 K 0.32 Cl KCl: ux for aluminum welding 0.67 Si 0.31 V Si: grinding with SiO2, SiC sandpaper

4961

24x10

22

20

0.15

PM10-2 outdoor
18

3 4

0.09 0.08

Concentration [ng/m3]

16

14

PM10-2 indoor

5 6 7 8

0.08 0.07 0.04 0.04

12

Time sampler x 5
10

PM10-1 outdoor

high Cl loading remains unclear. We should point out that the interpretation of the MW data would be more reliable if the timeresolved concentrations of Al were available too. During the weekend, a size-selected sampling in the MW was performed by a nine-stage cascade impactor 1-1L-Pixe international Co. Ltd. (Bauman et al., 1981). The micro-PIXE analysis of these samples at Tohoku University in Sendai, Japan, also detected relatively large concentrations of Pb, Ba and Zn (Matsuyama et al., 2008) and very recently, a single-particle micro-PIXE analysis of a number of particles was performed (Catella, 2010). The results show that Pb, Ba and Zn are found on distinct particles, even though they all originate from the removal of old paint. It is interesting that a number of Pb-containing particles display a relatively high concentration of Cl. A strong PbeCl correlation indicates that lead is also present in the form of Pattesons white lead PbCl2$Pb(OH)2 (Perry and Phillips, 1995). However, the White paint factor in Table 2 does not show a signicant Cl loading. This may be due to the relatively low absolute concentration of Pattesons white in the air which obviously does not prevent its detection in single-particle form. Two more helpful hints are given by the micro-PIXE studies of aerosol samples at Tohoku University. The analysis of a 24-h test sample, taken by a single-stage impactor on an MW working day, starting on January 16, 2008, 10 AM, detected a group of 16 particles, each of them containing high concentrations of Al, Zr and Cl. This signal relates to the machining of another aluminum alloy at that time, but more importantly, since it is unlikely that the Al Zr alloy contains Cl, these three elements probably become associated via the interaction of the AleZr particles with the cutting uid. Another useful hint is given by Matsuyama et al. (2008), who detected the presence of organic compounds with a small amount of S and suggested it probably originates from the lubricant oilvapor condensate. This hypothesis is supported by the observed reduction of the above-mentioned smooth background concentration of S during the weekend (Fig. 4): at that time the machines are off and oil-vapor generation is greatly reduced. It is interesting that the 2D step-sampler data shows basically the same trend as the Teom PM10 data (Fig. 5.) where the total mass is reported every 10 s (actually a 300 s sliding average). The match between the two is the closest during the maximum of the White paint factor signal, when the total 2-h average concentration detected by the 2D step-sampler reaches about 30% of the total

PM10-1 indoor

Time sampler x 5
0 Ba Br Zn Cu Mn Cr V Ti W Fe Si Pb Ca S Cl K

Fig. 5. Comparison of the time-integrated signal of the 2D step-sampler with the signal of Gent samplers situated inside and outside the MW for two different time periods (denoted by PM10-1 and PM10-2 in Fig. 4).

peak PM10 mass concentration of 230 mg m3. More typically, the ratio between the two signals is only about 10%. The average of the total PM10 concentration over the whole sampling period was measured to be 59 mg m3, but during the working hours the average was always higher. It went from 77 mg m3 on February 12, up to 207 mg m3 on February 19, while on Sunday, February 17, the average PM10 concentration was only 14 mg m3. Since the yearly average of the total PM10 concentration in Ljubljana for 2008 is reported to be 32 mg m3 (ARSO, 2008), we can conclude that the workers in the MW are exposed to an about 2-times higher PM10 average concentration because of the higher dust load they experience during working hours. In contrast to the CL case, an about 2-times higher Fe concentration was detected inside the MW than on the outside (Fig. 5), while similar to the CL case, the outside Ca concentration was found to be about 2-times higher. For the MW the comparison of the Gent samples is made for two time intervals: during the weekend (PM10-1) and during the weekdays (PM10-2). As expected, during the weekend a strong excess of Ba, Zn, Pb, and S concentrations was detected inside. Due to the intensive restoration activities, the Pb concentration inside also remained higher during the weekday sampling. In addition to Fe, other members of the metal group (Cu, Mn, Ti, W, Cr) also display larger concentrations inside the MW environment.

4. Conclusions To access the indoor air quality in terms of quantity and source assignment it is advantageous to measure the elemental

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concentrations with an hourly time resolution. As we have shown, this goal may be achieved by combining the results of a statistical data analysis with knowledge of the specic indoor activities and the results of complementary single-particle and time-integrated measurements. We assigned factors to different activities that were occurring simultaneously with the sampling: in the chemistry laboratory these were the preparation of Pd/Nd nanopowder, the synthesis of TieNi alloys, the whetting of an arc-melter electrode and occasional iron machining. The machine workshop activities, the factors of which are identied in our dataset, encompass the machining of high-speed-steel, Inconel and different types of aluminum alloys, as well as grinding and aluminum welding. We unexpectedly detected and characterized a strong emission source e the removal of an old white-paint layer in the course of some furniture restoration. Related to that, three types of white pigments were identied, and the removal injected an alarmingly large amount of Pb-, Ba-, and Zn-containing particulate matter into the air. The so-called Indoor dust factor, with the earth element Ca as a marker, is noted to maintain a memory of the specic past activities e due to an imperfect ventilation and cleaning the dust accumulates and re-enters the air due to movements of the people. The Outdoor dust factor was detected in the chemistry laboratory only; in the machine workshop the concentration of S is mainly obscured by the presence of sulfur-containing oil vapor. A relatively high Cl loading in the workshop is associated with the machining of aluminum alloys e chlorine might enter the air due to the dispersion of cutting-uid additives. The measured total PM10 trend in the mechanical workshop indicates that workers are, on average, exposed to about a two-times higher concentration of PM10 than people in the local outdoor environment. Our results are expected to be helpful for designing measures that aim to reduce indoor dust pollution in the two cases considered. The total 2D step-sampler concentration data shows practically the same trend as the total PM10 data recorded with the Teom at a much higher time resolution. While in our experiment the total step-sampler signal typically amounts to 10% of the Teom signal, in certain episodes a scaling factor as high as 30% was found. The comparison with the time-integrated PM10 concentrations shows that the absolute PM10 elemental concentrations, as determined by the 2D step-sampler, are underestimated by about a factor of 5 and a future redesign of the 2D step-sampler aims to reduce this discrepancy. Further improvements of the 2D step-sampler towards an in-situ instrument would greatly increase the relevance of the approach by closing the time gap between the sampling and the analysis. Acknowledgements We express our gratitude to Tanja Bolte and the Environmental Agency of the Republic of Slovenia for make available an instrument (Teom) for this study. The interest of Franc Setnikar from the workshop management and of the workers themselves was found to be very stimulating. References
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 M. Zitnik et al. / Atmospheric Environment 44 (2010) 4954e4963 highway Toll workers in Taipei. Science of the Total Environment 402, 163e170. Sotiriou, M., Ferguson, S.F., Davey, M., Wolfson, J.M., Demokritou, P., Lawrence, J., Sax, S.N., Koutrakis, P., 2008. Measurement of particle concentrations in a dental ofce. Environmental Monitoring and Assessment 137, 351e361. Toyoda, M., Kaibuchi, K., Nagasono, M., Terada, Y., Tanabe, T., Hayakawa, S., Kawai, J., 2004. X-ray analysis of a single aerosol particle with combination of scanning electron microscope and synchrotron radiation X-ray microscope. Spectrochimica Acta B 59, 1311e1315.

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Vechii, R., Bernardoni, V., Cricchio, D., DAlessandro, A., Fermo, P., Lucarelli, F., Nava, S., Piazzalunga, A., Valli, G., 2008. The impact of reworks on airborne particles. Atmospheric Environment 42, 1121e1132. Wilms, V., Bckler, M., Fendler, D., Goergens, U., Brucksch, E., Knopp, R., 2006. Lackaerosole beim Spritzlackieren Beschreibung der expositions situation. Gefahrstoffe Reinhaltung der Luft 6, 239e244.  Zitnik, M., Pelicon, P., Grlj, N., Karydas, A.G., Sokaras, D., Schtz, R., Kanngiesser, B., 2008. Three-dimensional imaging of aerosol particles with scanning proton microprobe in a confocal arrangement. Applied Physics Letters 93 (094104), 1e3.