INDOOR BIOMONITORING OF PARTICLE RELATED POLLUTION: TRACE ELEMENT CONCENTRATION IN AN OFFICE ENVIRONMENT

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1 INDOOR BIOMONITORING OF PARTICLE RELATED POLLUTION: TRACE ELEMENT CONCENTRATION IN AN OFFICE ENVIRONMENT Oldřich MOTYKA, Barbora MACEČKOVÁ, Jana SEIDLEROVÁ VSB Technical University of Ostrava, Ostrava, Czech Republic, EU; Abstract Since particulate pollution is becoming still bigger threat to human health and environment, there is an urgent need of monitoring its degree not only in the outdoors, but indoors, especially in the workplace, as well. Biomonitoring of atmospheric heavy metals and metalloids using bryophytes is rather common procedure. There has been discovered both strong affinity of these elements to the particulate matter and, albeit so far to a lesser extent, a correlation between the amount of the elements in question in the bryophyte material and concentration of the particulate matter in atmosphere. Two distinct ways of biomonitoring techniques were assessed in order to establish their applicability in indoor pollution monitoring. First one was the devitalization of the bryophyte matter (Hylocomium splendens) by drying and the second one was continuous irrigation of live matter with distilled water. Three transplants of both treatments were placed in a standard workplace (office) with the overall period of exposition of 49 days. The samples were taken in a weekly period and analyzed for the contents of Cu, Pb, Sb, Si and Hg by atomic absorption spectroscopy, advanced mercury analyser 254 and inductively coupled plasma atomic emission spectroscopy. The results are presented in figures and maps with isolines describing the accumulation of elements. It can be concluded that the irrigated moss bag method is more suitable for this kind of experiment and, generally, that active biomonitoring using bryophytes is useful for investigation of particle related pollution in such closed spaces. Keywords: biomonitoring, indoor, bryophytes, particulate pollution, heavy metals 1. INTRODUCTION Airborne fine and ultra-fine dust particles are associated with trace metals pollution being their main transferring agent. Particulate pollution is known to be detrimental to human health since they are susceptible to being inhaled and tend to be deposited in human respiratory system [1]. Associated trace metals are regularly toxic and were found to be of mutagenic nature, thus leading to enhanced risk of cancer development [2]. Biomonitoring of airborne trace metals and metalloids is gradually becoming a key contributor to our knowledge of distribution of those elements in the atmosphere either as a complementary tool to standard monitoring techniques or as a sole informant of the state of environment where, for various reasons, standard methods cannot be applied. Chakrabortty a Paratkar [3] highlighted amongst the main advantages of biomonitoring (in comparison to standard monitoring techniques) its low price and overall ease of application. Plethora of studies carried out have proven bryophytes to be suitable biomonitors of atmospheric pollution since their first use for biomonitoring of lead by Rühling and Tyler in 1968 [4]. There are several bryophytes properties rendering them to be utilizable, among those their bioaccumulation abilities related to their unique anatomy and physiology is the most prominent [5]. Both active and passive biomonitoring approach can be applied whilst using bryophytes as monitor species [6]. Active biomonitoring consisting, in general, of transplanting the moss material to the site of interest is

2 crucial when the site has no native moss of its own, e.g. when overly polluted or situated indoors. Indoor biomonitoring of airborne trace element pollution by the means of bryophytes is, however, still rather uncommon, though it was thoroughly discussed as early as in 1993 by Al-Radady et al. [7]. The aim of the study hereby presented was to determine whether indoor monitoring using bryophytes is applicable in evaluating a standard office workspace environment with special regard to particle-related pollution. Moreover, to compare two distinct designs of monitoring bags one with the oven-dried devitalized moss material and the other with continually irrigated vital moss. Both aims of the study represent novel approach, had the indoor monitoring by the means of bryophytes never been applied in Czech Republic before and comparison of such kind never been carried out. 2. MATERIALS AND METHODS Bryophyte material of Hylocomium splendens (Hedw.) Schimp. species was collected in a presumably unpolluted area of Protected Landscape Area of Moravskoslezské Beskydy, Červík Creek near Staré Hamry village. This particular species is widely used for biomonitoring purposes and, in a preliminary study, it was proven to have high bioaccumulation capability. Immediately after collection, the material was transferred to the laboratory where it was adjusted. After manual removal of all adhering material, apical segments (ca. 3-4 cm) were excised from the shoots, homogenized and thoroughly washed in distilled water for 30 s [8,9]. Half of the material was then devitalized in a dryer (24 h, 120 C) according to Adamo et al. [10] Non-devitalized moss material was placed on the top of capillary matting of polypropylene biomonitoring boxes full of distilled water and hold in this place by LDPE net (mesh size 0.5 cm). This boxes lids had two slits on opposite sides of them through which parts of the capillary matting were pulled inside providing the material with constant irrigation [11]. Devitalized material was placed in plastic bags made from the abovementioned net. All equipment in use was pre-treated with 1 M HNO 3. Three monitoring boxes and three plastic bags were deployed in the office space at height ca. 2 m above ground and exposed for total of 49 days. Samples for analysis were taken with a period of 7 days, ca. 2 g of dry weight from each transplant. Every time, samples were washed in distilled water and dried to constant weight at 50 C for higher temperatures may lead to loss of more volatile elements [12]. After the total decomposition in mix of acids, samples were analysed for Cu and Si by inductively coupled plasma atomic emission spectroscopy (SPECTRO Ciros Vision), Pb and Sb by atomic absorption spectroscopy (UNICAM 969) and Hg by advanced mercury analyser (AMA 254). Spatial interpolation of the element content in the bryophyte material was carried out using the statistical package R by the means of ordinary kriging [13]. 3. RESULTS AND DISCUSSION Element content in both irrigated and devitalized moss varied through the course of time of exposition. While the content in exposed material was in both treatments always higher than in the blind samples, it changed within weeks in both directions. This indicates that moss active biomonitoring may be used as a tool for determining the pollution even in such a short time scale contrary to its prevalent application hitherto [14,15,16]. Comparison of element contents in irrigated and devitalized moss is presented in Fig. 1; for the comparison, the case of two adjacent monitoring spots of both treatments was used. As is apparent, the accumulation rates were either comparable or higher in the case of irrigated moss with the most distinctive examples being the accumulations of silicon and antimony and, though to a lesser extent, lead. Higher accumulation rates in irrigated moss are in contrast with the recent recommendation of devitalization in biomonitoring as the most effective pre-treatment [17].

3 Fig. 1 Elements content through time As for the spatial distribution of elements, outcomes are presented in Fig. 2; figure represents element content in the last week (Cu, Hg, Pb), sixth week (Sb) and fourth week of exposition (Si) in Sb and Si the content in the devitalized moss material in the last week of exposition was below the detection limits. For Cu and Hg the spatial distribution is of the highest relevance mimicking the situation in Fig. 1 since here the element content was comparable for both treatments. In case of Pb, Sb and Si, the situation is more complex; isolines distribution mirrors the great discrepancy in accumulation rates between the two treatments, resulting in portraying the areas where devitalized material was deployed as of lower element presence. Overall, with the exception of Cu and Hg, the irrigated moss bags were found out to be more susceptible to bioaccumulation of elements than the devitalized material where the element content was in some cases lower than the detection limit.

4 Fig. 2 Spatial interpolation of element content in the last week (Cu, Hg, Pb), sixth week (Sb) and fourth week of exposition (Si) 4. CONCLUSIONS Presented research is the first of its kind in the Czech Republic and one of the few dealing with indoor biomonitoring worldwide; indoor active biomonitoring of particle related pollution by the means of bryophytes was hereby proven to be applicable in the office environment. Application of the irrigated moss bag method was found out to lead to higher accumulation rates of Pb, Sb and Si in the moss material compared to its

5 devitalisation. All surveyed elements have an affinity to particles dispersed in the atmosphere as a particulate pollution and method applied could thus be used to monitor nanoparticles pollution either in the outer environment or workspaces especially in places where these particles are produced or dealt with. ACKNOWLEDGEMENTS This paper has been elaborated in the framework of the project New creative teams in priorities of scientific research, reg. no. CZ.1.07/2.3.00/ , supported by Operational Programme Education for Competitiveness and co-financed by the European Social Fund and the state budget of the Czech Republic. LITERATURE [1] PÖSCHL, U. Atmospheric Aerosols: Composition, Transformation, Climate and Health Effects. Angewandte Chemie International Edition, 2005, č. 46, s [2] Monarca, S., Crebelli, R., Feretti, D., Zanardini, A., Fuselli, S., Filini, L., Resola, S., Bonardelli, P. G., NARDI, G. Mutagens and carcinogens in size-classified air particulates of a Northern Italian town. The Science of the Total Environment, 1997, č. 205, s [3] Chakrabortty, S., Paratkar, G. T., Biomonitoring of Trace Element Air Pollution Using Mosses, Aerosol and Air Quality Research 6, 2006, č. 6, s [4] RÜHLING, A.; TYLER, G. An ecological approach to the lead problem. Botaniska Notiser. 1968, č. 122, s [5] MULGREW, A., WILLIAMS, P: Biomonitoring of air quality using plants. Berlin: WHO Collaborating Centre for Air Duality Management and Air Pollution Control, s. [6] FALLA, J.; LAVAL-GILLY, P.; HENRYON, M.; MORLOT, D.; FERARD, J.-F. Biological air quality monitoring: a review. Environmental Monitoring and Assessment. 2000, č. 64, s [7] AL-RADADY, A. S., DAVIES, B. E., FRENCH, M. J., A new design of moss bag to monitor metal deposition both indoors and outdoor. The Science of the Total Environment. 1993, č. 133, s [8] BARGAGLI, R., BROWN, D. H., NELLI, L. Metal biomonitoring with mosses: procedures for correcting for soil contamination. Environmental Pollution. 1995, č. 89, s [9] CARBALLEIRA, A., LÓPEZ, J. Physiological and statistical methods to identify background levels of metals in aquatic bryophytes: dependence on lithology. Journal of Environmental Quality. 1997, č. 26, s [10] ADAMO, P., CRISAFULLI, P., GIORDANO, S., MINGANTI, V., MODENESI P., MONACI, F., PITTAO, E., TRETIACH, M., BARGAGLI, R.: Lichen and moss bags as monitoring devices in urban areas. Part II: Trace element content in living and dead biomonitors and comparison with synthetic materials. Environmental Pollution. 2007, č. 146: s [11] Fernández, J. A., Carballeira, A., Differences in the responses of native and transplanted mosses to atmospheric pollution: a possible role of Selenium, Environmental Pollution. 2000, č. 110 s [12] MARKERT, B. Sample preparation (cleaning, drying, homogenization) for trace element analysis in plant matrices. The Science of the Total Environment. 1995, č. 176, s [13] R DEVELOPMENT CORE TEAM. R: A language and environment for statistical computing. Vienna: R Foundation for Statistical Computing, URL: [14] FERNÁNDEZ, J. Á., ABOAL, J. R., CARBALLEIRA, A. Identification of pollution sources by means of moss bags. Ecotoxicology and Environmental Safety. 2004, č. 59, s [15] COUTO, J. A., ABOAL, J. R., FERNÁNDEZ, J. A., CARBALLEIRA, A. A new method for testing the sensitivity of active biomonitoring: an example of its application to a terrestrial moss. Chemosphere. 2004, č. 57, s [16] ZECHMEISTER, H. G., HOHENWALLNER, D., RISS, A., HANUS-ILLNAR, A. Variations in heavy metal concentrations in the moss species Abietinella abietina (Hedw.) Fleisch. according to sampling time, within site variability and increase in biomass. The Science of the Total Environment. 2003, č. 301, s

6 [17] GIORDANO, P., ADAMO, P., MONACI, F., PITTAO, E., TRETIACH, M., BARGAGLI, R. Bags with oven-dried moss for the active monitoring of airborne trace elements in urban areas. Environmental Pollution. 2009, č. 157, s

Ecology at the interface Science-based solutions for human well being

Ecology at the interface Science-based solutions for human well being Rome, September 21-25, 2015 A NOVEL BIOTECHNOLOGICAL TOOL TO MONITOR TRACE ELEMENTS AND PAHs BASED ON A DEVITALIZED MOSS CLONE: THE