Wojciech Dmuchowski, Aneta Helena Baczewska, Dariusz Gozdowski

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1 Ochron Środowisk i Zsobów Nturlnych nr 40, 2009 r. Wojciech Dmuchowski*, Anet Helen Bczewsk**, Driusz Gozdowski*** Evlution of the led environmentl pollution in Wrsw on the bsis of bioindictive methods Ocen znieczyszczeni środowisk ołowiem w Wrszwie n podstwie metod bioindykcyjnych Słow kluczowe: biomonitoring, mech, drzew liściste, metle ciężkie, znieczyszczenie powietrz, obszry miejskie. Key words: biomonitoring, moss, tree folige, hevy metls, ir contmintion, urbn re. Znieczyszczenie powietrz ołowiem w Wrszwie w ltch oceniono bioindykcyjną metodą moss-bg, polegjącą n określeniu kumulcji w eksponownym mchu torfowcu (Sphgnum fllx). Wyniki bdń przedstwiono w formie mp imisji wykreślonych z pomocą progrmu MpInfo, n podstwie 230 punktów pomirowych. W cłym cyklu bdń njwiększe znieczyszczenie wystąpiło w pobliżu huty stli w północnym rejonie mist. Poziom znieczyszczeni zmniejszł się wyrźnie w mirę upływu czsu, w związku ze stosowniem benzyn bezołowiowych do npędu smochodów. Tendencj t występowł we wszystkich rejonch Wrszwy. Znieczyszczenie środowisk ołowiem określono również n podstwie kumulcji w liścich lip krymskich (Tili Euchlor ), rosnących w psie międzyjezdniowym w l. Żwirki i Wigury i w Lsku Bielńskim. Zmniejszenie zwrtości ołowiu w liścich było zncznie większe w drzewch ulicznych niż n terenie leśnym, co potwierdz, że głównym źródłem emisji ołowiu w Wrszwie były i są znieczyszczeni związne z ruchem drogowym. * Doc. dr hb. Wojciech Dmuchowski Prcowni Ekologii Roślin; Ogród Botniczny- CZRB PAN, ul. Prwdziwk 2, Wrszw; tel.: ; e-mil: dmuchowski@ ob.neostrd.pl orz Szkoł Główn Gospodrstw Wiejskiego, Wydził Rolnictw i Biologii, ul. Nowoursynowsk 159, Wrszw; tel.: ; e-mil: wojciech_dmuchowski@sggw.pl ** Mgr Anet Helen Bczewsk Prcowni Ekologii Roślin, Ogród Botniczny-CZRB PAN, ul. Prwdziwk 2, Wrszw; tel.: ; e-mil:.h.bczewsk@wp.pl *** Dr inż. Driusz Gozdowski Wydził Rolnictw i Biologii, Szkoł Główn Gospodrstw Wiejskiego, ul. Nowoursynowsk 159, Wrszw; tel.: ; e-mil: drek12345@gfmil.com 431

2 Wojciech Dmuchowski, Anet Helen Bczewsk, Driusz Gozdowski 1. Introduction Monitoring of ir pollution in Wrsw is conducted by the Provincil Inspection of Environmentl Protection. The scope of ir pollution concentrtion monitoring, conform to the Regultion of the Minister of Environment of 6 June 2002 [DZ.U. No. 87] nd includes the following substnces: sulphur dioxide, nitrogen oxides, ozone, suspended dust PM10, crbon oxide, benzene, nd led. Concentrtion limits of these substnces re leglly defined In ccordnce with the CAFE progrmme (Clen Air for Europe) nd the directives of the Europen Union the mesurement progrm concerning other hevy metls: rsenic, cdmium, mercury nd nickel should get implemented in the coming yers [Słt et l. 2005]. In 2004, the Ntionl Environmentl Monitoring system in Wrsw included only six points, in which led (Pb) mesurements were mde [Słt et l. 2005]. The nnul verges rnged, depending upon the mesurement point, between nd µg/m 3 nd in no cse exceeded the leglly llowed mximum concentrtion of 0.5 µg/m 3 [DZ.U. No. 87, item 798, 2002]. In 2003 in Polnd the dmissible concentrtion of Pb in the ir ws exceeded in only one region of the country, nmely the Legnic country, where copper foundries re locted [Ochron Środowisk 2004]. Such n optimistic imge, though, is not confirmed by other studies, which indicte lso other res of the country experience high ir pollution with Pb. It should lso be remembered tht from the humn helth s point of view ny quntity of Pb is undesired in the environment. Appliction of the bio-indiction methods in ir pollution monitoring, owing to the possibility of mking use of lrge number of mesurement points nd brod rnge of the hevy metls considered, my complement the direct mesurements of ir pollution within the Stte Environmentl Monitoring. 2. Mterils nd methods 2.1. Moss bg Mosses bsorb pollutnts minly in pssive mnner through free ion exchnge [Polokinen et l. 2004]. Nturlly growing mosses hve been widely used s effective bioindictors of hevy-metl ir pollution [Hrmens et l. 2008]. However, there re limittions in using mosses s in situ bioindictors, such s the difficulties of finding single species spnning lrge study re; the influence of vrying climtic conditions on ccumultion of metls; nd the integrtion of ccumultion over long or imprecisely determined exposure periods [Suchrová nd Suchr 2004]. Trnsplnttion methods involving trnsfer of mosses from the res of their nturl occurrence to the res where informtion on hevy-metl contmintion is needed hve been developed to void t lest some of these problems. Goodmn nd Roberts [1971] 432

3 Evlution of the led environmentl pollution in Wrsw... were the first who trnsplnted moss (Hypnum cupressiforme) from clen forest re outside of mjor emissions to the urbnized industril region of Swnse in Wles, United Kingdom, to evlute contmintion of ir with hevy metls. Uncontminted moss ws plced in nylon hir nets nd exposed in res where informtion on metl contmintion ws needed [Roberts 1972]. The moss-bg method ws further developed by Mrtin nd Coughtrey [1982]. The moss-bg method is bsed on two principles: (1) ded dried moss thllus preserves the cpcity of bsorbing metls [Tvres nd Vsconcelos 1996], nd (2) concentrtions of hevy metls in the moss bgs correlte well with their tmospheric levels [Anicic et l. 2009; Vsconcelos nd Tvres 1998; Zechmeister et l. 2003]. Exmples of recent investigtions with moss bgs re study in Nples, Itly, [Giordno et l. 2005] nd Shnghi, Chin [Co et l. 2009] where evlutions of sptil distribution of hevy metls were performed. The study ws conducted in Wrsw between 1992 nd 2004 (with no mesurements mde in 1994). Investigtions were conducted t 230 selected rndomly mesurement points. The precise loction of moss bgs ws selected in the field, observing the principle tht the exposure point should be distnced sufficiently from the streets with high trffic intensity, i.e. by t lest 100 m. Loction of the mesurement points ws in the mjority of cses the sme in the consecutive yers of the study. Moss ws exposed during 12 weeks, between 15 June nd 15 September of ech consecutive yer. Moss Sphgnum fllx (H.Klinggr.) H.Klinggr., former nme: Sphgnum recurvum P. Beuv., ws used in the study. The moss ws collected in the Augustów Primevl Forest, considered to be n re of reltively low ir pollution in Polnd [Dmuchowski, Bytnerowicz 1995]. After hving been brought to the lbortory the moss ws clened by hnd from grss, leves nd litter. Then, the moss ws wshed with distilled wter nd dried t 50 C. Until the exposure the moss ws stored in n exictor. Preprtion for the exposures consisted of weighing bout 1 g of ir dry moss, putting it to plstic net with smll mesh, nd then dipping it in the distilled wter to complete sturtion nd formtion of sphere-shped bgs of bout 4 5 cm dimeter. Such prepred moss bgs were exposed for durtion of 12 weeks in the summer seson. The moss bgs were plced t the height of bout 3 m. After the exposures, the moss bgs were brought into the lbortory nd were dried in the temperture of 70 C. The dried moss ws tken out of the bg, weighed nd ground to powder in n impct mill. Chemicl nlyses of the smples of moss from the mesurement plots nd from the zero smples, not exposed in the field were crried out. The powdered smples moss, were dry-minerlized in the muffle oven [Allen et l. 1974]. These nlyses were performed with the tomic bsorption spectrophotometry using the Perkin Elmer 1100A instrument [Perkin Elmer 1990]. 433

4 Wojciech Dmuchowski, Anet Helen Bczewsk, Driusz Gozdowski 2.2. Cimen linden trees Folige of Crimen linden trees (Tili Euchlor, cross between T. cordt Mill. & T. dsystyl Steven), which were bout 60 yers old in 1994, ws used in the study. Smples from 113 trees growing long Żwirki i Wigury Avenue (herefter the venue ), one of the min city trnsporttion routes, nd from 13 trees in the Lsek Bielński Prk (herefter the prk ), recretionl re ner the city center (Fig. 1), were collected in lte July 1994, 1996, 1998, 2000, 2002 nd Six smll brnches were cut from the outer prt of the crown between 2 to 4 m boveground. Smples of unrinsed folige were dried for 24 h t 60 C, ground to fine powder, nd stored in plstic vils until chemiclly nlyzed. Concentrtions of Pb were determined the sme wy s for the moss smples (see section 2.1). 3. Results Atmospheric Pb pollution in Wrsw ws diversified (Fig. 1 nd 2). The mximum mesurement of 49.4 mg/kg ws recorded for the moss exposed in 1992 in the vicinity of the ArcelorMittl steel mill in Bielny, while the minimum concentrtion, 4.0 mg/kg in 2000 ws determined in Kbcki Forest-South Wrsw (with the Pb content in the reference moss being t 2.5 mg/kg). It cn generlly be sid tht the Pb contmintion decresed considerbly, due to the incresed use of the unleded gsoline. The highest level of contmintion with Pb occurred, in the yers 1992 nd In the consecutive yers tendency of decrese contmintion ws observed, with temporry exceptions from in this tendency in the yers 1997 nd This might hve been linked to different wether conditions nd higher emission cused by trffic jms. The territory of Wrsw ws divided into six ctegories from the point of view of the nture of lnd use: the centre of Wrsw, the industril res, the res outside of the centre with high-rise housing blocks, simple fmily housing re, the re of the metllurgic plnt (the ArcelorMittl steel mill), nd the griculturl nd forested res. The digrms (Fig. 3) show the chnges in ir pollution in the yers with the brekdown into the mentioned lnd use ctegories. Folige of Crimen linden trees (Tili Euchlor, cross between T. cordt Mill. & T. dsystyl Steven), which were bout 60 yers old in 1994, ws used in the study. Generlly, t both the prk nd the venue, there ws significnt decrese of metl concentrtions between 1994 nd Decrese of Pb contmintion ws most pronounced mong the three monitored metls, with much higher decline long the venue thn in the prk (Fig. 4). 434

5 Evlution of the led environmentl pollution in Wrsw... Fig. 1. Air contmintion with Pb in Wrsw bsed on its ccumultion in moss bgs Rys.1. Znieczyszczenie ołowiem w Wrszwie podstwie określeni kumulcji Fig. 1. Air contmintion withpowietrz Pb in Wrsw bsed on itsnccumultion in moss bgs w eksponownym mchu (metod moss bg) Atmospheric Pb pollution in Wrsw ws diversified (Fig. 1 nd 2). The mximum 435 mesurement of 49.4 mg/kg ws recorded for the moss exposed in 1992 in the vicinity of the

6 the chnges in ir pollution in the yers with the brekdown into the mentioned lnd use ctegories. Wojciech Dmuchowski, Anet Helen Bczewsk, Driusz Gozdowski 18 mg/kg d e bc bc bc bc b c Fig. 2. Contmintion of the ir with led in Wrsw, determinted on the bsis of mesure- Fig. 2. Contmintion of the ir with led in Wrsw, determinted on the bsis of ment ccumultion in exposed moss. Subsequent lphbet letters indicte homogenous mesurement groups ccumultion of mens for in yers exposed on the moss, bse of depending multiple comprisons upon the ccording lnd use Tukey s ctegory method t level letters of significnce indicte α=0.05 homogenous groups of mens for yers on the bse of (mg/kg). Subsequent lphbet multiple comprisons ccording Tukey s method t level of significnce α=0,05 Rys.2. Znieczyszczenie powietrz ołowiem w Wrszwie n podstwie określeni kumulcji w eksponownym mchu. Kolejne litery lfbetu oznczją wydzielone grupy jednorodne średnich z poszczególnych lt n podstwie porównń wielokrotnych według procedury Tukey, przy poziomie istotności α=0, metlurgig plnt center of Wrsw industril high-rise housing blocs single fmily housing forest end griculturl Fig. Fig Contmintion of of the the ir with ir led with in Wrsw, led in determinted Wrsw, determinted on the bsis of on mesurement the bsis of mesurement ccumultion ccumultion in exposed in exposed moss (mg/kg), moss (mg/kg), depending depending upon the upon lnd use the lnd ctegory use ctegory Rys. 3. Znieczyszczenie powietrz ołowiem w Wrszwie n podstwie określeni kumulcji w eksponownym mchu, w zleżności od ktegorii użytkowni terenu Folige of Crimen linden trees (Tili Euchlor, cross between T. cordt Mill. & T. dsystyl 436 Steven), which were bout 60 yers old in 1994, ws used in the study. Generlly, t both the prk nd the venue, there ws significnt decrese of metl concentrtions

7 th the prk nd the venue, there ws significnt decrese of metl concentrtion tween 1994 nd Decrese of Pb contmintion ws most pronounced mong the thre Evlution of the led environmentl pollution in Wrsw... nitored metls, with much higher decline long the venue thn in the prk. (Fig. 4). mg/kg 14,0 12,0 10,0 8,0 6,0 4,0 2,0 0,0 e d d c c c bc b b Fig. 4. Led concentrtion in Tili Euchlor leves (mg/kg in d.m.) in two loclities in Wrsw. g. 4. Led concentrtion Subsequent lphbet in Tili letters 'Euchlor' indicte homogenous leves groups (mg/kg of mens in d.m.) for yers in on two the loclities rsw. Subsequent bse lphbet of multiple comprisons letters indicte ccording homogenous Tukey s method t groups level of significnce of mens α=0.05 for yers on th se of multiple Rys. 4. comprisons Zwrtość ołowiu ccording w liścich Tili Tukey s Euchlor method w dwóch t loklizcjch level of n significnce terenie Wrsz- α=0,05 wy. Kolejne litery lfbetu oznczją wydzielone grupy jednorodne średnich z poszczególnych lt n podstwie porównń 4. CONCLUSIONS wielokrotnych według procedury Tukey, przy poziomie istotności α=0,05 Trends of hevy metl chnges determined throughout Wrsw with the moss-b 4. Conclusions thodology were confirmed by the nlyses of linden folige from the city prk nd lon Trends of hevy metl chnges determined throughout Wrsw with the moss-bg e mjor venue. There ws significnt decrese in concentrtions of the studied met methodology were confirmed by the nlyses of linden folige from the city prk nd long er time, with the mjor the venue. strongest There ws decrese significnt for decrese Pb found in concentrtions long the of venue the studied chrcterized met- b ls over time, with the strongest decrese for Pb found long the venue chrcterized by intensive motor vehicle trffic, indicting tht the observed decline ws mostly cused by the grdul elimintion of leded gsoline. During the study period, ir contmintion with hevy metls ws the highest in the vicinity of the ArcelorMittl steel mill. Consequently, the western, northern, nd centrl prts of Wrsw were more polluted thn its southern nd estern res. References Allen S.E., Grishw H.M., Prkinson J.A., Qurmby C Chemicl nlysis of Ecologicl mterils. Blckwell Scientific Publictions, Osney Med, Oxford, Englnd. Anicic M., Tsic M., Frontsyev M.V., Tomsevic M., Risic S., Mijic Z., Popovic A Active moss biomonitoring of trce elements with Sph. girgensohnii moss bgs in reltion to tmospheric bulk deposition in Belgrde, Serbi. Environ. Pollut. 157:

8 Wojciech Dmuchowski, Anet Helen Bczewsk, Driusz Gozdowski Co T., Wng M., An L., Yu Y., Lou Y., Gou S., Zuo B., Liu Y., Wu J., Co Y., Zhu Z Air qulity for metls nd sulfur in Shnghi, Chin, determined with moss bgs. Environ. Pollut. 157: Dmuchowski W., Bytnerowicz A Biomonitoring of the environmentl pollution in Polnd using chemicl nlysis of Scots pine (Pinus silvestris L.) needles. Environmentl Pollution 87, Giorgdno S., Admo P., Sorbo S., Vingini S Atmospheric trce metl pollution in the Nples urbn re bsed on results from moss nd lichen bgs. Environ. Pollut. 136: Goodmn G.T., Roberts T.M Plnts nd soil s indictors of metls in the ir. Nture 231: Hrmens H., Norris D.A., Koerber G.R., Buse A., Steinnes E., Ruhling A Temporl trends ( ) in the concentrtion of cdmium, led nd mercury in mosses cross Europe. Environ. Pollut. 151: Informcje i oprcownie sttystyczne Ochron Środowisk Główny Urząd Sttystyczny. Wrszw. Mrtin M.H., Coughtrey P.J Biologicl monitoring of hevy metl pollution. Lnd nd ir. Applied Science Publishers London, New York. Perkin Elmer Anlyticl methods for tomic bsorption spectrophotometry. Bodenseewerk, Publiction B: 233 i 353. Polokinen J., Kubin E., Piispnen J., Krhu J Atmospheric hevy metl deposition in Finlnd during using mosses s bioindictors. Sci. Totl Environ. 318: Roberts T.M Plnts s monitors of irborne metl pollution. J. Environ. Plnn. Pollut. Cont. 1: Słt M., Brńsk K., Trębińsk E Roczn ocen jkości powietrz w województwie mzowieckim Rport z rok Wojewódzki Inspektort Ochrony Środowisk w Wrszwie. Suchrová J., Suchr I Bio-monitoring the tmospheric deposition of elements nd their compounds using moss nlysis in the Czech Republic. Act Průhonicin 77: Tvres H.M.C.F., Vsconcelos M.T.S.D Comprison of led levels collected by Sphgnum uricultum nd by low-volume erosol smpler in the urbn tmosphere of Oporto. Toxicologicl Environmentl Chemistry 54: Vsconcelos M.T.S.D., Tvres H.M.F Atmospheric metl pollution (Cr, Cu, Fe, Mn, Ni, Pb nd Zn) in Oporto city derived from results for low-volume erosol smplers nd for the moss Sphgnum uricultum bioindictor. Sci. Totl Environ. 212: Zechmeister H.G., Grodzińsk K., Szrek-Łukszewsk G Bryophytes. In: Mrkert B.A., Breure H.G., Zechmeister H.G. (Eds). Bioindictors nd Biomonitors. Elsevier Science Ltd. Amsterdm:

Wojciech Dmuchowski*, Aneta Helena Baczewska**, Dariusz Gozdowski***

Wojciech Dmuchowski, Aneta Helena Baczewska, Dariusz Gozdowski