Mineralogical and oxygen isotope composition of inorganic dust-fall in Wrocław (SW Poland) urban area – test of a new monitoring tool

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Min er al og i cal and ox y gen iso to pe com po si tion of in or ganic dust-fall in Wroc³aw (SW Po land) ur ban area – test of a new mon i tor ing tool

Maciej GÓRKA, Mariusz-Orion JÊDRYSEK, Dominika LEWICKA-SZCZEBAK and Janusz KRAJNIAK

Górka M., Jêdrysek M.-O., Lewicka-Szczebak D. and Krajniak J. (2011) – Min er al og i cal and ox y gen iso tope com po si tion of in or ganic dust-fall in Wroc³aw (SW Po land) ur ban area – test of a new mon i tor ing tool. Geol. Quart., 55 (1): 71–80. Warszawa.

We have ana lysed the min er al og i cal and ox y gen iso tope com po si tion of solid in or ganic at mo spheric par ti cles (SIAP) in Wroc³aw (SW Po land) to de ter mine po ten tial nat u ral and anthropogenic sources of de pos ited dust. The min er al og i cal com po si tions of SIAP and lo cal soils are very sim i lar and quite typ i cal. Dust sources were at trib uted to high emis sion sources (two large coal-fired power gen er a tion plants, i.e., “Wroc³aw” and “Czechnica”) and low emis sion sources (mostly small fur naces for home heat ing). A mullite phase was con - firmed in the non-mag netic frac tion of high emis sion dust. The d¹⁸O (SIAP) val ues col lected dur ing the study pe riod (from 20th No vem - ber 2003 to 25th May 2005) vary be tween 8.6 and 21.8‰. The d¹⁸O val ues of soil gath ered near est to the pas sive dust col lec tor vary be tween 9.3 and 16.0‰. The d¹⁸O val ues ob tained for hy po thet i cal anthropogenic sources of at mo spheric in or ganic par ti cles are: (1) 7.4‰ for low emis sion and (2) from 13.4 to 16.1‰ for high emis sion dust com po nents. The range of d¹⁸O val ues ob tained for SIAP, soil and hy po thet i cal anthropogenic sources do not al low the un am big u ous par ti tion ing of anthropogenic par ti cles us ing iso to pic mass bal - ance. How ever, min er al og i cal and geo chem i cal ev i dence sug gests that a ma jor source (nat u ral or anthropogenic) of dust de pos ited in Wroc³aw prob a bly lies out side of the city. The pre dom i nant south-west wind di rec tion sug gests that ag ri cul tural ar eas, quar ries, the Sudety Moun tains, or in dus trial cen tres are pos si ble or i gins of SIAP in Wroc³aw. We also do not ex clude hy po thet i cal long-trans port pro cesses as a source of dust de pos ited in Wroc³aw.

Maciej Górka, Mariusz-Orion Jêdrysek, Dominika Lewicka-Szczebak and Janusz Krajniak, Lab o ra tory of Iso tope Ge ol ogy and Geoecology, De part ment of Ap plied Ge ol ogy and Geo chem is try, In sti tute of Geo log i cal Sci ence, Uni ver sity of Wroc³aw, Cybulskiego 30, PL-50-205 Wroc³aw, Po land, e-mails: maciej.gorka@ing.uni.wroc.pl, mariusz.jedrysek@ing.uni.wroc.pl, dominika.lewicka@ing.uni.wroc.pl, janusz.krajniak@ing.uni.wroc.pl (re ceived: Sep tem ber 18, 2010; ac cepted: March 21, 2011).

Key words: at mo spheric par ti cles, anthropogenic, ox y gen iso topes, Wroc³aw.

INTRODUCTION

At mo spheric dust rang ing from the fin est par ti cles (PM1 – par ti cles less than 1 mm) to to tal sus pended par ti cles (TSP) and dust-fall can im pair hu man health (Dockery and Pope, 1996;

Siegman et al., 1999; Inyang and Bae, 2006, van Zelm et al., 2008) and cause dam age to build ings (Wilczyñska-Michalik, 2004). In spite of mod ern iza tion of all branches of in dus try, the dust prob lem in large ur ban ar eas, in clud ing Wroc³aw (SW Po - land), re mains crit i cal. The con ur ba tion of Wroc³aw, with ca.

640 000 in hab it ants, still has an old com plex road sys tem, which re sults in prob lems with air qual ity. Gen er ally, two types of anthropogenic at mo spheric pol lut ants are usu ally pres ent in ur ban ar eas: (1) low emis sion (from lo cal heat ing and traf fic pol lut ants); (2) high emis sion (from large in dus trial emit ters).

Two heat and power plants are pres ent within the bor ders of the

Wroc³aw con ur ba tion: “Wroc³aw” (a larger one, sit u ated in the cen tral part of the city) and “Czechnica” (a smaller one, sit u ated in the sub urbs, in Siechnice). Al though these two plants sup ply the ma jor ity of the con ur ba tion with heat and elec tric ity, many parts of the city, es pe cially the old build ings down town, are still heated by in di vid ual home heat ers. Clas si cal meth ods of mon i - tor ing at mo spheric pol lut ants in gen er ally only pro vide in for - ma tion about the amount of the pol lut ants (con cen tra tion or de - po si tion) but do not pro vide qual i ta tive in for ma tion on the pol - lut ants’ or i gin. The main prob lem in clas si cal mon i tor ing is how to dis tin guish an anthropogenic in put of pol lut ants from the nat u ral back ground level.

Mineralogical and geochemical stud ies to de ter mine dust or i gins have been per formed in other parts of Po land (Wilczyñska-Michalik, 1981; Manecki et al., 1988;

Schejbal-Chwastek and Tarkowski, 1988, Jab³oñska and Janeczek, 2000; Jab³oñska et al., 2003) and else where in Eu -

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rope (Querol et al., 2002; Moreno et al., 2004). Air qual ity in Wroc³aw has been in ves ti gated by other au thors and con - cerned: (1) daily fluc tu a tions of CO and NOx con cen tra tion be - tween high build ings (Miko³ajczyk et al., 1999); (2) SODAR (Sonic De tec tion And Rang ing) meth ods to quan tify at mo - spheric pol lut ants (Drzeniecka et al., 2000); (3) PM2.5 and PM10

(dust par ti cles of di am e ter less than 2.5 and 10 mi crom e ter, re - spec tively) con cen tra tions (ZwoŸdziak and ZwoŸdziak, 2006;

Sówka et al., 2010); (4) vari a tions in d³⁴S (SO₄^2-) and d¹⁸O ( SO₄^2-) in pre cip i ta tion and com po si tion of dust (Jêdrysek, 2000, 2003; Górka and Jêdrysek, 2004; Górka et al., 2008);

and (5) car bon iso tope com po si tion of or ganic par ti cles in dust-fall (Górka and Jêdrysek, 2008).

The geo chem i cal and min er al og i cal anal y ses pre sented here are part of a multiparameter in ves ti ga tion of dust-fall in Wroc³aw dur ing 2003–2005. Car bon iso tope com po si tions from the or ganic frac tion of dust-fall have al ready been pub lished and il lus trate po ten tial pit falls in the use of pas sive col lec tion meth - ods for geo chem i cal anal y sis of dust-fall in a tem per ate cli mate (Górka and Jêdrysek, 2008). The main prob lem con cern ing car - bon iso topes in or ganic mat ter as de scribed by Górka and Jêdrysek (2008) was de com po si tion and mat u ra tion pro cesses con nected with the growth of al gae, fungi and bac te ria in col lec - tors and pos si ble con tam i na tion of the sam ples col lected. Ac - cord ing to in ves ti ga tions by other au thors (Jack son, 1981; Jires et al., 2002), in flu ence of pas sive col lect ing method on the in or - ganic frac tion of dust-fall, which is the case here.

In this study we ap ply two an a lyt i cal tech niques (i.e., min - er al og i cal com po si tion and ox y gen iso to pe anal y ses of the in - or ganic frac tion) of de pos ited dust to de ter mine rel a tive con tri - bu tions of nat u ral and anthropogenic sources. The ox y gen iso - tope com po si tion of aero sol-hosted quartz grains has been used to trace dust or i gin (Jack son, 1981; Mizota et al., 1996; Aléon et al., 2002) or to dis tin guish be tween ma rine and ter res trial sands (Yang et al., 2008). Many au thors have used the ox y gen and car bon iso tope com po si tion of car bon ate to trace the or i gin of fu gi tive dust (Wang et al., 2005; Cao et al., 2008). The most re cent min er al og i cal and iso tope geo chem i cal tech niques have been able to ap ply sin gle par ti cle anal y sis (Coz et al., 2009;

Kita et al., 2009).

The po ten tial ap pli ca tion of the ox y gen iso tope tool to dis - crim i nate be tween the pri mary nat u ral soil min er als (mainly quartz) and sec ond ary anthropogenic min er als (mainly quartz and mullite), is sup ported by three as sump tions: (1) that anthropogenic min er als are en riched in ¹⁸O due to iso to pic ex - change with at mo spheric ox y gen (d¹⁸O value about +23.5‰) in in dus trial pro cesses; (2) that nat u ral soil min er als have dif fer ent ox y gen iso to pic com po si tions from anthropogenically gen er ated min er als; (3) that de pos ited at mo spheric dust col lected in Wroc³aw has in ter me di ate ox y gen iso tope com po si tions due to two-com po nent mix ing (Equa tion 1). The above as sump tions should al low us to cal cu late the anthropogenic im pact on Wroc³aw us ing iso to pic mass bal ance (Equa tions 2 and 3).

d¹⁸O_NAT<d¹⁸O_ATMO<d¹⁸O_ANTH [1]

d¹⁸O_ATMO=X_NAT´d¹⁸O_NAT+X_ANTH´d¹⁸O_ANTH [2]

%ANTH O O

O O

ATMO NAT

ANTH NAT

= -

-

d d

18 18

[3]

The d¹⁸O value of nat u ral quartz de rived from ig ne ous and meta mor phic rocks var ies be tween 8 to 16‰, whereas quartz of low tem per a ture or i gin (chert) shows d¹⁸O val ues from 14 to 33‰ de pend ing on for ma tion tem per a ture (Jack son, 1981).

The idea min eral ox y gen may ex change with ox y gen in air has been re ported in ex per i ments of ox y gen ex change in the BaSO4-O2 sys tem (Ha³as et al., 1982) or the melt ing of ba salt glass (Burkhard, 2001). Ha³as et al. (1982) re ported ox y gen iso to pic ex change be tween bar ite and ox y gen in air at 800°C.

Burkhard (2001) con firmed that the ox y gen iso to pic com po si - tion of ba saltic glass (d¹⁸O value about 4.8‰) be came en riched in ¹⁸O (to about 10.8‰) when heated to its melt ing tem per a ture of 1250°C in the pres ence of air. Lower tem per a tures did not in flu ence the ox y gen iso to pic com po si tion of glass. A very slight ox y gen ex change with gas eous ox y gen in an ex tremely thin layer (1–20 nm) has been also doc u mented in ex per i men tal stud ies with SiO2 (Trimaille and Ganem, 1997) and mullite (Fielitz et al., 2003).

On the other hand, in the ar chae o log i cal in ves ti ga tions, one of main as sump tions us ing the ox y gen iso to pic com po si tion is the in vari abil ity of iso to pic com po si tion of sil ica sand in glass pro duc tion pro cess. It is com monly as sumed that the melt ing time and tem per a ture do not in flu ence the fi nal ox y gen iso to pic com po si tion of glass, which de pends only on the pri mary ox y - gen iso to pic sig na ture of used sil ica (Brill, 1970; Henderson et al., 2005; Silvestri et al., 2010).

In sum mary, we in fer that in our case the dust gen er ated in heat and power sta tions Wroc³aw will show al tered ox y gen iso - tope com po si tions due to iso to pic ex change with ox y gen in air dur ing com bus tion at tem per a tures of 1200–1400°C, and that this is dif fer ent from that of nat u ral soil de flated dust.

EXPERIMENTAL PROCEDURES

Nine pe ri ods of sam pling of at mo spheric par ti cles have been car ried out in Wroc³aw (SW Po land). Pas sive col lec tors, built of non-re ac tive ma te ri als (plas tic) as de scribed by Jires et al. (2002), were lo cated through out the city (Fig. 1). Col lec tors were lo cated 2.5 m above the ground. The col lect ing area of the col lec tor was 0.0398 m² and the vol ume ca. 5 L. To avoid de - po si tion of large non-dust com po nents (leaves, in sects) each col lec tor was cov ered by a plas tic grid (mesh size 2 mm).

12 pas sive col lec tors were placed in ar eas of pre dom i nantly old-com pact set tle ments, high traf fic pol lu tion, and dis trib uted 1–3 km around the hard coal-fu elled heat and power sta tion

“Wroc³aw”, the larg est sin gle emit ter in Wroc³aw (Fig. 1). All the col lec tors were in stalled in No vem ber 2003 and the sam ples were gath ered ev ery two months for nine col lec tion-pe ri ods.

Be fore ox y gen iso tope and XRD (X-Ray Dif frac tion) anal - y ses, the dust ma te rial was dried, weighed and washed in 0.3 M HCl so lu tion (1 hour) in or der to re move in or ganic car bon phases (mainly car bon ates and hy drox ides) (Connin et al., 1997; Col lins et al., 1999). Af ter wards, the sam ples were

72 Maciej Górka, Mariusz-Orion Jêdrysek, Dominika Lewicka-Szczebak and Janusz Krajniak

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washed with hy dro gen per ox ide (30% H2O2) in or der to re - move or ganic mat ter (solid or ganic at mo spheric par ti cles – SOAP), as de scribed by Jack son (1985) by 3–4 weeks. The con tri bu tion of the or ganic frac tion to to tal dust has been de ter - mined by the weight loss and the to tal dust, the in or ganic min - eral frac tion (acid-in sol u ble in or ganic dust; SIAP) and the or - ganic frac tion (SOAP) were cal cu lated and ex pressed in mg/m²/day. Af ter wards, rep re sen ta tive sam ples were cho sen rep re sent ing: (1) the sum mer sea son (pe riod 5: from 20.07.2004–23.09.2004) for all col lec tors; (2) the win ter sea - son (pe riod 7: from 22.11.2004–26.01.2005) for all col lec tors and (3) the whole study pe riod (from 20.11.2003 to 25.05.2005) from one col lec tor WR9 sit u ated 1 km north of the heat and power sta tion “Wroc³aw”. These se lected sam ples have been ana lysed for min er al og i cal and iso to pic com po si - tions. The min er al og i cal com po si tions were de ter mined us ing the XRD method (XRD Philips, In sti tute of Geo log i cal Sci - ence, Uni ver sity of Wroc³aw). No ad di tional min er al og i cal treat ment or sep a ra tion of in or ganic dust phases and soils was car ried out be fore ox y gen iso to pic anal y sis. The anthropogenic ash from the elec tro-fil ters from heat and power sta tion

“Wroc³aw” and “Czechnica” was sep a rated as mag netic and non-mag netic frac tions us ing a per ma nent mag net. Be fore the d¹⁸O anal y sis sam ples were de hy drated at 300°C. The d¹⁸O anal y ses were made us ing the la ser flu o ri na tion method (Sharp, 1990; Wiechert and Hoefs, 1995; Jêdrysek and Weber-Weller, 2000) at the Lab o ra tory of Iso tope Ge ol ogy and Geoecology, Uni ver sity of Wroc³aw. The re agent gas was BrF5 and a CO2

la ser was used. Ox y gen pro duced in the re ac tion was cryo gen i -

cally pu ri fied (on two N2-traps). Fi nal pu ri fi ca tion was in a Toepler mer cury pump, where any pos si ble flu o ride re ac tion prod uct not frozen in the two N2-traps, was caught by mer cury fill ing the pump. Fi nally, ox y gen was con verted to CO2 us ing a graph ite/plat i num re ac tor. Ox y gen iso to pic ra tios were de ter - mined us ing a Finnigan MAT Delta E mass spec trom e ter. The an a lyt i cal un cer tainty of the d¹⁸O de ter mi na tion was be low 0.2‰. The ox y gen iso tope stan dards used were the IAEA NBS-28 quartz and two inter-lab o ra tory stan dards (Laussane 1 Quartz d¹⁸O = 18.15‰ and GeeWhiz Quartz d¹⁸O = 12.55‰).

The d¹⁸O val ues are ex pressed in ‰ rel a tive to the V-SMOW in ter na tional stan dard.

The same an a lyt i cal meth ods were used to ana lyse the po - ten tial sources of in or ganic at mo spheric dust. The min er al og i - cal and ox y gen iso tope com po si tions of soil min er als, anthropogenic high emis sion dust, anthropogenic low emis sion ash and min er als from the near est build ing cover were ana - lysed. Soil sam ples were col lected next to each pas sive col lec - tor dur ing one sam pling (on the 24.03.2005). The rep re sen ta - tive sam ples of elec tro-fil ter dust (from the “Wroc³aw” heat and power plant), ash (from the “Czechnica” plant and from lo - cal home heat ers) and build ing plas ter were col lected once dur - ing the en tire sam pling process, homogenized and ana lysed.

Me te o ro log i cal data were ob tained from the Me te o ro log i - cal Ob ser va tory of Wroc³aw (Uni ver sity of Wroc³aw). Com - plete me te o ro log i cal data were col lected ev ery min ute. Pre - dom i nant wind di rec tions and wind ve loc i ties were cal cu lated as a sum of fre quency within in di vid ual an gle in ter vals. Maps of the spa tial dis tri bu tion of pas sive col lec tors in Wroc³aw and

Fig. 1. Lo ca tion of the 12 pas sive col lec tors in Wroc³aw

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the dis tri bu tion of soil d¹⁸O val ues were made us ing the Golden Soft ware Surfer 8.0, whereas graphs and cor re la tions were de - ter mined us ing the Golden Soft ware Grapher 6.0 soft ware.

RESULTS

The geo chem i cal and min er al og i cal data of in or ganic phases of soil next to pas sive col lec tors are re ported in Ta - ble 1. The mass of the par ti cles col lected us ing the pas sive col lec tors has been cal cu lated as to tals and in or ganic dust de -

po si tion [mg/m²/day] for all the dust sam ples col lected dur ing the en tire study pe riod from all the pas sive col lec tors. The de - po si tion of the to tal dust var ied from 4.53 to 195.76 mg/m²/day (Fig. 2) with a min i mum value in Jan u ary 2004 and a max i mum value in July 2004; the av er age value for each sam pling pe riod var ied from 18.56 to 86.85 mg/m²/day. The de po si tion of in or ganic dust var ied from 1.20 to 135.08 mg/m²/day (Fig. 2) with a min i mum value in De cem ber 2003 and a max i mum value in Au gust 2004; the av er age for each sam pling pe riod var ied from 10.29 to 55.89 mg/m²/day. A pos i tive cor re la tion (R² = 0.78, n = 97, p <0.05) be tween to tal and in or ganic dust de po si tion has been ob served (Fig. 2). In Fig ure 2 the sam ples are di vided into 2 groups: veg e ta tive sea - son (rep re sent ing pe ri ods from late spring to early au tumn) and non-veg e ta tive sea son (rep re sent ing pe ri ods from late au - tumn to early spring). The con cen tra tion of in or ganic par ti cles in soils var ies from 95.91 to 99.12% (Ta ble 1), whereas their d¹⁸O val ues vary from 9.3 to 16.0‰ (Ta ble 1). The mass of the par ti cles col lected us ing the pas sive col lec tors has been cal cu lated as to tals and in or ganic dust de po si tion [mg/m²/day]

for all the dust sam ples col lected dur ing the en tire study pe - riod from all the pas sive col lec tors. The de po si tion of the to tal dust var ied from 4.53 to 195.76 mg/m²/day (Fig. 2) with a min i mum value in Jan u ary 2004 and a max i mum value in July 2004; the av er age value for each sam pling pe riod var ied from 18.56 to 86.85 mg/m²/day. The de po si tion of in or ganic dust var ied from 1.20 to 135.08 mg/m²/day (Fig. 2) with a min i - mum value in De cem ber 2003 and a max i mum value in Au - gust 2004; the av er age for each sam pling pe riod var ied from 10.29 to 55.89 mg/m²/day. A pos i tive cor re la tion (R² = 0.78, n = 97, p <0.05) be tween to tal and in or ganic dust de po si tion has been ob served (Fig. 2). In Fig ure 2 the sam ples are di - vided into 2 groups: veg e ta tive sea son (rep re sent ing pe ri ods from late spring to early au tumn) and non-veg e ta tive sea son

Sam ple name

Soil sam ple near pas sive col lec tors d¹⁸OV-SMOW

[‰]

In or ganic mat ter of soil [%]

Min eral com po si tion of soil (XRD)

WR 1 14.0 97.67 quartz, microcline

WR 2 13.2 98.53 quartz, microcline, al bite

WR 3 13.4 96.39 quartz, al bite

WR 8 9.3 96.78 quartz, microcline,

mus co vite

MIN 9.3 95.91

MAX 16.0 99.12

AVERAGE 13.6 97.62

T a b l e 1 Min eral com po si tion, con cen tra tion and av er age d¹⁸O val ues

of in or ganic par ti cles in soil

Anthropogenic in or ganic sources of SIAP Or i gin of sam ple d¹⁸OV-SMOW

[‰]

Min eral com po si tion of mat ter (XRD) Non-mag netic frac tion of in dus -

trial dust from heat and power

sta tion “Wroc³aw” in Wroc³aw 15.6 quartz, mullite, graph ite, gyp sum Mag netic frac tion of in dus trial

dust from heat and power sta tion

“Wroc³aw” in Wroc³aw 16.1 maghemite, chro -

mite, he ma tite Non-mag netic frac tion of in dus -

trial ash from heat and power sta - tion “Czechnica” in Siechnica

13.4 quartz, mullite

Ash from lo cal home heater 7.4 quartz, cal cite, portlandite,

anhydrite Plas ter from build ings cover n.a. quartz, cal cite, gyp -

sum, anorthoclase

n.a. – not ana lysed

T a b l e 2 Min eral com po si tion and av er age d¹⁸O val ues

of anthropogenic po ten tial sources of SIAP

Fig. 2. Re la tions be tween de po si tion of to tal and in or ganic dust in Wroc³aw in the pe riod 20.11.2003–25.05.2005

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(rep re sent ing pe ri ods from late au tumn to early spring). The spa tial dis tri bu tion of iso tope sig na tures in soil in or ganic par - ti cles next to the 12 pas sive col lec tors in Wroc³aw is shown graph i cally in Fig ure 3.

The geo chem i cal and min er al og i cal data of in or ganic phases of the po ten tial anthropogenic sources of dust col lected in Wroc³aw are shown in Ta ble 2. Their d¹⁸O val ues (Ta ble 2)

vary from 7.4‰ (ash from lo cal heat ers) to 16.1‰ (mag netic frac tion of in dus trial dust).

The geo chem i cal and min er al og i cal data of in or ganic phases of dust gath ered us ing all 12 pas sive col lec tors in pe riod 5 (20.07.2004–23.09.2004) rep re sent ing sum mer and pe riod 7 (22.11.2004–26.01.2005) rep re sent ing win ter are shown in Ta - ble 3. The d¹⁸O val ues of in or ganic par ti cles in sum mer vary from 10.9 to 18.8‰ and in win ter from 8.6 to 21.8‰ (Ta ble 3).

Fig. 3. Spa tial dis tri bu tion of d¹⁸O val ues of soil min er als next to the 12 pas sive col lec tors in Wroc³aw (back ground: layer of anthropogenic soil in Wroc³aw)

Solid In or ganic At mo spheric Par ti cles (SIAP) from 12 pas sive col lec tors Pe riod 5 (sum mer)

(20.07.2004–23.09.2004) Pe riod 7 (win ter)

(22.11.2004–26.01.2005) Col lec tor

name

d¹⁸OV-SMOW

[‰]

Min eral com po si tion

of SIAP (XRD) SIAP in to tal par ti cles fall [%]

d¹⁸OV-SMOW

[‰] Min eral com po si tion of SIAP (XRD) SIAP in to tal par ti cles fall [%]

WR 1 18.8 n.a. 62.40 19.3 quartz, microcline, mus co vite, he ma tite 98.12

WR 2 14,0 n.a. 40.63 19.1 quartz, al bite, illite 84.03

WR 3 16.8 n.a. 84.81 19.1 quartz, al bite, mus co vite n.a.

WR 4 12.7 n.a. 86.50 18.2 quartz, al bite, mus co vite 91.17

WR 5 10.9 n.a. n.a. n.a. quartz, microcline, mus co vite 95.38

WR 6 18.4 n.a. 86.87 17.3 quartz, al bite, illite, he ma tite 94.25

WR 7 18.1 n.a. 58.09 18.8 quartz, microcline, al bite, mus co vite 86.69

WR 8 16.5 n.a. 53.50 n.a. n.a. n.a.

WR 9 n.a. n.a. 45.76 14.3 quartz, microcline, illite 70.42

WR 12 n.a. n.a. 64.32 8.6 quartz, microcline, mus co vite 79.14

MIN 10.9 40.63 8.6 70.42

MAX 18.8 86.87 21.8 98.12

AVERAGE 15.8 64.34 17.6 87.88

Ex pla na tions as in Ta ble 2

T a b l e 3 Min eral com po si tion and av er age d¹⁸O val ues of SIAP from Wroc³aw dur ing two pe ri ods: period 5 (20.07.2004–23.09.2004) rep re sent ing

sum mer (veg e ta tive) par ti cles, while pe riod 7 (22.11.2004–26.01.2005) re port ing win ter (heat ing) par ti cles

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The geo chem i cal and min er al og i cal data of in or ganic phases of dust gath ered by col lec tor WR9 dur ing the en tire study pe riod (20.11.2003–25.05.2005) are shown in Ta ble 4.

The d¹⁸O val ues of in or ganic par ti cles vary from 14.1 to 18.2‰

(Ta ble 4).

Fig ure 4 shows the d¹⁸O val ues of in or ganic at mo spheric par ti cles col lected in Wroc³aw and all the as sumed nat u ral and anthropogenic sources. The re la tion be tween the iso tope ra tios and amount of in or ganic dust de po si tion is shown in Fig ure 5.

The me te o ro log i cal data for the study pe riod in di cate that the pre dom i nant wind di rec tions in Wroc³aw are south-west and north-east, and ad di tion ally south-east (ex cept in sum mer).

Winds in Wroc³aw are typ i cally of low speed (lower than 3 ms^–1). How ever, di rect com par i son of geo chem i cal and me te - o ro log i cal data is not pos si ble due to dif fer ences in the spa tial lo cal isa tion of geo chem i cal sam pling points (spa tial data) and of me te o ro log i cal mon i tor ing sta tions (sin gle point data).

DISCUSSION

Sea sonal vari a tions in to tal dust con cen tra tion (or ganic and in or ganic) as well as in the con cen tra tion of in or ganic dust phases have been ob served. Dur ing the veg e ta tive sea son (from late spring to early au tumn) de po si tion of to tal dust and in or - ganic phases of dust in Wroc³aw is higher than in the heat ing (win ter) sea son (Fig. 2). A sim i lar pat tern was ob served by Norra and Stüben (2004) in Karlsruhe, Ger many. The larger amount of to tal dust and in or ganic dust phases dur ing the veg e - ta tive sea son are due to eas ier de fla tion pro cesses (Norra and Stüben, 2004; Górka and Jêdrysek, 2008). Dur ing the heat ing sea son the frozen and snow-cov ered soil is more re sis tant to de - fla tion, hence the lower amount of de flated par ti cles, both in or - ganic and or ganic. On the other hand, the amount of to tal and

Solid In or ganic At mo spheric Par ti cles (SIAP) from pas sive col lec tor WR9 Pe riod d¹⁸OV-SMOW

[‰]

Min eral com po si tion of SIAP (XRD) 20.11.2003–13.01.2004 n.a. quartz, mus co vite

05.01.2004–15.03.2004 14.1 quartz

11.03.2004–19.05.2004 15.9 quartz, microcline, mus co vite 17.05.2004–22.07.2004 18.2 quartz, al bite, mus co vite 20.07.2004–23.09.2004 n.a. quartz, al bite, microcline,

mus co vite

21.09.2004–24.11.2004 n.a. quartz

22.11.2004–26.01.2005 14.3 quartz, microcline, illite 24.01.2005–24.03.2005 14.3 quartz, mus co vite, microcline 23.03.2005–25.05.2005 14.1 quartz, al bite, mus co vite

MIN 14.1

MAX 18.2

AVERAGE 15.1

Ex pla na tions as in Ta ble 2

T a b l e 4 Min eral com po si tion and av er age d¹⁸O val ues of SIAP from Wroc³aw in 9 pe ri ods (from 20.11.2003–25.05.2005)

from pas sive col lec tor WR 9

Fig. 4. d¹⁸O val ues of SIAP col lected in Wroc³aw and their po ten tial nat u ral (soil or i gin)

and anthropogenic (in dus trial and lo cal heater or i gin) sources

Fig. 5. Re la tion of iso to pic com po si tion to amount of in or ganic dust de po si tion (men tion: for all sites – pe ri ods 5 and 7)

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or ganic dust phases is con trolled by the higher con cen tra tion of or ganic mat ter in the at mo sphere dur ing the veg e ta tive sea son (pol len, frag ments of plants, in sects, etc.; Norra and Stüben, 2004; Górka and Jêdrysek, 2008).

There fore, dur ing heat ing sea sons we ob served lower de - po si tion of to tal dust and strong cor re la tion (R² = 0.86) with in - or ganic phases of dust (Fig. 2), which is caused by lower con - cen tra tions of at mo spheric or ganic par ti cles and lower lo cal de - fla tion. Con se quently, SIAP in heat ing sea son orig i nate mainly from anthropogenic sources or from long-trans port pro cesses (i.e. de flated in other re gions). Dur ing veg e ta tive sea sons the de po si tion of to tal dust is sig nif i cantly higher and we noted a lower cor re la tion (R² = 0.72) with in or ganic phases of dust (Fig. 2) than in heat ing sea sons. Dur ing veg e ta tive sea sons, the higher to tal dust de po si tion is prob a bly caused by higher amounts of the or ganic par ti cles and higher lo cal de fla tion.

Con se quently, SIAP in veg e ta tive sea son orig i nate mainly from lo cal de fla tion, as well as from anthropogenic sources or from long-trans port pro cesses. The wide dis per sion of veg e ta - tive sea son sam ples from “pure in or ganic mat ter line” re ported on Fig ure 2 is caused by higher con cen tra tions of or ganic mat - ter in the at mo sphere dur ing the veg e ta tive sea son in flu enc ing the pro por tional amount of SIAP in to tal de pos ited dust.

We sup posed that one of the ma jor nat u ral sources of col - lected at mo spheric dust could be rep re sented by par ti cles de - flated in near est neigh bour hood of col lec tors and trans ported over short dis tances. The min er al og i cal and ox y gen iso to pic com po si tion of ana lysed soils re ported in Ta ble 1 is typ i cal of tem per ate cli mate soils (Jack son, 1981; Mizota et al., 1992;

Norra et al., 2006). The spa tial dis tri bu tion of d¹⁸O val ues from whole in or ganic soil mat ter dem on strate good graph i cal cor re - la tion with anthropogenically de graded soils (Fig. 3). An ¹⁸O en rich ment is ob served in Wroc³aw ar eas with anthropogenic soils (d¹⁸O >15‰), when com pared to ar eas with out anthropogenic soils (d¹⁸O » 13‰; Fig. 3). In our opin ion, pos - si ble ex pla na tions for these val ues are: (1) sig nif i cant amounts of rub ble (ther mally treated build ing ma te ri als) in soils char ac - ter ised by higher d¹⁸O val ues or (2) dif fer ences in min er al og i - cal com po si tion be tween anthropogenic and nat u ral soils.

The range of d¹⁸O val ues ob tained for the cho sen hy po thet i - cal anthropogenic sources of at mo spheric in or ganic par ti cles was rather sur pris ing. In spite of the ex is tence of mullite (a min - eral formed at high tem per a ture) in non-mag netic phases of in - dus trial dust, the high est d¹⁸O value (about 16‰) is lower than ex pected if iso to pic ex change with air ox y gen (23.5‰) is as - sumed. We sup posed that sed i ment (ig ne ous or i gin) quartz in coal will get en riched in ¹⁸O as it is burned due to ex change with ox y gen in air re sult ing in very high d¹⁸O val ues of gen er - ated dust. But the d¹⁸O val ues ob tained sug gest that the hy poth - e sis of to tal ex change of ox y gen iso topes dur ing high tem per a - ture com bus tion must be re jected. How ever, when com par ing the d¹⁸O val ues of high emis sion (mag netic and non-mag netic in dus trial dust) and low emis sion (home heater ash) dust sam - ples, sig nif i cant dif fer ences were ob served (d¹⁸O about 15 and 7‰, re spec tively, Ta ble 2). The ob served en rich ment in ¹⁸O of high emis sion sam ples may be a re sult of dis tinct com bus tion tem per a tures of both pro cesses. Pos si bly the ex change may oc - cur only par tially in the very thin layer of quartz grains

(Trimaille and Ganem, 1997; Fielitz et al., 2003) and the mag - ni tude of the ex change layer de pends on the com bus tion tem - per a ture: the higher the tem per a ture, the larger the layer of ex - change and the higher the d¹⁸O value. But the dif fer ence in iso - to pic com po si tion of high and low emis sion sam ples can be also caused by the dif fer ent min er al og i cal com po si tion of dust formed in these com bus tion pro cesses (Ta ble 2). Thus, we in fer that the dust-hosted sil i cate min er als ei ther do not ex change ox - y gen iso topes with at mo spheric ox y gen dur ing burn ing (Brill, 1970; Henderson et al., 2005; Silvestri et al., 2010) or the ex - change oc curs in a very thin sur face layer (Trimaille and Ganem, 1997; Fielitz et al., 2003). Prob a bly, the ex per i men - tally con firmed en rich ment in ¹⁸O (Burkhard, 2001) does not oc cur in typ i cal burn ing pro cesses (heat and power sta tion as well as home heater coal burn ing) due to in suf fi cient tem per a - tures of the com bus tion pro cess or in suf fi cient com bus tion time to al low com plete iso to pic ex change. In the ex per i ment men - tioned above (Burkhard, 2001) ¹⁸O en rich ment has been ob - served only af ter melt ing pro cesses at a tem per a ture of 1250°C.

Such con di tions do not oc cur in home heater burn ing pro - cesses, and may oc cur only par tially dur ing in dus trial burn ing, hence the ob served en rich ment is lower than ini tially ex pected.

The d¹⁸O val ues ob tained for ae rial dust sam ples (Ta ble 3) have shown a wide range from 10.9 to 18.8‰ for the sum mer pe riod (20.07.2004–23.09.2004) and from 8.6 to 21.8‰ for the win ter pe riod (22.11.2004–26.01.2005). Com par ing the av er - age d¹⁸O val ues ob tained for the sum mer pe riod (15.8‰) and the win ter pe riod (17.6‰; Ta ble 3) with the ear lier con clu sions con cern ing the de po si tion of to tal and in or ganic par ti cles in veg e ta tive and heat ing sea sons it can be con cluded that the ob - served en rich ment of the SIAP in ¹⁸O in win ter is caused by in - creased amounts of anthropogenically changed par ti cles in the to tal pool of SIAP gen er ated in situ or de rived from long dis - tance trans port. Con versely, the en rich ment of SIAP in ¹⁸O in sum mer is lower than in the win ter pe riod due to a larger amount of soil orig i nated par ti cles (av er age 13.6‰, Ta ble 1) in the to tal SIAP and a lower in put of anthropogenically changed par ti cles gen er ated in situ or de rived from long dis tance trans - port. Un for tu nately, for the fi nal iso to pic mass bal ance cal cu la - tion, the ma jor ity of the d¹⁸O data ob tained from the pas sive col lec tors are higher than those of the pro posed nat u ral and anthropogenic sources for Wroc³aw dust (Fig. 4 and Ta - bles 3, 4). But when ana lys ing the re la tion of iso tope com po si - tion and amount of SIAP in the dust sam ples col lected (Fig. 5) a dom i nant source of SIAP can be indentified. This source iso to - pic com po si tion dif fers from the soil in or ganic par ti cles show - ing higher d¹⁸O val ues (about 18‰). The d¹⁸O val ues ob tained for quartz dust mea sured in the north ern hemi sphere (Jack son, 1981) for long-range par ti cles var ies from 17 to 21‰. There - fore, a pos si ble ex pla na tion is that the most of in or ganic par ti - cles col lected as dust-fall in Wroc³aw orig i nates from long-dis - tance trans port rather than from lo cally de flated soil par ti cles.

In this case, a part of the in or ganic dust phase de pos ited in Wroc³aw is de rived from out side of the city. The south and south-west pre dom i nant wind di rec tion in di cate the pos si ble sources for this ex ter nal dust in put:

– de fla tion of par ti cles from ag ri cul tural fields sur round - ing Wroc³aw;

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– min eral phases orig i nat ing from the Sudety Moun tains sit u ated about 80–100 km SW from Wroc³aw or from quar ries local ised about 40 km S and SW of Wroc³aw;

– pro duc tion of in or ganic dust by in dus trial cen tres (such as the cop per works sit u ated about 70 km W from Wroc³aw).

The 1.5 year long (9 pe ri ods) min er al og i cal and ox y gen iso to pic re cord for a pas sive col lec tor (WR 9 – lo cated 1 km north ward from heat and power sta tion “Wroc³aw”) is shown in Ta ble 4. The min er al og i cal com po si tion of these sam ples is very sim i lar to those col lected dur ing sum mer and win ter pe ri - ods (Ta ble 3) and from the near est soil (Ta ble 1). The d¹⁸O val - ues scat ter around 14‰, ex clud ing two pe ri ods (11.03.2004–19.05.2004 and 17.05.2004–22.07.2004), when an ¹⁸O-en rich ment ap pears.

One of the ma jor goals of this study was to as sess the in put of the anthropogenic at mo spheric par ti cles in the to tal mass of dust de pos ited in Wroc³aw. The range of d¹⁸O val ues ob tained for SIAP, soil and hy po thet i cal anthropogenic sources do not ful fil the con di tions of equa tion 1. We did not find any hy po thet i cal sources (nat u ral or anthropogenic) with high enough d¹⁸O to ex - plain all the SIAP de pos ited in Wroc³aw. There fore, in this case, cal cu la tion of the amount of anthropogenic par ti cles us ing iso to - pic mass bal ance equa tions 2 and 3 is not pos si ble.

CONCLUSIONS

The larger amount of to tal dust and in or ganic dust phases ob - served dur ing the veg e ta tion pe riod are due to eas ier de fla tion pro cesses. Dur ing the heat ing pe riod the frozen and snow-cov - ered soil is more re sis tant to de fla tion, hence the lower amount of de flated par ti cles, as in or ganic as well as or ganic. In our opin ion, the at mo spheric dust in the heat ing sea son orig i nates mainly from anthropogenic sources or from long dis tance trans port pro - cesses, whereas in the veg e ta tive sea son it orig i nates mainly

from lo cal de fla tion, as well as from anthropogenic sources or from long dis tance trans port pro cesses.

The min er al og i cal com po si tion of SIAP de pos ited in Wroc³aw is very sim i lar to the soil near est the pas sive col lec tor lo ca tion. How ever, the d¹⁸O val ues of SIAP and soil ob tained show dif fer ent ranges and, as a con se quence, ex clude lo cal soil as a ma jor po ten tial nat u ral source of SIAP.

The d¹⁸O val ues ob tained for hy po thet i cal anthropogenic sources (low and high emis sion sources) are not en riched in ¹⁸O as would be ex pected in the case of iso to pe ex change pro cesses with at mo spheric ox y gen. There fore, the ox y gen iso tope ex - change be tween min er als and ox y gen in air prob a bly does not oc cur in typ i cal com bus tion pro cess (rep re sent ing as high as well as low emis sions).

The lack of known sources en riched in ¹⁸O (higher than or equal to SIAP) makes it im pos si ble to con struct an iso to pic mass bal ance equa tion and to cal cu late the amount of anthropogenic par ti cles in the to tal dust. This sug gests the dom i nance of other sources of in or ganic dust than orig i nally as sumed.

Min er al og i cal and geo chem i cal data in di cate that the ma jor source (nat u ral or anthropogenic) of in or ganic dust de pos ited prob a bly lies out side Wroc³aw. The pre dom i nant south-west wind di rec tion may in di cate ag ri cul tural ar eas, quar ries, the Sudety Moun tains, or in dus trial cen tres as sources of SIAP in Wroc³aw. We also do not ex clude long-dis tance dust trans port as an ad di tional source of dust de pos ited in Wroc³aw.

Ac knowl edge ments. We would like to ac knowl edge Dr.

A. Ka³u¿ny for his sub stan tial help in field work. The au thors are very grate ful to A. Becker, A. Demény and one anon y mous re viewer for their crit i cal re marks on the manu script and for their valu able sug ges tions. Great thanks are due to Dr. P. Sauer for lan guage cor rec tion and sci en tific advice. This study was sup ported by the Min is try of Ed u ca tion and Sci ence of Po land:

grant No. 3 T09D 086 28 and Wroc³aw Uni ver sity grants No.

1017/S/ING/05-IX, 1017/S/ING/10-IX, 2022/W/ING/05-49, 2022/W/ING/10-02, 2022/W/ING/05-12.

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