crit i cal re marks on the pas sive method

Geo log i cal Quar terly, 2008, 52 (2): 5 26 3 C of or ganic at mo spheric dust de pos ited in Wroc³aw (SW Po land): crit i cal re marks on the pas sive method Maciej GÓRKA and Mariusz-Orion JÊDRYSEK Górka M. and Jêdrysek M.-O. (2008) 3 C of or ganic at mo spheric dust de pos ited in Wroc³aw (SW Po land): crit i cal re marks on the pas sive method. Geol. Quart., 52 (2): 5 26. Warszawa. This pa per re ports the re sults of the ap pli ca tion of pas sive col lec tors to the col lec tion of solid or ganic at mo spheric par ti cles (SOAP) in Wroc³aw (SW Po land) to carry out sta ble car bon iso tope anal y ses. 3 C (SOAP) val ues col lected dur ing the veg e ta tion-free pe riod, from No vem ber to March, vary in a nar row range from 24.5 to 27.8. We show that 3 C (SOAP) is able to pro vide in for ma tion about at - mo spheric pol lu tion with re spect to dif fer ent emis sion sources. 3 C (SOAP) val ues col lected dur ing the pe riod of veg e ta tion growth, from April to Oc to ber, show a wide range from 20.5 to 26.9. The most prob a ble ex pla na tions for the 3 C-en riched val ues in sum mer are that: (i) the SOAP have been con tam i nated with fresh and de com posed or ganic mat ter in the pas sive col lec tor and/or (ii) SOAP are de - rived from out side the city or from out side Po land (C 4 plant par ti cles). There fore, the 3 C (SOAP) may not rep re sent a strictly anthropogenic im pact. The pas sive col lec tor method for the (SOAP) col lec tion should be ap plied only in ar eas with dry de po si tion of at - mo spheric dust where de pos ited or ganic mat ter is not de com posed in the wa ter con tained in col lec tors. We rec om mend the use of ac tive sam pling meth ods (hi-vol ume sam pler) to col lect SOAP use ful for car bon iso tope anal y ses. Maciej Górka and Mariusz-Orion Jêdrysek, 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 (re ceived: Au gust 7, 2007; ac cepted: March 6, 2008). Keywords: solid or ganic at mo spheric par ti cles, pas sive col lec tor method, car bon iso topes. INTRODUCTION Atmospheric dust, especially its finest fractions (PM0, PM2,5 and PM), is very haz ard ous to hu man health (lung dis - eases, al ler gies, can cers and oth ers; Siegmann et al., 999; Inyang and Bae, 2006). In spite of the mod ern iza tion of all branches of in dus try, the dust prob lem in large ur ban ar eas, in - cluding Wroc³aw, remains critical. The agglomeration of Wroc³aw, with ca. 640000 in hab it ants and com plex old road geometry, results in problems with air quality. Generally, two types of anthropogenic at mo spheric pol lut ants are in di cated: () low emis sion (from lo cal heat ing and traf fic pol lut ants); (2) high emis sion (from large in dus trial plants, which are also lo - cated in Wroc³aw). In this pa per we re port the re sults of car bon iso tope mea - sure ments on solid at mo spheric or ganic par ti cles (SOAP) col - lected us ing the pas sive col lec tor method. The car bon iso tope anal y ses have been made as part of a larger in ves ti ga tion of at - mospheric particles (including carbon isotopes from organic particles and oxygen isotopes from mineral particles). The isotopic composition of carbon in SOAP may provide information about its po ten tial sources (soil or ganic mat ter, fresh or ganic mat ter, or ganic mat ter from combusted fos sil fu els and oth ers) and in di cate ar eas with stron ger anthropogenic im pact. In ves ti - ga tions of the air qual ity in Wroc³aw, de scribed by other au - thors, con cerned daily fluc tu a tions of CO and NO x concentration be tween high build ings (Miko³ajczyk et al., 999), SODAR (Sonic Detection And Ranging) methods indicating atmospheric pollutants (Drzeniecka et al., 2000), vari a tions of 34 S (SO 4 2 ) and 8 O (SO 4 2 ) in precipitation and in mineralogical com po si tion of dust (Jêdrysek, 2000, 2003; Górka and Jêdrysek, 2004a, b, c). The main goals of our study were: () to as sess the re li abil - ity of the pas sive col lec tion method for car bon isotope mon i tor - ing of at mo spheric dust; (2) to de ter mine sources of or ganic mat ter in SOAP (anthropogenic or nat u ral); (3) to ob serve sea - sonal variations in 3 C (SOAP); (4) to dis crim i nate po ten tial zonation in atmospheric pollution using isotope analyses combined with meteorological observations.

6 Maciej Górka and Mariusz-Orion Jêdrysek Fig.. Lo ca tion of 2 pas sive col lec tors in Wroc³aw EXPERIMENTAL PROCEDURES Nine pe ri ods of sam pling of at mo spheric dust have been car ried out in Wroc³aw (SW Po land). Pas sive col lec tors, built of non-reactive materials as described by Jires et al. (2002), were lo cated through out the city. Col lec tors were lo cated 2.5 m above the ground. The col lect ing area is 0.0398 m 2 and the vol - ume is 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). 2 pas sive col lec tors were place in ar eas of pre dom i nantly old-compact settlement, high traffic pollution, and distributed 3 km around the hard coal-fueled heat and power sta tion Wroc³aw (po ten tially the larg est sin gle emit ter in Wroc³aw; Fig. ). All the col lec tors were in stalled in No vem ber 2003 and the sam ples were gath ered ev ery two months over nine col lec - tion-periods. Be fore the car bon iso tope anal y ses, the dust ma te rial from the col lec tors was dried, weighed and washed with a 0.3M HCl so lu tion ( hour) in or der to re move in or ganic car bon phases (mainly carbonates and hydroxides; Connin et al.,997; Col - lins et al.,999). The dust sam ples were then di vided in half, and dried for 24 hours at 50 C. One part was washed with perhydrol (30% H 2 O 2 ) in or der to re move or ganic mat ter (SOAP), as de scribed by Jack son (985). The con tri bu tion of the SOAP frac tion to the to tal dust was de ter mined by the weight loss and the to tal dust, the in or ganic min eral frac tion and the or ganic frac tion were cal cu lated and ex pressed in mg/m 2 /day. The other frac tion of to tal dust par ti cles con tain ing SOAP was combusted with cop per ox ide (CuO) wire, un der vac uum at 900 C us ing the sealed quartz tube method (Boutton, 99; Skrzypek and Jêdrysek, 2005). The CO 2 ob - tained was cryo gen i cally pu ri fied and col lected in glass am - poules. Car bon iso tope ra tios were analyzed us ing mass spec - trometer MI-305 (pro duced at the Su mach fac tory, USRR) (Department of Mass Spectrometry at UMCS, Lublin, Po land) and a Finnigan MAT Delta E mass spectrometer (Laboratory of Isotope Geology and Geoecology at Uni ver sity of Wroc³aw, Po land). The er ror of the 3 C determination was below 0., for both the types of mass spec trom e ter used. The car bon sta ble iso tope stan dards used were IAEA NBS-22 and NBS-9. We also mea sured the car bon isotope com po si tion of other po ten tial sources of car bon in dust par ti cles (soil, grass, leaf, in - sect, build ing plas ter, coal, fur nace black, and soot from die sel and gas o line car en gines). Leaves, grass, and in sects were in cu - bated in rain wa ter for one month to sim u late the de com po si tion pro cesses of SOAP in the wa ter stored in the passive collectors. Meteorological data were obtained from the Meteorological Observatory of Wroc³aw (University of Wroc³aw). Com plete meteorological data were collected 60 times per hour. Predominant wind di rec tions and wind ve loc i ties were cal cu lated as a sum of fre quency in the in di vid ual an gle in ter val. Maps of the spatial distribution of SOAP deposition and 3 C val ues were made us ing the Golden Soft ware Surfer 8.0 (choos ing the in ter - polation kriging method). Graphs and cor re la tions were ob tained using Golden Soft ware Grapher 5.0 software.

3 C of organic atmospheric dust deposited in Wroc³aw (SW Poland): critical remarks on the passive method 7 RESULTS The geo chem i cal and iso tope data were ob - tained over nine col lec tion pe ri ods from 20..2003 to 25.05.2005. The mass of the par ti - cles col lected us ing the pas sive col lec tors has been cal cu lated as to tal and SOAP dust de po si - tion [mg/m 2 /day] and re ported in Tables and 2, respectively. Deposition of the total dust varied from 4.53 to 95.76 mg/m 2 /day with a min i mum value on Jan u ary 2004 and a max i mum value on July 2004; the av er age value for each sam pling pe riod var ied from 8.56 to 86.85 mg/m 2 /day. The de po si tion of the SOAP var ied from 0.62 to 4.34 mg/m 2 /day with a min i mum value on Jan - u ary 2005 and a max i mum value on July 2004; the av er age for each sam pling pe riod var ied from 3.62 to 3.86 mg/m 2 /day. The stan dard de vi a - tions of to tal dust and SOAP de po si tion for win - ter pe ri ods are less than 4 and 5 re spec tively. Table 3 reports the percentage contribution of or ganic mat ter to to tal dust de po si tion. The or - ganic mat ter con tri bu tion var ied from.88 to 74.56% with a min i mum value on Jan u ary 2005 and a max i mum value on July 2004; the av er age for each sam pling pe riod var ied from 2.2 to 50.00%. In Table 4 and Figure 2 we re port the car bon iso tope com po si tion of SOAP. The stan - dard deviation of 3 C (SOAP) val ues var ied around 0.5. The 3 C PDB value of SOAP var ied from 27.8 to 20.5 with a min i mum value on March 2004, and a max i mum value on July 2004; the av er age for each sam pling pe riod var ied be - tween 26.8 and 23.4. The spa tial dis tri bu - tion of the SOAP de po si tion in Wroc³aw dur ing the nine pe ri ods is re ported graph i cally in Figure 3. The spa tial dis tri bu tion of the 3 C val ues of SOAP in Wroc³aw dur ing the nine pe ri ods in ves - ti gated is shown in Figure 4. The correlation between the amount of de pos ited SOAP [mg/m 2 /day] and its 3 C [ ] val ues is rather low, R 2 = 0.28 (Fig. 5). The 3 C val ues of soil or ganic mat ter sam - pled on 24.03.2005 at each dust sam pling sta tion var ied from 26.8 to 24.0, the av er age be ing 25.7 (Table 5). The con cen tra tion of the or - ganic mat ter in the soil var ied from 0.88 to 4.09% with an av er age of 2.38% (Table 5). Al though in gen eral there is no cor re la tion be tween the sys - tem 3 C (SOAP) and the cor re spond ing 3 C (soil), there are two pe ri ods of re mark able cor re la tion be tween soil and SOAP car bon iso - tope composition (Table 4): R 2 = 0.28 (pe riod from 7.05.2004 to 22.07.2004) and R 2 = 0.35 (pe riod from 2.09.2004 to 24..2004). The 3 C val ues ob tained for other or ganic matter sampled randomly in Wroc³aw (Wroc³aw organic matter WOM) and be ing a po ten tial T a b l e T otal dust deposition [mg/ m 2 / day] i n W ro c ³aw (20..2003 25.05.2005 ) T otal (organic and inorganic) solid atmospheric particles deposition [mg/ m 2 /day ] Period Passive collector M in. M ax. S tand. dev. Averag e 23.03.2005 25.05.2005 24.0.2005 24.03.2005 22..2004 26.0.2005 2.09.2004 24..2004 20.07.2004 23.09.2004 7.05.2004 22.07.2004.03.2004 9.05.2004 05.0.2004 5.03.2004 20..2003 3.0.2004 W R 2 0.7 2 3 4. 9 9 6. 9 5 0.3 4 7 5.3 7 8 4.2 3 2.9 7 8. 7.6 3 8. 9 6. 9 3 0.6 3 52.6 4 2.30 3 4.9 6 63.4 4 02.86 3.6 7 2.30 6 2.0 0 4 5.9 8 5.3 2 04.43 W R2 3 4. 0 4 4.3 3.6 7 W R3 4.5 3 n.a. 3 6.5 6 2 8.7 2 0. 2 3 9.7 3 6. 0 7.4 4 3 4.2 5 4.5 3 3 9.7 3 2. 2 24.6 8 W R4 6.2 8 2 6. 7 6 7.6 0 6 0.7 2 5.4 2 9 9.9 9 3 0.9 6 2 4.3 7 6 2.7 8 6.2 8 9 9.9 9 2 8.5 5 47.8 7 49.34 4 4.7 8 63.3 2 49.34 7. 4 W R5 2.4 4 4 2.8 3 9 4.7 7 7 7.9 2 n.a. 7 2.2 2 3 0.8 8 7. 4 55.50 4 4.8 6 59.0 9 55.50 5 3.9 2 2 2.6 5 2.2 3 7 3.4. 5 W R6. 5 3 9.6 3 9 2.6 3 6.6 9 47.42 4 6.8 7 76.3 3 37.5 8.4 7 02.59 9 2.7 6 7 5.4 3 3 3.8 0 4 2.3 7 47.42 W R7 8.4 7 3 6.9 8 05.8 3 3.2 8 5.7 05.8 8 9.9 9 3.4 2 n.a. n.a. 3 3.3 5 2. 3 2 0. 6 W R8 2 0. 6 2 9. 6 24.3 3 5.6 6 43.3 6 24.3 3.2 2 2 6.2 3 2 8.2 5 6 7.7 8 3.2 2 W R9 3.6 4 5 9.3 4 3 2.3 2 2 5. 6 58.54 4 9.0 6 89. 0 26.54 3 5.3 5 58.54 5 2.5 7 3 5.3 5 38.34 29.44 7 8.7 7 W R0 3 5.6 8 4 6. 7 95.76 5 8.7 4 67.6 7 95.76 7 2.2 5 3 7.0 4 2 0.5 3 4.2 6 3.3 8 2 0.5 3 32.4 W R 2 8.4 9 5 0.2 W R2 8.0 6 8.2 5 9.2 7 9 3.4 7 8.5 9 2.6 2 2.3 2 0.4 6 6 0.9 8 8.0 6 9 3.4 7 3 5.0 0 38.5 5 M in. 4.5 3 8.2 3.6 7 2 5. 6 2 0. 2 2.6 2 2.3 2 8. 3.3 8 49.34 58.54 5 2.5 7 5.3 2 55.50 95.76 47.42 M ax. 3 5.6 8 5 9.3 4 S tand. dev. 0.3 8 3.6 2 4 2.6 4 4.7 3 4 3. 3 4.8 2.0 5 3.4 8 39.2 A verage 8.5 6 3 8.0 2 8 3.9 9 8 0.8 0 8 6.8 5 6 4.4 5 2 9.5 4 2 7.5 5 80.8 5 n.a. not analyze d

8 Maciej Górka and Mariusz-Orion Jêdrysek T a b l e S OAP dust deposition [mg/ m 2 / day] i n W ro c ³aw (20..2003 25.05.2005) Passive collector 20..2003 3.0.2004 05.0.2004 5.03.2004.03.2004 9.05.2004 7.05.2004 22.07.2004 S olid organic atmospheric particles (SOAP) deposition [mg/ m 2 /day ] 20.07.2004 23.09.2004 2.09.2004 24..2004 Period 22..2004 26.0.2005 24.0.2005 24.03.2005 23.03.2005 25.05.2005 M in. M ax. S tand. dev. Averag e W R 7.2 0 3.2 5 0.4 4 6.4 9 2 8.3 4 9. 7 0.6 2 n.a. 0.0 3 0.6 2 2 8.3 4 9.0 6.9 4 W R2 3. 9 7. 8 6. 2 5 2.0 9 6 6.6 7 5.3 9 7.3 5 7.3 6 4 7.5 9 6. 2 6 6.6 7 2 3.7 4 24.7 7 W R3 3.3 3 n.a. 3.4 9.0 2 3.0 6 5.3 7 n.a. n.a. 2.7 3.0 6 5.3 7 5.3 3 9.8 3 W R4 3.5 0 6.6 2 3 5. 2 3 5.3 0 6.9 4 4.4 9 2.7 3.7 0 3 3.7 5.7 0 3 5.3 0 4.8 4 5.5 7 W R5 6.6 2 8.5 4 2 3.6 7 2 9.8 9 n.a. 2 7.2 0.4 3 n.a. 3 0.8 2.4 3 3 0.8 2 2.3 5 8.3 W R6 3.8 6 6.5 3.5 2 3.2 2 2 0.4 2 8.3 9.3 0 n.a. 0.3 5.3 0 2 0.4 2 6.6 9 0.7 0 W R7 0.2 8 3.2 2 6 4. 9 5 9. 8 3 8.8 8 4 0.4 5 4.5 0 6.9 8 5.3 4.5 0 8 5.3 2 9. 8 35.8 8 W R8 5.0 3 7.6 4 6.6 0 2 7.9 7 4.6 n.a. n.a. 7.0 6 8.5 7 4.6 6.6 0 6.9 0 24.6 4 W R9 8.7 8 2 2.9 0 2 0.0 5.5 6 6 7.4 3 3.0 2 7.7 6 0.9 5 3 2. 7 0.9 5 6 7.4 3 2.0 0 8.7 3 W R0 0.2 5 6.9 7 3 8. 3 3 5.0 7 4 3.4 2 W R.8 2.0 5 4.0 7 00.03 6. 3.4 4 7.4 3 3.4 4.34 3.6 6.3 4.7 9 7.9 2 7. 8.7 9 00.03 3 0.8 8 32.3 4.34 3 5.0 7 27.0 W R2 5.4 0 2.7 9.7 3 3 5.5 7 2 9. n.a. 2.5 7 n.a. 8.7 7 2.5 7 3 5.5 7 3. 8 5. 3 M in. 3.3 3 2.7 9 6. 2 5.5 6 3.0 6 3.0 2 0.6 2 0.9 5 7. 8 M ax. 5.0 3 2 2.9 0 6 4. 9 4.34 6 7.4 3 00.03 7.7 6 7.06 85.3 S tand. dev. 3.9 2 6. 3 9.9 5 2 9.3 7 2.3 5 2 7.4 2 2.6 3 5.4 4 22.4 6 A verage 8.2 7 9.7 0 2 8.0 9 3 6.3 3.8 6 2 6.9 9 3.6 2 6.4 7 29.5 6 E xplanations as in Table 2

3 C of organic atmospheric dust deposited in Wroc³aw (SW Poland): critical remarks on the passive method 9 T a b l e C ontribution of SOAP in W ro c ³aw (20..2003 25.05.2005) Passive collector 20..2003 3.0.2004 05.0.2004 5.03.2004.03.2004 9.05.2004 7.05.2004 22.07.2004 20.07.2004 23.09.2004 Contribution 2.09.2004 24..2004 of organic Period 22..2004 26.0.2005 matter in dust [%] 24.0.2005 24.03.2005 23.03.2005 25.05.2005 M in. M ax. S tand. dev. Averag e W R 3 4.7 3 9.5 0 0.8 5 3 2.7 7 3 7.6 0 2 2.7 7.8 8 n.a. 4.0 0.8 8 3 7.6 0 3.3 8 20.5 W R2 3 8.6 8 6.2 4 4.8 4 9.8 8 5 9.3 7 2 4.8 2 5.9 7 4.3 4 4 6.2 7 4.3 4 5 9.3 7 6.9 4 34.4 8 W R3 7 3.5 0 n.a. 3 6.9 2 3 8.3 7 5. 9 3 8.6 8 n.a. n.a. 3 7.0 9 5. 9 7 3.5 0 8.7 6 39.9 6 W R4 5 5.7 5 2 4.7 9 5.9 5 5 8. 4 3.5 0 4.4 9 8.8 3 6.9 8 5 3.7 7 6.9 8 5 8. 4 2 2.3 32.0 2 W R5 3 0.8 7 9.9 4 2 4.9 7 3 8.3 5 n.a. 3 7.6 6 4.6 2 n.a. 2 0.6 4 4.6 2 3 8.3 5.7 8 25.2 9 W R6 3 4.6 3 6.4 6 2.4 3 2.4 3 3. 3 3 4. 5.7 5 n.a. 4. 0 5.7 5 3 4.6 3 0.4 3 9.0 W R7 5 5.6 5 3 5.7 6 4 3.5 5 5 7.6 8 4.9 5 3.6 2 3.3 6. 3 6 2.2 3.3 6 2.2 7.6 8 42.2 2 W R8 7 4.5 6 6 0.4 9 5 8.2 2 3.0 8 4 6.5 0 n.a. n.a. 5.2 2 3 5.6 3 3.0 8 7 4.5 6 5.0 0 5. 0 W R9 6 4.3 6 3 8.6 6.9 2 2 2. 5 4.2 4 2 2.8 3 2 9.5 8 3.3 5 4 7.4 7 3.3 5 6 4.3 6 2 0.5 4 38.2 7 W R0 2 8.7 2 4.9 4 2 9.4 6 4 4.5 2 3.3 8 6 3.0 9.6 2 9.6 5 3 7.4 8 9.6 5 6 3.0 9 7. 2 30. 0 W R 4.4 8 2 2.0 0 3.0 8 5 8.4 4 3.7 5 4 4. 0 8.7 4 9. 9 2 2.8 8 8.7 4 5 8.4 5.6 5 32.4 0 W R2 6 7.0 7 3 4.0 0 9.7 9 3 8.0 6 3 5.6 8 n.a. 2 0.8 6 n.a. 3 0.7 8 9.7 9 6 7.0 7 5.7 5 35. 8 M in. 2 8.7 2 9.5 0 0.8 5 2.4 3 3. 3 4.4 9.8 8 3.3 5 4.0 0 M ax. 7 4.5 6 6 0.4 9 6.9 2 5 8.4 5 9.3 7 6 3.0 9 2 9.5 8 5.2 2 62.2 S tand. dev. 7.0 7 4.6 3 7.0 3 3. 2 6.0 3 5. 2 8.3 5.9 3 5.4 8 A verage 5 0.0 0 2 6.6 3 5.5 0 4 0.9 0 3 5.6 6 3 5.6 2 2. 2 7.2 9 35. 9 E xplanations as in Table 3

20 Maciej Górka and Mariusz-Orion Jêdrysek e T a b l 3 C of SOAP i n W ro c ³aw (20..2003 25.05.2005) Passive collector 20..2003 3.0.200 4 05.0.2004 5.03.2004.03.2004 9.05.2004 7.05.2004 22.07.2004 20.07.2004 23.09.2004 3 C 2.09.2004 24..2004 P DB [ ] (SOAP ) Period 22..2004 26.0.2005 24.0.2005 24.03.2005 23.03.2005 25.05.2005 M in. M ax. S tand. dev. Averag e W R 25. 9 26. 8 25. 9 24. 4 2. 8 2. 5 26. 6 26. 7 26. 7 26. 8 2. 5 2. 25. W R2 24. 5 26. 7 25. 7 24. 6 22. 4 25. 6 26. 26. 5 22. 9 26. 7 22. 4.5 2 25. 0 W R3 n.a. n.a. 25. 6 24. 8 26. 0 25. 4 25. 8 26. 26. 26. 24. 8 0.4 8 25. 7 W R4 n.a. 27. 8 26. 9 23. 7 24. 7 20. 9 27. 0 27. 3 24. 4 27. 8 20. 9 2.3 4 25. 3 W R5 26. 0 27. 24. 20. 6 n.a. 22. 8 26. 7 26. 25. 8 27. 20. 6 2.2 5 24. 9 W R6 n.a. 26. 8 25. 5 24. 3 22. 6 2. 7 26. 3 26. 3 26. 2 26. 8 2. 7.9 3 25. 0 W R7 25. 9 27. 0 24. 5 20. 5 23. 25. 0 26. 5 26. 9 24. 5 27. 0 20. 5 2.0 9 24. 9 W R8 26. 0 26. 9 24. 2 25. 3 22. 8 n.a. n.a. 27. 3 24. 4 27. 3 22. 8.6 25. 3 W R9 n.a. 26. 2 24. 6 25. 5 26. 9 23. 8 25. 6 26. 2 26. 2 26. 9 23. 8 0.9 9 25. 6 W R0 25. 5 26. 5 24. 5 2. 5 2. 7 2. 7 25. 8 26. 3 2. 4 26. 5 2. 4 2.2 5 23. 9 W R 25. 0 25. 9 23. 3 23. 0 23. 0 25. 8 26. 8 26. 6 25. 9 26. 8 23. 0.5 5 25. 0 W R2 n.a. n.a. 25. 7 22. 2 24. 0 24. 9 26. 7 27. 2 26. 0 27. 2 22. 2.7 4 25. 3 M in. 26. 0 27. 8 26. 9 25. 5 26. 9 25. 8 27. 0 27. 3 26. 7 M ax. 24. 5 25. 9 23. 3 20. 5 2. 7 20. 9 25. 6 26. 2. 4 S tand. dev. 0.5 6 0.5 2.0.7 8.7 0.8 8 0.4 7 0.4 7.5 9 A verage 25. 6 26. 8 25. 23. 4 23. 5 23. 6 26. 4 26. 6 25. 0 R 2 3 t o 3 C (SOAP ) C (soil ) 0.0 0. 0 0.2 8 0.0 3 0.3 5 0. 2 0.0 3 0.0 8 E xplanations as in Table 4

3 C of organic atmospheric dust deposited in Wroc³aw (SW Poland): critical remarks on the passive method 2 Sam ple sta tion Or ganic mat ter from soil 3 C PDB [ ] Or ganic mat ter [%] WR 26.3 2.33 WR 2 26.2.47 WR 3 26.8 3.6 WR 4 24.5 4.09 WR 5 24.0 0.88 WR 6 25.6 0.9 WR 7 26.2 2.24 WR 8 26.6 3.22 WR 9 25.9 2.09 WR 0 24.7 2.53 WR 25.7 3.22 WR 2 26..95 Min. 26.8 0.88 Max. 24.0 4.09 Av er age 25.7 2.38 Ta ble 5 Con tri bu tion and the 3 C value of or ganic mat ter from soil sam pled on 24.03.2005 Ta ble 6 3 C PDB [ ] value of the Wroc³aw or ganic mat ter col lected for the ex per i ment Sam ple name Wroc³aw or ganic mat ter (WOM) 3 C PDB [ ] be fore in cu - ba tion 3 C PDB [ ] af ter month of in cu ba tion grass 30.5 30.7 al gae n.a. 30.7 leaf 27.3 28.4 al gae 2 n.a 28.8 in sect 30.0 30.3 coal 3 24.2 n.a. coal 4 25.7 n.a. fur nace black 5 24.5 n.a. die sel soot 28.3 n.a. gas o line soot 26.8 n.a. Min. 30.5 30.7 Max. 24.2 28.8 Av er age 27.2 29.8 al gae formed in the beaker dur ing in cu ba tion of grass (see In tro duc tion); 2 al gae formed in the beaker dur ing in cu ba - tion of leaf (see In tro duc tion); 3 low-qual ity black coal used in heat ing and power sta tion Czechnica in Siechnice high emis sion; 4 high-qual ity black coal used in lo cal hearts low emis sion; 5 fur nace black ob tained from the chim ney where high-qual ity black coal (low emis sion) has been burned; n.a. not an a lyzed Fig. 2. Sea sonal vari a tions in the 3 C value of the solid or ganic at mo spheric par ti cles (SOAP) in Wroc³aw source of SOAP are shown in Table 6. The 3 C (WOM) val ues vary from 24.2 to 30.5. The 3 C value of or ganic mat ter sam ples in cu bated in rain wa ter var ied from 28.4 to 30.7. Be side SOAP and WOM, we also mea sured the 3 C value of car bon ates from that plas ter that cov ers build ings ( 5.0 ; n = 6). Meteorological data indicate that predominant wind directions in Wroc³aw are south-west and north-east, and ad di tion - ally south-east (ex cept in sum mer). Winds in Wroc³aw are clas - si fied as of low speed, the two month-pe riod av er age ve loc ity be ing lower than 3 m/s. The ma jor wind ve loc i ties are well cor - re lated with the ma jor wind di rec tions (SW), but the stron gest wind ep i sodes cor re spond mainly to a NNW wind di rec tion. Al though it is not pos si ble to com pare, spa tially, geo chem i cal data (SOAP deposition and 3 C (SOAP)) to sin gle-point me te - orological data, meteorological data indicate the potential di - rec tions of air pol lut ant trans port (SW NE).

Fig. 3. Spatial distribution of solid organic atmospheric particle fall [mg/m2/day] in Wroc³aw 22 Maciej Górka and Mariusz-Orion Jêdrysek

23 Fig. 4. The spatial distribution of the d3cpdb [ ] value of solid organic atmospheric particles in Wroc³aw d3c of organic atmospheric dust deposited in Wroc³aw (SW Poland): critical remarks on the passive method

24 Maciej Górka and Mariusz-Orion Jêdrysek Fig. 5. Re la tions be tween the 3 C (SOAP) and SOAP fall in Wroc³aw DISCUSSION Firstly, we have ob served sea sonal vari a tions in SOAP con - cen tra tions as well as in their 3 C val ues (Figs. 2 and 5). Dur ing the heat ing pe riod (from late au tumn to early spring), SOAP fall and the 3 C var ies within rel a tively nar row ranges (Figs. 2 and 5). When veg e ta tion grows (from late spring to early au - tumn), SOAP fall and the 3 C var ies within wide ranges (Figs. 2 and 5). The spring to au tumn de po si tion of to tal (or ganic and in - or ganic) dust in Wroc³aw is higher (Table and 2) than in the win ter pe riod. A sim i lar pat tern has been ob served at Karlsruhe, Germany (Norra and Stüben, 2004). We sug gest that this is due to higher con cen tra tions of or ganic mat ter in the at mo sphere dur - ing the grow ing pe riod (pol len, frag ments of plants, in sects, etc.) as well as to stron ger de fla tion (par ti cles from soil that is un - frozen and not cov ered by snow are eas ily de flated). Also, the growth of algae, fungi and bacteria in collectors contaminating the SOAP concentrations is possible. The explanation of the 3 C (SOAP) vari a tions is prob lem - atic. More over, the ex pected SOAP 3 C val ues dur ing the heat - ing pe riod should vary be tween 24 (when the com bus tion of coal dom i nates) and 27 (when the com bus tion of die sel and oil dominates). Our expectations are supported by observations relating to liquid fuels reported by Widory et al. (2004), e.g. reg - ular and unleaded fuel combustion generates particles showing 3 C val ues 24.2 ±0.6, whereas die sel fuel par ti cles have 3 C val ues of 26.5 ±0.5. Through in ves ti ga tions on the car - bon iso tope com po si tion of Pol ish coal car ried out by Kotarba and Clay ton (2003) in di cated val ues of about 23.8 ±0.4 for Lower Silesia. The SOAP 3 C value dur ing the veg e ta tion pe riod was ex pected to vary be tween 28 and 30 due to the 3 C of lo cal C 3 plants, which can be the main source of SOAP dur ing the grow ing sea son. The data ob tained dur ing the heat ing sea son are close to the ex pected val ues (Table 4), but only in those ar eas of Wroc³aw where old set tle ments with low emissions dominated (Fig. 4). How ever, sur - pris ingly, the SOAP 3 C dur ing the grow ing pe riod var ied within a wide range from 20.5 to 27.8 (Table 4 and Fig. 2). The higher car bon iso tope ra tio dur ing the grow ing sea son can not be ex plained by the pres ence of soil par ti cles in the to tal dust fall. This is be cause the 3 C value of the soil or ganic mat ter col lected close to the pas sive col lec tors var - ied be tween 24.0 and 26.8 (Table 5). Weak positive correlations between the 3 C (soil) and 3 C (SOAP) val ues were ob served only dur ing the late spring (7.05.2004 to 22.07.2004; R 2 = 0.28) and early au tumn (2.09.2004 to 24..2004; R 2 = 0.35). This im plies in creased de po si tion of wind-borne soil or ganic mat ter in the col lec tors, and meteorological data indicate that wind directions and ve loc ity were sim i lar dur ing these two pe ri ods. The higher 3 C of the C 3 soil or ganic mat ter ob - served by pre vi ous au thors re ported 3 C val ues rang ing be tween 23 and 20 (Staddon, 2004) is not ap pli ca ble in our case, be cause Wroc³aw 3 C val ues are lower (Table 5). There fore, or ganic mat ter of soil or i gin can not ex plain the high est 3 C val ues (close to 2 ) ob tained in passive collectors (Table 4 and Fig. 2). We have to con sider whether it is pos si ble that SOAP were potentially partially altered or decomposed in situ in the wet con - ditions inside the rainwater-filled plastic collectors during the grow ing pe riod. The iso tope ra tios of the SOAP in the col lec tors could per haps be in flu enced by at mo spheric CO 2 dis solved in rain wa ter with the con se quent abun dant growth of al gae, fungi and bacteria contaminating the SOAP isotopic values. The 3 C value of the at mo spheric CO 2 in the city down town var ies be - tween 8 and 3 (Szaran, 990; Kuc, 99; Staddon, 2004; Szaran et al., 2005) this re sults in higher 3 C of the or ganic mat ter grown in the col lec tors if dis solved CO 2 can be used for the pro duc tion of this or ganic mat ter. It fol lows that, both the amount of col lected or ganic mat ter and its car bon iso tope ra tios may not be rep re sen ta tive of pris tine SOAP. A weak positive correlation between SOAP [mg/m 2 /day] and its 3 C PDB [ ] (R 2 = 0.28) was found (Fig. 5), but this is not evidence that the 3 C of SOAP is con trolled by the or i gin of the accumulated SOAP. For further evidence, a simple experiment was car ried out. Lo cal or ganic mat ter soaked for one month in rainfall water had 3 C val ues that were slightly lower than those obtained from fresh organic matter before incubation (Table 6). Al though a one-month in cu ba tion is a short time com pared to the two-month sam pling pe ri ods, the slight neg a tive change in 3 C val ues goes in the op po site di rec tion com pared to the ex pected strong pos i tive change. A sim i lar 3 C isotope depletion resulting from de com po si tion of or ganic mat ter in the soil has been no -

3 C of organic atmospheric dust deposited in Wroc³aw (SW Poland): critical remarks on the passive method 25 ticed by other au thors (Deines, 980; Benner et al., 987; Lichtfouse et al., 995). Plant lipids and lignin are 3 C-depleted rel a tive to bulk tis sue, whereas amino ac ids, cel lu lose and hemicellulose are usu ally 3 C-enriched (Lichtfouse et al., 995). Since lipids and lignin are more re sis tant to biodegradation rel a - tive to other plant con stit u ents, and be cause the ma jor part of plant car bon is rap idly re cy cled to the at mo sphere, the ac cu mu la - tion of plant mat ter into soil (or other de com posed mat ter) by se - lec tive pres er va tion of plant lipids, or lignin, vs. polysaccharides should have led to a no ta ble shift of the iso tope com po si tions of soil organic components towards 3 C-depleted values (Lichtfouse et al., 995). This may be a plau si ble ex pla na tion for our ex per i men tal re sults, but does not ex plain the rel a tively high 3 C val ues ob tained dur ing the grow ing pe riod (Table 4 and Fig. 2). Ac cord ing to these re sults, we con clude that the pas sive col lec tor method can not be ap plied in re gions with pre dom i - nantly wet deposition, especially in summer. The cause of the high- 3 C val ues also can not re sult from the con tri bu tion of plas ter from the build ing sur face ( 3 C = 5.0 ) be cause car bon ates were re moved from each SOAP sam ple (XRD con firmed) be fore the iso tope anal y ses and because high- 3 C val ues ob tained dur ing sum mer were not ob - served dur ing the win ter pe riod when a con sid er ably more ac tive physical weathering of building plaster is expected. We hypothetically suggest (not confirmed by palynological in ves ti ga tions) that the or ganic dust is de liv ered from out side of the city or even out side of Po land (par ti cles, es pe cially pol - len, de liv ered from C 4 plants have a dis tinctly higher 3 C value, close to 3 (Staddon, 2004)). At this stage we are un able to ex plain the high 3 C (SOAP) val ues col lected dur ing the grow ing pe riod (Table 4 and Fig. 2). A plau si ble mech a nism could be the for ma tion and ac - cumulation of microbiological organic matter within or/and on the sur face of SOAP and min eral par ti cles. This newly formed or ganic mat ter should be ex pected to show high 3 C val ues re - sulting from the assimilation of 3 C-enriched dissolved inorganic car bon (DIC) be ing close to iso to pic equi lib rium with at - mospheric CO 2. Also, sequential degradation would enrich the car bon pool, as the light CO 2 leaves the sys tem. Alternatively, we can hypothetically suggest that the dust collected in Wroc³aw may be trans ported from out side the city or even from out side of Po land. High 3 C val ues are char ac ter - is tic of C 4 plants which are typ i cal of warmer cli mates. The main C 4 plant cul ti vated in Po land is maize, but its amount in agricultural crops is still of negligible importance. No relatively significant correlation has been observed between meteorological data (wind roses) and geochemical data as spatial distribution of SOAP deposition (Table 2) and spa tial distribution of 3 C (SOAP) (Table 4). Regardless of the previous considerations, the passive method of col lec tion of solid or ganic at mo spheric par ti cles dur - ing the grow ing pe riod to carry out car bon isotope anal y ses is prob lem atic and per haps not ap pli ca ble in rainy ar eas. Con se - quently, SOAP car bon iso to pic anal y ses should be pref er en - tially col lected by means of high-flow analyzers (pumps) with quartz filters, particularly during summer. CONCLUSIONS. The pas sive method for the col lec tion of solid or ganic at - mospheric particles for carbon isotope analyses is not applicable in rainy ar eas dur ing the grow ing pe riod. 2. The use the ac tive sam pling meth ods (hi-vol ume sam - pler) for the col lec tion of SOAP for car bon isotope anal y ses should al ways be pre ferred. 3. Dur ing the win ter (heat ing pe riod) the de po si tion of SOAP and its 3 C (SOAP) val ues in di cate the fos sil fuel-burn - ing or i gin of SOAP in Wroc³aw. 4. Dur ing the sum mer (grow ing pe riod) the de po si tion of SOAP and its 3 C (SOAP) val ues may not be rep re sen ta tive of pris tine SOAP or in di cate the C 4 SOAP or i gin from out side the city or from out side Po land. 5. Meteorological data do not indicate unequivocal directions of trans port of air at mo spheric pol lut ants in the ag glom er - ation of Wroc³aw. Acknowledgements. Meteorological data were obtained from the Meteorological Observatory of Wroc³aw (Sec tion for Meteorology and Climatology, University of Wroc³aw). We would like to ac knowl edge A. Ka³u ny for his sub stan tial help in field work, G. Skrzypek, D. Lewicka and A. Trojanowska for their crit i cal re marks. We thank C. Turich for lan guage cor rec - tion and scientific consultancy. 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. 07/S/ING/05-IX. 2022/W/ING/05-49. 2022/W/ING/05-2. Au thors are very grate ful to A. Longinelli and M. Zimnoch for their crit i cal re marks of the manu script and for their valu - able suggestions. REFERENCES BENNER R., FOGEL M. L., SPRAGUE E. K. and HODSON R. E. 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