d
13C 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) — d13C 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): 115–126. 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. d13C (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 d13C (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. d13C (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 13C-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 (C4 plant par ti cles). There fore, the d13C (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 17, 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
At mo spheric dust, es pe cially its fin est frac tions (PM10, PM2,5 and PM1), is very haz ard ous to hu man health (lung dis - eases, al ler gies, can cers and oth ers; Siegmann et al., 1999;
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 - clud ing Wroc³aw, re mains crit i cal. The ag glom er a tion of Wroc³aw, with ca. 640000 in hab it ants and com plex old road ge om e try, re sults in prob lems with air qual ity. Gen er ally, two types of anthropogenic at mo spheric pol lut ants are in di cated:
(1) 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 - mo spheric par ti cles (in clud ing car bon iso topes from or ganic
par ti cles and ox y gen iso topes from min eral par ti cles). The iso - to pic com po si tion of car bon in SOAP may pro vide in for ma tion 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 NOx con cen tra - tion be tween high build ings (Miko³ajczyk et al., 1999), SODAR (Sonic De tec tion And Rang ing) meth ods in di cat ing at mo spheric pol lut ants (Drzeniecka et al., 2000), vari a tions of d34S (SO42-) and d18O (SO42-) in pre cip i ta tion and in min er al og i - cal com po si tion of dust (Jêdrysek, 2000, 2003; Górka and Jêdrysek, 2004a, b, c).
The main goals of our study were: (1) 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 vari a tions in d13C (SOAP); (4) to dis crim i nate po ten tial zonation in at mo spheric pol lu tion us ing isotope anal y ses com - bined with me te o ro log i cal ob ser va tions.
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-re ac tive ma te ri als as de scribed 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 m2 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).
12 pas sive col lec tors were place in ar eas of pre dom i nantly old-com pact set tle ment, high traf fic pol lu tion, and dis trib uted 1–3 km around the hard coal-fu eled heat and power sta tion
“Wroc³aw” (po ten tially 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 over nine col lec - tion-pe ri ods.
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 (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). 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% H2O2) in or der to re move or ganic mat ter (SOAP), as de scribed by Jack son (1985). 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/m2/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, 1991; Skrzypek and Jêdrysek, 2005). The CO2 ob - tained was cryo gen i cally pu ri fied and col lected in glass am - poules. Car bon iso tope ra tios were an a lyzed us ing mass spec - trom e ter MI-1305 (pro duced at the Su mach fac tory, USRR) (De part ment of Mass Spec trom e try at UMCS, Lublin, Po land) and a Finnigan MAT Delta E mass spec trom e ter (Lab o ra tory of Iso tope Ge ol ogy and Geoecology at Uni ver sity of Wroc³aw, Po land). The er ror of the d13C de ter mi na tion was be low 0.1‰, 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-19.
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.
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 60 times per hour. Pre dom i - nant 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 spa tial dis tri bu tion of SOAP de po si tion and d13C val ues were made us ing the Golden Soft ware Surfer 8.0 (choos ing the in ter - po la tion kriging method). Graphs and cor re la tions were ob tained us ing Golden Soft ware Grapher 5.0 soft ware.
Fig. 1. Lo ca tion of 12 pas sive col lec tors in Wroc³aw
RESULTS
The geo chem i cal and iso tope data were ob - tained over nine col lec tion pe ri ods from 20.11.2003 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/m2/day] and re ported in Ta bles 1 and 2, re spec tively. De po si tion of the to tal dust var ied from 4.53 to 195.76 mg/m2/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 18.56 to 86.85 mg/m2/day.
The de po si tion of the SOAP var ied from 0.62 to 114.34 mg/m2/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 31.86 mg/m2/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 14 and 5 re spec tively.
Ta ble 3 re ports the per cent age con tri bu tion 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 1.88 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 12.12 to 50.00%. In Ta ble 4 and Fig ure 2 we re port the car bon iso tope com po si tion of SOAP. The stan - dard de vi a tion of d13C (SOAP) val ues var ied around 0.5. The d13CPDB 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 Fig ure 3. The spa tial dis tri bu tion of the d13C val ues of SOAP in Wroc³aw dur ing the nine pe ri ods in ves - ti gated is shown in Fig ure 4. The cor re la tion be - tween the amount of de pos ited SOAP [mg/m2/day] and its d13C [‰] val ues is rather low, R2 = 0.28 (Fig. 5).
The d13C 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‰ (Ta ble 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% (Ta ble 5). Al though in gen eral there is no cor re la tion be tween the sys - tem d13C (SOAP) and the cor re spond ing d13C (soil), there are two pe ri ods of re mark able cor re la tion be tween soil and SOAP car bon iso - tope com po si tion (Ta ble 4): R2 = 0.28 (pe riod from 17.05.2004 to 22.07.2004) and R2 = 0.35 (pe riod from 21.09.2004 to 24.11.2004).
The d13C val ues ob tained for other or ganic mat ter sam pled ran domly in Wroc³aw (Wroc³aw or ganic mat ter — WOM) and be ing a po ten tial
evi ssaP ro tce lloc
/gm[ noi ti so ped sel ci trap cirehp so mta dilos )cina gr oni dna cina gro( la toTm2 ]yad/ doi reP –3002.11.02 4002.10.31–4002.10.50 4002.30.51–4002.30.11 4002.50.91–4002.50.71 4002.70.22–4002.70.02 4002.90.32–4002.90.12 4002.11.42–4002.11.22 5002.10.62–5002.10.42 5002.30.42–5002.30.32 5002.50.52.niM.xaM.ved .dnatSeg ar evA 1RW27.0291.4391.6943.0573.5712.4879.2311.8 36.1711.8 91.6936.0346.25 2RW01.4313.4476.31 34.401 03.21100.2689.5423.15 68.20176.31 03.21169.4344.36 3RW35.4 .a.n65.6317.8221.0237.9301.6144.7152.4335.4 37.9321.2186.42 4RW82.6 7.6206.7627.0624.1599.9969.0373.4287.2682.6 99.9955.8278.74 5RW44.1238.2477.4929.77.a.n22.2788.0341.71 43.94141.71 43.94187.4423.36 6RW51.1136.9336.2996.16 05.55129.3556.2232.1214.3751.11 05.55168.4490.95 7RW74.8189.63 24.741 95.20167.2934.5708.3373.24 51.73174.81 24.74178.6433.67 8RW61.0261.92 18.50199.9824.13.a.n.a.n13.3331.2561.02 18.50182.3317.15 9RW46.3143.9523.2361.52 13.42122.3132.6252.8287.7622.31 13.42166.5363.34 01RW86.537.64 44.92177.87 43.831 45.85175.2553.53 45.62153.53 45.85160.9401.98 11RW94.8212.05 41.231 67.59152.2740.7335.0262.1483.1335.02 67.59147.8576.76 21RW60.8 12.8 72.9574.3995.1826.2123.2164.0189.0660.8 74.3900.5355.83 niM.35.4 12.8 76.3161.5221.0226.2123.2111.8 83.13 .xaM86.5343.95 24.741 67.591 05.551 45.85175.2523.15 43.941 .ved .dnatS83.0126.3116.2437.4431.3418.1450.2184.3112.93 eg ar evA65.8120.8399.3808.0858.6854.4645.9255.7258.08 ton — .a.n dezy l ana 1el baT /gm[ noi ti so ped tsud la toTm2ni ]yad/corW)5002.50.52–3002.11.02( wa³
evi ssaP ro tce lloc
/gm[ noi ti so ped )PAOS( sel ci trap cirehp so mta cina gro diloSm2]yad/ doi reP –3002.11.02 4002.10.31–4002.10.50 4002.30.51–4002.30.11 4002.50.91–4002.50.71 4002.70.22–4002.70.02 4002.90.32–4002.90.12 4002.11.42–4002.11.22 5002.10.62–5002.10.42 5002.30.42–5002.30.32 5002.50.52.niM.xaM.ved .dnatSeg ar evA 1RW02.7 52.3 44.0194.6143.8271.9126.0.a.n30.0126.043.8260.9 49.11 2RW91.3181.7 21.6 90.2576.6693.5153.763.795.7421.676.6647.3277.42 3RW33.3 .a.n94.3120.1160.3 73.51.a.n.a.n17.2160.373.5133.5 38.9 4RW05.3 26.6 21.5303.5349.6 94.4137.207.157.3307.103.5348.4175.51 5RW26.6 45.8 76.3298.92.a.n02.7234.1.a.n28.0334.128.0353.2113.81 6RW68.3 35.6 25.1122.3124.0293.8103.1.a.n53.0103.124.0296.6 07.01 7RW82.0122.3191.4681.9588.8354.0405.419.613.5805.413.5881.9288.53 8RW30.5146.7106.1679.7216.41.a.n.a.n 60.7175.81 16.4106.1609.6146.42 9RW87.8 09.2210.0265.5 34.7620.3 67.759.071.2359.034.7600.1237.81 01RW52.0179.6 31.8370.5324.34 30.00111.614.334.7414.3 30.00188.0313.23 11RW28.1150.1170.14 43.41116.1343.6197.129.781.7 97.1 43.41170.5310.72 21RW04.5 97.2 37.1175.5311.92.a.n75.2.a.n77.8175.275.5381.3131.51 niM.33.3 97.2 21.6 65.5 60.3 20.3 26.059.081.7 xaM.30.5109.2291.46 43.41134.76 30.00167.7 60.7113.58 .ved .dnatS29.3 31.6 59.9173.9253.1224.7236.244.564.22 eg ar evA72.8 07.9 90.8213.6368.1399.6226.374.665.92 ni sa snoi ta nal pxE1 el baT 2el baT /gm[ noi ti so ped tsud PAOSm2 ni ]yad/corW )5002.50.52–3002.11.02( wa³
evi ssaP ro tce lloc
]%[ tsud ni re ttam cina gro fo noi tu bir tnoC doi reP –3002.11.02 4002.10.31–4002.10.50 4002.30.51–4002.30.11 4002.50.91–4002.50.71 4002.70.22–4002.70.02 4002.90.32–4002.90.12 4002.11.42–4002.11.22 5002.10.62–5002.10.42 5002.30.42–5002.30.32 5002.50.52.niM.xaM.ved .dnatSeg ar evA 1RW37.4305.9 58.0177.2306.7377.2288.1 .a.n00.4188.1 06.7383.3115.02 2RW86.8312.6118.4488.9473.9528.4279.5143.4172.6443.4173.9549.6184.43 3RW05.37.a.n29.6373.8391.5186.83.a.n.a.n90.7391.5105.3767.8169.93 4RW57.5597.4259.1541.8505.3194.4138.8 89.6 77.3589.6 41.8513.2220.23 5RW78.0349.9179.4253.83.a.n66.7326.4 .a.n46.0226.4 53.8387.1192.52 6RW36.4364.6134.2134.1231.3111.4357.5 .a.n01.4157.5 36.4334.0110.91 7RW56.5567.5355.3486.7519.1426.3513.313.6112.2613.3112.2686.7122.24 8RW65.4794.0622.8580.1305.64.a.n.a.n22.1536.5380.1365.4700.5101.15 9RW63.46 6.8329.1611.2242.4538.2285.9253.3 74.7453.3 63.4645.0272.83 01RW27.8249.4164.9225.4483.1390.3626.1156.9 84.7356.9 90.3621.7101.03 11RW84.1400.2280.1314.8557.3401.4447.8 91.9188.2247.8 14.8556.5104.23 21RW70.7600.4397.9160.8386.53.a.n68.02.a.n87.0397.9170.7657.5181.53 niM.27.8205.9 58.0134.1231.3194.4188.1 53.3 00.41 xaM.65.4794.0629.1614.8573.9590.3685.9222.1512.26 .ved .dnatS70.7136.4130.7121.3130.6121.5113.8 39.5184.51 eg ar evA00.0516.6205.5309.0466.5326.5321.2192.7191.53 ni sa snoi ta nal pxE1 el baT 3el baT ni PAOS fo noi tu bir tnoCcorW )5002.50.52–3002.11.02( wa³
