The polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic

BioMed Cen al Page 1 o 21 (page numbe no o ci a ion pu poses) Geochemical T ansac ions Open Access Resea ch a icle The polycyclic a oma ic hyd oca bon concen a ions in soils in he Region o Valasske Mezi ici, he Czech Republic Daniela Plachá*1, Helena Racla ská2, Dalibo Ma ýsek2 and Ma k H Rümmeli3 Add ess: 1Cen e o Nano echnology, VSB - Technical Uni e si y o Os a a, 17.lis opadu 15, 708 33 Os a a - Po uba, Czech Republic, 2Ins i u e o Geological Enginee ing, VSB - Technical Uni e si y o Os a a, he Facul y o Mining and Geology, 17.lis opadu 15, 708 33 Os a a - Po uba, Czech Republic and 3Leibniz Ins i u e o Solid S a e and Ma e ials Resea ch D esden, IFW D esden, P.O. Box 27016, Helmholzs ase 20, 01069 D esden, Ge many Email: Daniela Plachá* - daniela.placha@ sb.cz; Helena Racla ská - [email p o ec ed]; Dalibo Ma ýsek - [email p o ec ed]; Ma k H Rümmeli - m. uemmeli@i w-d esden.de * Co esponding au ho Abs ac The polycyclic a oma ic hyd oca bon (PAH) con amina ion o u ban, ag icul u al and o es soil samples was in es iga ed om samples ob ained in he su oundings o Valasske Mezi ici. Valasske Mezi ici is a own loca ed in he no h-eas moun ainous pa o he Czech Republic, whe e a coal a e ine y is si ua ed. 16 PAHs lis ed in he US EPA we e in es iga ed. O ganic oxidizable ca bon was also obse ed in he o es soils. The PAH concen a ions anged om 0.86-10.84 (wi h one anomalous alue o 35.14) and 7.66-79.39 mg/kg dm in he u ban/ag icul u al and o es soils, espec i ely. While he PAH le els in he u ban/ag icul u al soils a e wi hin he ange ypically ound in indus ialized a eas, he o es soils showed ele a ed PAH concen a ions compa ed o o he o es soils in Wes e n and No he n Eu ope. The PAH concen a ions and hei molecula dis ibu ion a ios we e s udied as unc ions o he sample loca ion and he me eo ological his o y. The soils om locali ies a highe al i udes abo e sea le el ha e he highes PAH concen a ions, and he PAH concen a ions dec ease wi h inc easing dis ance om he own. 1. Backg ound Many si es in he Czech Republic ha e been nega i ely a ec ed by indus ial pollu ion. The own o Valasske Mezi ici and i s su oundings, in he no heas o he epublic, is one o hese si es. In he 1960s, a coal a e in- e y was es ablished he e. Coal a e ine ies a e known sou ces o pollu ion; among he pollu an s hey p oduce a e a ious o ganic compounds, including polycyclic a o- ma ic hyd oca bons (PAHs). The PAHs o m a g oup o chemical compounds ha a e ubiqui ous in he en i onmen [1]. These compounds a e well known o hei cha ac e is ic p ope ies, such as ox- ici y and ca cinogeni y, en i onmen al pe sis ence and endency o bioaccumula ion [1-5]. They o m h ough he incomple e combus ion o py olysis o o ganic ma e , and hei elease in o he a mosphe e is connec ed wi h ene gy and hea p oduc ion, local hea ing acili ies, ehi- cle exhaus s, e use bu ning, coke o ens, and so on. They also en e he en i onmen ia na u al p ocesses such as olcanic ac i i y o o es and p ai ie i es [6,7]. A e being emi ed in o he a mosphe e, hey a e edis ibu ed be ween he gas and pa icle phases, and subsequen ly deposi ed o he e es ial en i onmen h ough d y o Published: 14 Decembe 2009 Geochemical T ansac ions 2009, 10:12 doi:10.1186/1467-4866-10-12 Recei ed: 6 Ma ch 2009 Accep ed: 14 Decembe 2009 This a icle is a ailable om: h p://www.geochemical ansac ions.com/con en /10/1/12 © 2009 Plachá e al; licensee BioMed Cen al L d. This is an Open Access a icle dis ibu ed unde he e ms o he C ea i e Commons A ibu ion License (h p://c ea i ecommons.o g/licenses/by/2.0), which pe mi s un es ic ed use, dis ibu ion, and ep oduc ion in any medium, p o ided he o iginal wo k is p ope ly ci ed. Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 2 o 21 (page numbe no o ci a ion pu poses) we deposi ion [8]. Be o e being deposi ed, hey can be anspo ed o e long dis ances. Thus, he soil is con amina ed wi h PAHs mainly om a mosphe ic deposi ions, di ec ly o ia ege a ion, o in he case o a able soil wi h biowas e used as e ilize s [2]. Soil con amina ion by PAHs is conside ed o be a good indica o o he le el o en i onmen al pollu ion by human ac i i ies [8,9]. I can p o ide in o ma ion on egional pollu ion sou ces, he long- ange anspo o PAHs, he a es o pollu an e en ion and hei ul ima e des ina ion [10,11]. The aim o his pape is o in es iga e he occu ence o PAHs in u ban and ag icul u al soils ha a e di ec ly impac ed by human ac i i y (u ban/ag icul u al soils) and in o es opsoils in he Valasske Mezi ici Region in he Czech Republic, in he icini y o a coal a e ine y and ca bon black p oduc ion. This in o ma ion on PAH dis i- bu ion can be used o heal h isk assessmen and u u e u ban de elopmen . 2. Ma e ials and me hods 2.1. Si e loca ion and desc ip ion The s udy a ea is loca ed in he no heas o he Czech Republic, in he dis ic o Zlin (Figu e 1). The own o Valasske Mezi ici is si ua ed a he oo hills o he Mo a- ian-Silesian Beskydy Moun ains, he Hos yn Hills and he Vse in Hills, nea he con luence o he Rozno Bec a and he Vse in Bec a Ri e s (49°27' - 49°30'N and - 18°0' E), a al i udes 400-17°56' 600 m abo e sea le el. The su - ace a ea is 5,481 ha [12]. Acco ding o he gene al en- yea wind da a (Figu e 2), he p e ailing wind di ec ion is om he sou h (30.8%), ollowed by calm (17.2%) and no he ly wind di ec ion (12.60%). The o he wind di ec- ions accoun o up o 10% o he da a. The eas e n wind di ec ion has he lowes equency. The own is an impo an indus ial cen e and a signi i- can ailway and oad junc ion, wi h a ela i ely high a - ic densi y. The main indus ial sou ce o PAH pollu ion is he coal a e ine y (DEZA Co po a ion) and he ca bon black p oduc ion plan (CABOT CS). Bo h o hese sou ces a e loca ed in he no h o he own (Figu e 1). DEZA a.s. is he only Czech p oduce o a oma ic hyd o- ca bons ha a e ob ained by p ocessing coal a and ben- zol. The annual p ocessing capaci y o DEZA is 160,000 M o c ude benzol and 450,000 M o c ude coal a . The company's business is p ocessing coal a , mixed a oils, benzol and aw ma e ials o he p oduc ion o phenols. Coal a s a e composed o hund eds o o ganic com- pounds: a oma ic compounds, including PAHs, he e ocy- clic PAHs, phenols, benzene, oluene, and xylenes, as well as alipha ic and pola hyd oca bons, bu he chemical composi ion o coal a may a y as a unc ion o many ac o s, including eed s ock, plan ope a ing condi ions and wea he ing once eleased o he en i onmen [13,14]. The p oduc s o DEZA a e mainly a oma ic hyd oca bons - benzene, oluene, mix u es o xylenes, phenols, c esols, and xylenols - ollowed by polycyclic a oma ic hyd oca - bons - an h acene, ca bazol and naph halene, ph halic anhyd ide, dioc yl ph hala e. Coal a pi ch is also among hei impo an p oduc s. The company is he supplie o aw ma e ials o he p oduc ion o ca bon black in he a ilia ed company CS-CABOT [15]. Acco ding o he Czech In eg a ed pollu ion egis e , he company epo ed annual naph halene emissions o 50,000 kg. The emi ed quan i ies o he o he PAH compounds a e no epo ed [16]. 2.2 Sampling o soils and analy ical me hods Fo y samples we e collec ed o he de e mina ion o he PAH dis ibu ion in soils om he a ea o Valasske Mezi - ici. Twen y samples we e collec ed om u ban g ass-co - e ed and ag icul u al soils in he own and in i s nea es su oundings. Ag icul u al soil e e s o soil ha is used o ag icul u al uses, o example, soil o ood p oduc- ion, pas u e land and g assland. U ban soil e e s o soil no used o ag icul u e, occu ing in he e i o y o he u ban se lemen . In his con ex , i ep esen s soil in own ga dens, soil along he oads and oad junc ions, pa king places, and so on. These ype o soils a e a ec ed by human ac i i ies [17,18]. The sampling si es we e selec ed in o de o e lec he di e se exposu e o soils o he pol- lu ion sou ces and dominan wind di ec ions. They ep e- sen samples di ec ly a ec ed by indus ial emissions, and di ec ly subjec ed o anspo and/o local hea ing emis- sions. Twen y samples we e collec ed om he humus laye o o es soils on he hill slopes in he su oundings o he own; 15 in coni e ous o es s and 5 in mixed o es s. The sampling si es we e also selec ed o ep esen a di e si y o dominan wind di ec ions. The sampling si es a e shown in Figu e 3 and desc ibed in Tables 1 and 2. The sampling p ocedu e, he physical sam- ple p epa a ions and he ep esen a i e sample di ision we e accomplished by using simple andom shallow sam- pling acco ding o Tan (2005) and ISO 10381-4:2003 and ISO 10381-5:2005 [19-21]. The samples we e collec ed om he su ace laye ( om A-ho izon o 0-10 cm dep h), a e emo ing g ass in u ban/ag icul u al soil and needles and li e in o es soil. App oxima ely 2 kg o ma e ial we e collec ed om a squa e a ea o 10 × 10 m in each sampling si e. All samples we e pu in o glass con aine s wi h a minimum headspace o ai , and immedia ely ans- po ed o he labo a o y. In each se ies o samples, one Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 3 o 21 (page numbe no o ci a ion pu poses) The local landscape a ound he own o Valasske Mezi ici own and he coal a e ine yFigu e 1 The local landscape a ound he own o Valasske Mezi ici own and he coal a e ine y. Some al i udes a e ma ked (in o ange). Os a a Valašské Meziříčí P aha B no Czech Republic DEZA 1023 km Scale Beč a Rožno ská Beč a Vse ínská Beč a Valašské Meziříčí Mo a sko sle zské Be sky d y M s. Ro žno - Vse ín Up la nd 397 639 508 411 709 748 502 285 375 344 424 321 409 439 515 534 608 572 534 578 557 458 485 449 378 420 Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 4 o 21 (page numbe no o ci a ion pu poses) sample was collec ed o he dep h o he A- and B- (14-50 cm) ho izons. Analyses o 16 PAHs iden i ied by he US En i onmen al P o ec ion Agency (EPA) as p io i y pollu an s we e pe - o med a he Ins i u e o Public Heal h, The Depa men o Hygienic Labo a o ies in F ydek-Mis ek, wo king in acco dance wi h EN ISO/IEC 17025 and acc edi ed by The Czech Acc edi a ion Ins i u e. The labo a o y is he Czech Na ional Re e ence Labo a o y o Pe sis en O ganic Pol- lu an s. All he sol en s used (pu chased om Sigma Ald ich) we e o HPLC g ade. The s ock e e ence s anda d mix u e o 16 PAH EPA 610 PAH MIX (Supelco Co., Ca . No. 48743), including naph halene, acenaph hylene, acenaph hene, luo ene, phenan h ene, an h acene, luo an hene, py ene, benz [a]an h acene, ch ysene, benzo [b] luo an hene, benzo [k] luo an hene, benzo [a]py ene, indeno [1,2,3-cd]py ene, dibenzo [a,h]an h a- cene and benzo [ghi]pe ylene o 100-2000 ng/ml in me hanol, was used as an ex e nal calib a ion s anda d. The calib a ion was pe o med by di ec injec ion o dilu ed s anda d solu ions in o GC o HPLC de ices, and he eg essions o peak a eas agains concen a ions we e calcula ed (R2 > 0.9998). The s anda ds we e simul ane- ously ea ed using all p ocedu e s eps o elimina e losses o PAH compounds du ing sample p epa a ions and ex ac ions. No su oga e s anda d was used, bu ma ix The en-yea wind ose in he Valasske Mezi ici RegionFigu e 2 The en-yea wind ose in he Valasske Mezi ici Region. 0 5 10 15 20 25 30 35 N NE E SE S SW W NW 0 - 2.5 m/s 2.6 - 7.5 m/s >7.5ms/ To al Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 5 o 21 (page numbe no o ci a ion pu poses) in luence was ollowed o di e en PAH-spiked ma e ials (sewage sludge, di e en soils, ashes, ubbish). The limi s o de ec ion and measu emen unce ain ies o PAH compounds a e shown in Table 3. The alues o he limi s o de ec ion we e de i ed 1) om he smalles in e- g able a eas o each compound peaks in signal and 2) om he a io be ween he analy e signal and he baseline noise (limi o de ec ion = peak heigh /noise a io o 3). The limi s o de ec ion we e de e mined o con amina ed soil ma ices [22]. The measu emen unce ain ies a e expanded unce ain ies calcula ed by mul iplying he combined s anda d unce ain ies by a co e age ac o k = 2 o an app oxima e le el o con idence o 95% [23]. A su icien pa o each sample was aken o he PAH ex ac ion. The samples we e no d ied be o e ex ac ion. The PAH compounds we e ex ac ed om he soil samples Loca ions o sampling si es in he Valasske Mezi ici RegionFigu e 3 Loca ions o sampling si es in he Valasske Mezi ici Region. 1 2 3 4 5 6 9 8 12 11 10 21 20 7 18 13 17 16 14 15 1023 km Scale New analysis o u ban/ag icul u al soils New analysis o o es soils Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 6 o 21 (page numbe no o ci a ion pu poses) using a 1:1 ( : ) mix u e o ace one and hexane in a Sox- wa 3.6 mic owa e ex ac o (5 min o 20% mic owa e pe o mance, ollowing 55 min o 60% pe o mance). The inal ex ac s we e il e ed, d ied wi h Na2SO4 and e apo a ed o p oduce nea -d y esidue. The esidue was edissol ed in 1 ml o hexane and di ided in o wo aliq- uo s; one hal o he olume was used o gas ch oma og- aphy - mass spec ome y (GC/MS) analysis and he second hal was analyzed by high p essu e liquid ch oma- og aphy wi h luo escence de ec o (HPLC/FD) a e sol- en exchange (hexane o me hanol). The ch oma og aphic analyses we e pe o med using a GCQ/ Pola is Q The moFinnigan gas ch oma og aph, equipped wi h a DB-5MS 30 m × 0.25 mm × 0.25 μm column, and Table 1: Desc ip ion o u ban/ag icul u al soil sampling si es Sample ID Soil sample ype Al i ude (m a.s.l.) Coo dina es X.Y Di ec ion* pH/KCl pH/H20 6 u ban 441 499076 1138446 Sou h-Wes 6,61 5,79 7 ag icul u al 427 498619 1137867 Sou h 7,45 7,03 11 u ban 181 495031 11440205 Sou h-Eas 6,62 5,83 12 u ban 409 494700 1138994 Sou h-Eas 6,19 4,95 13 ag icul u al 192 497293 1136156 No h 6,14 5,08 14 u ban 403 496516 1138738 Sou h 7,24 6,98 15 ag icul u al 350 496016 1136550 Eas 6,28 4,74 16 ag icul u al 352 496356 1134721 No h 7,04 6,36 17 u ban 316 496189 1140722 Sou h 6,63 5,95 18 u ban 318 497084 1141013 Sou h 6,48 5,93 19 u ban 336 496803 1139240 Sou h 5,71 4,69 20 semi-u ban 400 493484 1135740 No h-Eas 6,10 5,06 41 u ban 207 498198 1137905 Sou h 6,73 5,83 54 ag icul u al 337 494944 1133779 No h-Eas 6,80 5,76 78 ag icul u al 313 498421 1135172 No h 5,55 4,62 108 ag icul u al 359 498827 1141290 Sou h 6,13 5,28 109 u ban 300 497943 1140006 Sou h 7,68 7,12 116 ag icul u al 357 495296 1141360 Sou h-Eas 6,60 5,68 137 u ban 321 497250 119944 Sou h 7,30 6,86 138 u ban 404 495636 11338848 Eas 6,86 5,92 *di ec ion om coal a e ine y Table 2: Desc ip ion o o es soil sampling si es Sample ID Al i ude (m a.s.l.) Coo dina es X.Y Di ec ion* Dis ance** pH/KCl pH/H20 O ganic ox ca bon (%) 1 400 495130.11 1133851.02 No d 5,6 2,85 3,30 15,60 2 290 499432.48 1132383.39 No d 7,0 2,88 3,35 18,01 3 275 500649.60 1136282.43 Wes 5,2 2,88 3,41 13.89 4 350 503261.27 1138848.46 Wes 6,5 3,06 3,51 11,05 5 400 502271.46 1141773.46 Sou h-Wes 6,1 3,16 3,66 19,20 6 330 500403.36 1140301.10 Sou h-Wes 3,8 3,06 3,59 10,25 7 500 499647.69 1142466.15 Sou h 4,1 2,90 3,80 12,90 8 365 499887.02 1137853.47 Wes 3,6 3,35 3,84 10,31 9 400 498311.52 1138633.84 Sou h 2,1 3,06 3,52 8,88 10 300 495502.65 1136669.43 Eas 3,1 2,81 3,24 16.45 11 295 498040.78 1135367.05 No d-Wes 4,7 3,47 4,03 10,59 12 350 504876.07 1135413.47 Wes 9,3 3,23 3,71 10,31 13 450 495988.96 1143370.04 Sou h 4,1 3,23 3,61 3,45 14 625 492916.90 1143460.66 Sou h-Eas 5,7 3,10 3,48 13.54 15 670 491938.90 1149477.01 Sou h 11,4 2,82 3,31 17.21 16 550 496606.90 1148941.20 Sou h 9,7 3,04 3,49 15.78 17 400 502434.54 1146456.76 Sou h 9,1 2,99 3,50 14.27 18 400 500554.75 1144153.94 Sou h 6,4 2,74 3,26 18.91 20 400 493353.48 1137947.81 Eas 3,6 3,12 3,52 16.47 21 400 493050.59 1135369.90 No d Eas 5,3 3,09 3,38 17.85 * di ec ion om coal a e ine y * *app oxima e dis ance o he middle own. Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 7 o 21 (page numbe no o ci a ion pu poses) a Hewle Packa d Se ies 1100 liquid ch oma og aph wi h a luo escence de ec o , equipped wi h a Me ck LiCh o- CART 250-3 column. The GC/MS analysis was used o he de e mina ion o ligh PAHs - naph halene, acenaph- hene, acenaph hylene and luo ene; he o he PAHs we e analyzed by HPLC/FD me hod. The d y ma e con en o each soil sample was de e - mined a e d ying in an o en a 105 ± 3°C o cons an weigh . The o ganic oxidizable ca bon (Cox) con en (in pe cen age) was de e mined in each o es soil sample by he modi ied Walkley-Black (VB) dich oma e me hods [24]. The alues we e de e mined o be in he ange 3.45- 19.20% (Table 2). ISO 10390:2005 was used o he ou- ine de e mina ion o pH using a glass elec ode in a 1:5 ( olume ac ion) suspension o soil in wa e (pH in H2O) and 1 mol.l-1 po assium chlo ide solu ion (pH in KCl) (Table 1 and 2). 3. Resul s and discussion 3.1 PAH con en in u ban/ag icul u al soil The esul s o he PAH analysis o u ban/ag icul u al soil samples a e shown in Tables 4, 5 in mg/kg dm, and he s a is ical e alua ion appea s in Table 6. The o al concen- a ions o PAHs ( iz. he selec ed 16 PAHs) a ied om 0.861-10.840 mg/kg dm, wi h one anomalous alue o 35.140 mg/kg dm; he a i hme ic mean o he PAH con- cen a ions was 5.527 mg/kg dm and he median was 3.370 mg/kg dm. Only he concen a ions o hose PAHs wi h alues abo e he de ec ion limi s a e calcula ed. The sum o 7 ca cinogenic PAHs (acco ding o IARC - benzo [a]an h acene, ch ysene, benzo [b] luo an hene, benzo [k] luo an hene, benzo [a]py ene, dibenzo [a,h]an h a- cene, indeno [1,2,3-cd]py ene) anged om 0.400 o 5.090 mg/kg dm, wi h one alue o 16.000 mg/kg dm belonging o he anomalous PAH concen a ion. The sum o hese 7 ca cinogenic PAHs o med 40-57% o he o al PAHs; only one sample om locali y K ho a (ID sample 138) had he sum 30%. An analysis o he sample wi h A- and B-ho izons is shown in Table 7. The obse ed alues o he PAH concen a ions in he B-ho izon we e simila o he concen a ions in he A-ho izon. The alues we e in he ange ha was obse ed o ypical concen a ions in u ban soils (0.600-3.000 mg/kg), and hey a e highe han ypical concen a ions in o es and u al soils (up o 1.000 mg/kg) [25]. We do no know he ull his o y o he si e, bu he ela i ely high PAH concen a ion alues show an in luence due o human ac i i y. The concen a- ions o he ca cinogenic ac ion - benzo [a]py ene we e in he ange o 0.06-2.25 mg/kg dm, wi h an a i hme ic mean o 0.36 mg/kg dm and a median o 0.22 mg/kg dm. The highes concen a ions o he 16 selec ed PAHs we e iden i ied in he u ban soils in he Valasske Mezi ici own e i o y (ID 137, 109, 17, 18, 41, 11), and a he Ju inka (ID 6) and Policna (ID 108) si es. All o hese sampling si es a e si ua ed sou h o he coal a e ine y and a e in he p oximi y o he own cen e and he coal a e ine y. In luences om all PAH sou ces (indus ial ac i i y, local hea ing and anspo ) a e e iden . The emaining sam- ples we e collec ed no h o he s udy a ea, and he iden- i ied PAH concen a ions we e lowe in hese si es. The si es (ID 13, 15, 20, 54, 78) a e si ua ed in he di ec ion o he p e ailing wind low, and he landscape o his egion dec eases in al i ude in his di ec ion. The PAH a mos- Table 3: Limi o de ec ion and measu emen unce ain y PAHs Limi o de ec ion mg/kg Measu emen unce ain y* % Naph halene 0.050 30 Acenaph hylene 0.050 30 Acenaph hene 0.050 30 Fluo ene 0.050 30 Phenan h ene 0.010 20 An h acene 0.005 20 Fluo an hene 0.005 20 Py ene 0.005 20 Benzo [a]an h acene 0.005 20 Ch ysene 0.005 20 Benzo [b] luo an hene 0.005 20 Benzo [k] luo an hene 0.005 20 Benzo [a] py ene 0.002 20 Dibenzo [a.h] an h acene 0.010 20 Benzo [ghi] pe ylene 0.005 20 Indeno [123-cd] py ene 0.010 20 * The measu emen unce ain ies a e expanded unce ain ies calcula ed by mul iplying he combined s anda d unce ain ies by a co e age ac o k = 2 o an app oxima e le el o con idence o 95%. Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 8 o 21 (page numbe no o ci a ion pu poses) phe ic dispe sion is g ea e in his di ec ion, and a lowe le el o PAH deposi ion occu s a hese si es. Anomalous concen a ions o he PAHs (35.16 mg/kg dm) and benzo [a]py ene (2.25 mg/kg dm) we e iden i- ied in he sample ID 116, in S epano . The alues o he PAHs we e signi ican ly highe han in he o he soil sam- ples. This sample was collec ed in ag icul u al soil on he slope abo e he own in he sou heas di ec ion. I sug- ges s ha PAH deposi ion a highe al i udes in he p ox- imi y o PAH sou ces can occu as a consequence o un a o able me eo ological condi ions associa ed wi h he low wind di ec ions o calm condi ions ha a e e- quen in his egion (see 2.1). These condi ions a e a o- able o he occu ence o nea g ound high pollu an concen a ions and a e no app op ia e o good a mos- phe ic dispe sion o pollu an s [26]. G aphical p esen a- ions o he esul s a e shown in Figu es 4 and 5, illus a ing he concen a ions o he s udied PAHs and benzo [a]py ene in u ban/ag icul u al as well as o es soils. The a e age PAH16 dis ibu ion pa e n is shown in Table 8 and in Figu e 6. Fluo an hene, py ene, ch ysene and indeno [1,2,3-cd]py ene a e he mos p ominen com- pounds in he samples (calcula ed om a e age alues). The p edominance o 4-6 ing compounds in he soil sam- ples sugges s py ogenic sou ces [27]. Howe e , highe concen a ions o naph halene we e ound in 12 samples (IDs 7,12,13,15,16,17,18,19,20,54,78,138). Six o hese samples we e collec ed in he coal a e ine y su ound- ings (IDs 7,13,15,16,54,78), ou we e collec ed in he own e i o y (IDs 12,17,18,19) in he p oximi y o he main ou es, and one (ID 20) was om he backg ound si e. The p opo ion o naph halene in he PAH samples was gene ally in he ange o 6.2-22.3%, and in one case e en 35.3% (ID 138). The p esence o 2- and 3- ing PAHs can indica e mo e ecen PAH deposi ion [27]. I is well known ha ligh PAH compounds occu in soils in lowe p opo ions han hea ie ones, due o hei physico-chemical p ope ies, such as highe wa e solubili y, ola ili y and biodeg ada- bili y and lowe so p ion abili y o soil o ganic ma e o pa icles [28,29]. Remo al o he PAHs om he a mos- phe e is accomplished by d y o we deposi ion o pa i- cles and apo s [30,31]. Gene ally, i is known ha o high le el sou ces, he le el o deposi ion nea he sou ce Table 4: PAH concen a ions in selec ed u ban/ag icul u al soils Sample ID/ locali y 6/ Ju inka 7/Ju inka o cha d 11/Valmez swimming pool 12/ H acho ec 13/ Přiluky 14/ Obo a III 15/ Bynina 16/ Jasenice 17/ Valmez hospi al 18/ Valmez Sou h PAHs mg/kg dm Naph halene 0.100 0.400 0.190 0.120 0.720 0.100 0.140 0.130 0.470 1.050 Acenaph hylene 0.006 < 0.005 0.006 0.003 0.007 0.007 < 0.005 < 0.005 0.007 0.015 Acenaph hene 0.074 0.062 0.048 0.025 0.050 0.058 0.020 0.190 0.036 0.073 Fluo ene 0.071 0.052 0.037 0.028 0.047 0.046 0.020 0.110 0.030 0.064 Phenan h ene 0.350 0.180 0.180 0.057 0.170 0.290 0.054 0.074 0.270 0.370 An h acene 0.047 0.030 0.041 0.009 0.036 0.046 0.009 0.012 0.066 0.044 Fluo an hene 1.000 0.350 0.830 0.160 0.390 0.610 0.120 0.210 0.830 0.800 Py ene 0.700 0.240 0.620 0.120 0.280 0.410 0.087 0.150 0.620 0.560 Benzo [a] an h acene 0.320 0.150 0.310 0.071 0.190 0.240 0.054 0.096 0.430 0.300 Ch ysene 0.460 0.230 0.440 0.100 0.280 0.330 0.079 0.140 0.600 0.450 Benzo [b] luo an hene 0.240 0.140 0.230 0.053 0.180 0.180 0.053 0.082 0.310 0.240 Benzo [k] luo an hene 0.150 0.082 0.140 0.032 0.110 0.110 0.029 0.048 0.190 0.140 Benzo [a] py ene 0.290 0.160 0.280 0.060 0.220 0.210 0.056 0.093 0.400 0.260 Dibenzo [a.h] an h acene 0.220 0.140 0.240 0.052 0.180 0.160 0.050 0.080 0.300 0.210 Benzo [ghi] pe ylene 0.070 0.039 0.063 0.012 0.050 0.048 0.011 0.019 0.093 0.055 Indeno [123-cd] py ene 0.440 0.260 0.440 0.083 0.320 0.310 0.079 0.130 0.550 0.390 Σ 16 PAHs 4.538 2.515 4.095 0.985 3.230 3.155 0.861 1.564 5.202 5.021 Σ 7 ca cinogenic PAHs 2.120 1.162 2.080 0.451 1.480 1.540 0.400 0.669 2.780 1.990 Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 9 o 21 (page numbe no o ci a ion pu poses) is small and inc eases wi h downwind dis ance om he sou ce un il i eaches a maximum, a e which i dec eases. Fo g ound-le el sou ces, he highes d y depo- si ion is di ec ly nex o he sou ce, and dec eases down- wind. Thus, i is possible o explain highe naph halene con en s in he soils in he e i o y o Valasske Mezi ici due o naph halene in PAH emissions om anspo , local hea ing and he coal a e ine y. Diagnos ic a ios o selec ed PAH compounds a e gene - ally conside ed o be a good indica o o he pollu ion sou ces and o he mechanism o PAH anspo in o he soil. The a ios Ind/(Ind+BghiP) and Fl /(Fl +Py ) a e o en used o dis inguish be ween py ogenic and pe o- genic sou ces. The alue o Ind/(Ind+BghiP) > 0.5 indi- ca es g ass/coal/wood combus ion sou ces. The alues o Fl /(Fl +Py ) > 0.4 indica es py ogenic sou ces, and we can dis inguish be ween he alues 0.4-0.5 o uel combus- ion and > 0.5 o g ass/coal/wood combus ion sou ces. The a io BaP/BghiP can also be used as an indica o o he de e mina ion o a ic and non- a ic sou ces, when he alue > 0.6 is cha ac e is ic o a ic sou ces [2,11]. The alues o An /(An +Phe) < 0.1 and Baa/(Baa+Ch y) < 0.2 co espond o pe ogenic sou ces; alues > 0.1 and >0.35, espec i ely, indica e py ogenic sou ces. The alues o he a io Baa/(Baa+Ch y) be ween 0.20-0.35 indica e mixed pe ogenic and py ogenic sou ces [32,33]. In ou da a se , he alues o Ind/(Ind+BghiP) ange be ween 0.86-0.89, hose o Fl /(Fl +Py ) a e in he ange o 0.55-0.60 and hose o BaP/BghiP a e be ween 4.10- 5.11. The alues o Ind/(Ind+BghiP) and BaP/BghiP a e signi ican ly highe han hose p esen ed in Maliszewska- Ko dybach e al. (2008), whe e he alues a e in he anges o 0.45-0.7, 0.3-0.6 and 0.7-1.4, espec i ely [2]. The cha - ac e is ic a ios indica e p edominan ly py ogenic sou ces and coal/wood/g ass combus ion. The alues o An / (An +Phe) a e in he ange o 0.09-0.2, and he Baa/ (Baa+Ch y) a io anges om 0.37-0.43. These a io al- ues con i med ha py ogenic sou ces a e he main pollu- ion sou ces, e en in he case o ID 116, whe e he highes PAH con en s we e de e mined. All hese diagnos ic a ios a e illus a ed in Figu e 7 and in Table 9. The pe cen age o he sum o 8 PAHs compounds (wi h 4 o mo e a oma ic ings, excluding luo an hene and py ene) and he sum o naph halene and phenan h ene concen a ions om he ull se o PAHs a e al e na i e Table 5: PAH concen a ions in selec ed u ban/ag icul u al soils Sample ID/ locali y 19/ Valmez cas le 20/ back ound 41/nea coal a e ine y 54/ Hos ašo ice 78/ Vysoká 108/ Poličná 109/ Valmez con luence 116/on Š Еpáno 137/ Valmez Janáčko a 138/ K ho á PAHs mg/kg dm Naph halene 0.230 0.230 0.180 0.220 0.200 0.180 0.210 0.210 0.440 0.500 Acenaph hylene 0.007 0.013 0.007 0.007 0.006 0.006 < 0.05 < 0.05 < 0.04 0.022 Acenaph hene 0.065 0.230 0.060 0.039 0.027 0.065 0.150 0.250 0.680 0.084 Fluo ene 0.049 0.150 0.043 0.035 0.032 0.050 0.083 0.210 0.480 0.050 Phenan h ene 0.210 0.140 0.280 0.220 0.200 0.550 0.490 3.300 0.760 0.078 An h acene 0.027 0.015 0.045 0.030 0.025 0.120 0.160 0.720 0.140 0.008 Fluo an hene 0.470 0.440 0.640 0.660 0.500 1.200 2.000 8.300 1.800 0.140 Py ene 0.330 0.310 0.460 0.530 0.360 0.800 1.400 5.700 1.300 0.100 Benzo [a] an h acene 0.180 0.170 0.320 0.250 0.200 0.490 0.750 2.600 0.780 0.057 Ch ysene 0.310 0.280 0.480 0.380 0.310 0.740 1.000 3.500 1.100 0.093 Benzo [b] luo an hene 0.210 0.170 0.300 0.210 0.180 0.390 0.470 1.600 0.570 0.058 Benzo [k] luo an hene 0.110 0.097 0.170 0.120 0.110 0.240 0.300 1.100 0.350 0.031 Benzo [a] py ene 0.190 0.180 0.340 0.220 0.220 0.460 0.610 2.300 0.720 0.056 Dibenzo [a.h] an h acene 0.180 0.160 0.280 0.190 0.200 0.370 0.470 1.800 0.580 0.050 Benzo [ghi] pe ylene 0.041 0.039 0.081 0.049 0.047 0.096 0.130 0.450 0.150 0.012 Indeno [123-cd] py ene 0.320 0.270 0.530 0.350 0.340 0.630 0.860 3.100 0.990 0.077 Σ 16 PAHs 2.929 2.894 4.216 3.510 2.957 6.387 9.083 35.140 10.840 1.416 Σ 7 ca cinogenic PAHs 1.500 1.327 2.420 1.720 1.560 3.320 4.460 16.000 5.090 0.422 Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 16 o 21 (page numbe no o ci a ion pu poses) Compa ing he dis ibu ions o single PAHs compounds wi h al i ude, we ound ha all he compounds had he same end, excep luo ene, acenaph hene and phenan- h ene, whe e some de ia ions appea ed. Fluo ene, acenaph hene and an h acene a e he leas abundan in o es soil. The beha io o lowe molecula PAHs is a ec ed by he collec ing e ec o he ba k. Due o hei physico-chemical cha ac e is ics, lowe molecula PAHs a e mo e e icien ly adso bed by he ba k, hey a e leached om he o ganic laye s, hey can be e- ola ilized o bio- deg aded, and so on [40]. The sum o he 7 ca cinogenic PAHs (acco ding o IARC, see 3.1) in he selec ed o es soil anged om 4.260-44.400 mg/kg dm, and hey o med 47-61% o he sum o he 16 PAHs. The a e age PAH dis ibu ion pa e n o o es soils is shown in Table 8 and in Figu e 6. Fluo an hene, py ene, ch ysene, indeno [1,2,3-cd]py ene and he sum o benzo [b,k] luo an- henes a e he mos p ominen compounds in he sam- ples (calcula ed om a e age alues) as in he u ban/ ag icul u al soil da a se . The con ibu ion o naph halene o he sum o he 16 PAHs (0.38-1.95%) is lowe han in u ban/ag icul u al soil. The diagnos ic a ios Ind/(Ind+BghiP) and Fl /(Fl +Py ) we e also used o dis inguish possible sou ces o high con- cen a ions o PAHs in o es soils. The alues o Ind/ (Ind+BghiP), Fl /(Fl +Py ), BaP/BghiP, An /(An +Phe) and Baa/(Baa+Ch y) anged om 0.85-0.90; 0.58-0.62; 4.07-6.39; 0.10-0.20; 0.29-0.39, espec i ely. These alues a e close o hose calcula ed in he u ban/ag icul u al soils in ou s udy (Figu e 7). The dominan pollu ion sou ces acco ding o hese alues a e py ogenic sou ces, coal/ wood/g ass combus ion, and he a io o BaP/BghiP con- i ms a con ibu ion om a ic. We can obse e some di e ences in he Baa/(Baa+Ch y) a io, whose alues a e lowe han 0.35, co esponding o a mix u e o py ogenic and pe ogenic sou ces in he 10 samples o o es soils. Only py ogenic sou ces a e ound in u ban/ag icul u al soils using his molecula a io. Mos o he o es soil samples had a highe alue o Ind/(Ind+BghiP) han he u ban/ag icul u al soils (Figu e 7). The pe cen age o he sum o 8 PAH compounds (4-6) and o he sum o naph halene and phenan h ene con- cen a ions in he comple e PAH se we e in he anges 48- 63% and 5-10%, espec i ely. In case o he naph halene and phenan h ene sum, we see a lowe p opo ion in he sum o he 16 PAHs han in he case o u ban/ag icul u al soil, whe eas he p opo ion o he 8-PAH sum is sligh ly highe . Table 11: PAH concen a ions in selec ed o es soils Sample ID/ locali y 11/ P iluky 12/ Doub a a 13/ Podlesi 14/Velka Lho a 15/ Dusna 16/ Ruzdka 17/ Mikulu ka 18/ Oznice 20/K ho a- Jehlicna PAHs mg/kg dm Naph halene 0.190 0.110 0.360 0.290 0.200 0.110 0.100 0.120 0.160 Acenaph hylene <0.03 <0.04 0.055 0.043 0.043 <0.07 0.023 0.049 0.032 Acenaph hene 0.300 0.190 0.580 1.200 1.300 0.190 0.310 0.180 0.360 Fluo ene 0.210 0.088 0.370 1.000 1.000 0.086 0.170 0.170 0.220 Phenan h ene 1.400 0.660 3.800 6.900 5.000 0.950 1.100 1.700 2.400 An h acene 0.260 0.076 0.830 1.000 0.700 0.130 0.160 0.240 0.320 Fluo an hene 2.800 1.700 17.000 15.000 12.000 2.600 3.100 4.400 5.700 Py ene 2.000 1.100 11.000 10.000 7.400 1.800 2.100 2.700 3.800 Benzo[a] an h acene 1.200 0.500 6.400 5.000 3.300 0.910 1.000 1.400 1.800 Ch ysene 2.100 1.200 10.000 8.500 5.300 1.700 1.800 2.700 3.500 Benzo[b] luo an hene 1.600 0.940 6.000 5.400 3.700 1.300 1.300 2.000 2.600 Benzo[k] luo an hene 0.780 0.400 3.200 2.700 1.800 0.600 0.610 0.960 1.200 Benzo[a] py ene 1.600 0.640 6.200 5.300 3.400 1.000 1.100 1.500 2.100 Dibenzo[a.h] an h acene 1.100 0.570 4.500 3.600 2.500 0.820 0.880 1.300 1.600 Benzo[ghi] pe ylene 0.270 0.130 0.990 0.830 0.630 0.190 0.270 0.340 0.370 Indeno[123-cd] py ene 2.200 1.100 8.100 6.600 4.700 1.500 1.500 2.500 3.000 Σ 16 PAHs 18.010 9.404 79.385 73.363 52.973 13.886 15.523 22.259 29.162 Σ 7 ca cinogenic PAHs 10.580 5.350 44.400 37.100 24.700 7.830 8.190 12.360 15.800 cox (%) 10.59 10.31 3.45 3.54 7.21 15.78 14.27 18.91 16.47 Cox con en o o ganic oxidizable ca bon in soil samples (%) Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 17 o 21 (page numbe no o ci a ion pu poses) 3.3 Compa ison o he PAHs in soils om o he geog aphic loca ions The PAH concen a ions in he o es soils in he Valasske Mezi ici Region a e much highe han he concen a ions p esen ed in [10,27,29,41]. PAH concen a ions we e sig- ni ican ly highe a uppe han a lowe slope si es, indi- ca ing long-dis ance anspo [40]. The compa ison o PAH concen a ions in o es soils o di e en egions in Eu ope wi h a ea o Valasske Mezi ici is summa ized in Table 13. The PAHs concen a ions p esen ed in his pape co espond o hose iden i ied in o es soils in egions wi h ele a ed a mosphe ic PAH deposi ion: in No he n Ba a ia (0.644-19.919 mg/kg dm in A-ho izon) and nea a blas u nace plan loca ed in he egion o Hoogo ens, in he Ne he lands [39,42]. The PAH le els in u ban/ag icul u al soils a e in acco dance wi h hose in indus ialized a eas [11,32,43-45]. In o al, he PAH con- cen a ions in o es soils we e signi ican ly g ea e han hose iden i ied in u ban/ag icul u al soils. In hei s udies, Fa a e al. (2005) and Tao e al. (2007) obse ed clea dec easing ends in PAH concen a ions in he e ical dis ibu ion in he u ban bounda y a mos- phe ic laye . The e a e h ee possible scena ios o he e - ical concen a ion p o iles due o di e ences in emission sou ces, ad ec ion and e ical mixing condi ions: 1) e en e ical mixing, wi h weak esh emissions, dominan ad ec ion and well-mixing condi ions, 2) dec ease wi h heigh , wi h g ound sou ce domina ion and s able a mos- phe ic bounda y laye condi ions, 3) inc ease wi h heigh wi h uppe bounda y laye emission sou ces [46,47]. We can suppose, especially in he win e and au umn pe iods ha Scena io 2 p edomina es in he s udied a ea, when py ogenic sou ces and a ic a e he dominan pollu ion sou ces acco ding o he de e mined alues o molecula diagnos ic a ios (see 3.1 and 3.2). Local hea ing and a - ic a e sou ces ha emi pollu an s a g ound le el. How- e e , an impo an sou ce o PAH pollu ion is loca ed in his egion he coal a e ine y. Du ing coal a ea men , some ope a ions a e pe o med ( o example coal a launching) ha lead o o ganic compound escape o he ambien ai . The escape le el depends on he ai empe a- u e. The possible emissions sou ces in coal a e ine y a e 15 m o heigh and hey can con ibu e o he pollu ion sou ces a g ound le el no only in he win e days, bu also in pe iods wi h highe empe a u es. A highe le el o deposi ion o PAH compounds on he hill slopes in he icini y o he own occu s in his egion as a consequence o he p e ailing me eo ological condi- ions (on a e age, 66% o me eo ological si ua ions a e calm wi h wind eloci ies 0-2.5 m/s, 27.5% ha e wind Table 12: S a is ical e alua ion o PAH concen a ions in o es soils PAHs Uni Minimum Maximum A i hme ic mean S anda d de ia ion Geome ic mean Median Numbe o samples Naph halene mg/kg dm 0.100 0.360 0.210 0.100 0.180 0.190 20 Acenaph hylene mg/kg dm LD* 0.100 0.020 0.020 0.040 0.040 20 Acenaph hene mg/kg dm 0.110 1.300 0.370 0.320 0.290 0.250 20 Fluo ene mg/kg dm 0.080 1.000 0.270 0.280 0.190 0.170 20 Phenan h ene mg/kg dm 0.570 6.900 1.990 1.550 1.580 1.400 20 An h acene mg/kg dm 0.080 1.000 0.310 0.260 0.230 0.210 20 Fluo an hene mg/kg dm 1.400 17.000 5.010 4.300 3.860 3.300 20 Py ene mg/kg dm 0.900 11.000 3.270 2.790 2.520 2.200 20 Benzo[a] an h acene mg/kg dm 0.450 6.400 1.690 1.500 1.290 1.100 20 Ch ysene mg/kg dm 0.960 10.000 3.010 2.330 2.430 2.150 20 Benzo[b] luo an hene mg/kg dm 0.710 6.000 2.090 1.390 1.760 1.700 20 Benzo[k] luo an hene mg/kg dm 0.320 3.200 1.030 0.740 0.850 0.780 20 Benzo[a] py ene mg/kg dm 0.530 6.200 1.850 1.480 1.470 1.300 20 Dibenzo[a.h] an h acene mg/kg dm 0.460 4.500 1.420 1.010 1.180 1.100 20 Benzo[ghi] pe ylene mg/kg dm 0.110 0.990 0.340 0.230 0.280 0.270 20 Indeno[123- cd)py ene mg/kg dm 0.830 8.100 2.630 1.840 2.180 2.050 20 Σ 16 PAHs mg/kg dm 7.660 79.390 25.510 19.660 20.470 18.210 20 Σ 7 ca cinogenic PAHs mg/kg dm 4.260 44.400 13.927 10.474 11.261 10.580 20 LD - limi o de ec ion Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 18 o 21 (page numbe no o ci a ion pu poses) eloci y 2.6-7.5 m/s and 6.5% ha e wind eloci ies >7.6 m/s, acco ding o he Czech Hyd ome eo ological Ins i- u e) and opog aphical e ain. The me eo ological con- di ions a e no a o able o a mosphe ic pollu an dispe sion, and he pollu an s a e accumula ed in he bounda y laye , he al i ude o he in e sion laye gene - ally eaches a numbe o ens o hund eds me e s) [26]. The un a o able me eo ological condi ions usually pe sis o se e al days and a e epea ed (see 3.1). The molecula diagnos ic a ios indica e py ogenic sou ces and combus ion o coal, wood and g ass as main pollu ion sou ces. Howe e , he coal a composi ion is o med especially om naph halene (10% by weigh ), phenan h ene (4.5% by weigh ), luo an hene (3.0% by weigh ), acenaph hylene (2.5% by weigh ), py ene (2.0% by weigh ), luo ene (1.8% by weigh ), an h acene (1.3% by weigh ), ch ysene (1.0% by weigh ) and acenaph hene (0.2% by weigh ) [48]. This ac can explain he highe concen a ions o ligh e PAHs, especially naph halene, in u ban/ag icul u al soils in he icini y o he e ine y and hei highe con ibu ions o he sum o he 16 PAHs in he u ban/ag icul u al soils compa ed o he o es soils (Table 8, Figu e 6). The diagnos ic a ios de e mined o coal a a e 0.18 o An /(An +Phe), 0.58 o Fl /(Fl +Py ), 0.54 o Baa/(Baa+Ch y) and 0.53 o Ind/(Ind+BghiP) [49]. Thus, hese alues co espond o hose in ou sam- ples in he case o An /(An +Phe) and Fl /(Fl +Py ). The alues o Baa/(Baa+Ch y) we e lowe , and hose o Ind/ (Ind+BghiP) we e highe in ou samples. All he alues co espond o coal/wood/g ass combus ion and py o- genic sou ces. B own e al. (2006) compa ed ele en sam- ples o coal a s om 10 o me manu ac u ed gas plan si es in he Eas e n Uni ed S a es [16]. The diagnos ic a ios de e mined in hese coal a samples we e wi hin he anges (Table 9): 0,22-0,27 o An /(An +Phe), 0,36- 0,58 o Fl /(Fl +Py ), 0,48-0,58 o Baa/(Baa+Ch y), 0,38-0,59 o Ind/(Ind+BghiP) and 1,67-3,25 o BaP/ BghiP. Thus, hese alues co espond o hose in ou sam- ples in case o An /(An +Phe) and Fl /(Fl +Py ). I is no possible o dis inguish be ween py ogenic sou ces and he coal a e ine y in his way, because he a ios p esen ed a e de e mined o c uel coal a , bu he coal a e ine y may con ibu e o soil by emi ed PAH deposi ion. The diagnos ic a ios in deposi ions can be comple ely di e - en . We obse ed in ou samples highe concen a ions o indeno [1,2,3-cd]py ene compa ed o benzo [ghi]pe yl- ene. Yunke e al. (2002) lis ed in his wo k ypical a ios The o al PAH concen a ion as a unc ion o al i udeFigu e 8 The o al PAH concen a ion as a unc ion o al i ude. Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 19 o 21 (page numbe no o ci a ion pu poses) o pe oleum, single sou ce combus ion and en i on- men al samples; he Ind/(Ind+BghiP) alues we e in he ange o 0.09-0.70, while we de e mined hese alues o be abo e 0.85 in ou samples, and highe in o es soils han in u ban soils [49]. Indeno [1,2,3-cd]py ene and benzo [ghi]pe ylene a e deg aded pho ochemically a compa able a es, and he o iginal composi ion is p e- se ed du ing a mosphe ic anspo . The concen a ions o benzo [a]py ene we e also signi ican ly highe han hose o benzo [ghi]pe ylene (4-6 imes highe ), and he a io alues we e highe in o es soils han u ban/ag icul- u al ones. An in e se end was obse ed in he case o Baa/(Baa+Ch y), whe e mixed sou ces (py ogenic and pe ogenic) we e de e mined in mos o o es soils, and py ogenic sou ces in he u ban soils. Because we did no suppose pe oleum sou ces in o es soils ( he samples we e collec ed in emo e a eas) his ac may co espond o as e benzo [a]an h acene deg ada ion in o es soils o in he ai du ing he a mosphe ic anspo . 4. Conclusions The u ban, ag icul u al and o es soils in he egion o Valasske Mezi ici a e con amina ed wi h polycyclic a o- ma ic hyd oca bons, which a e emi ed h ough indus ial p ocesses, anspo and local hea ing sou ces. The highes PAH concen a ions we e ound in o es soils om he o es -co e ed slopes o hills. The obse ed alues we e much highe han he PAH concen a ions epo ed o o es soils in Wes e n and No he n Eu ope. The PAH concen a ions in he u ban soils we e highe han in he ag icul u al soils, bu compa able wi h o he soils om u ban a eas in he wo ld. The highes PAH concen a ions we e obse ed in o es soils collec ed a highe al i udes abo e sea le el. The PAH dis ibu ion in he moun ainous egion is ela ed o al i ude and in luenced by me eo olog- ical condi ions. The equen calm condi ions ha a e connec ed wi h in e sion condi ions con ibu e o PAH deposi ion a highe al i udes in he su oundings o he own. Ele a ed PAH concen a ions we e iden i ied a si es u he om he own, bu he concen a ions dec eased in compa ison wi h si es in he p oximi y o he own. Compa ed o he PAH load in o he wo ld a eas, i is clea ly con i med ha he soils in he egion o Valasske Mezi ici, especially he o es soils, a e highly pollu ed. The e is a p ima y sou ce o PAH pollu ion in he egion a coal a e ine y. The e a e also con ibu ions om o he sou ces local hea ing, ehicle anspo and long ange pollu an anspo . I is no possible o dis inguish he con ibu ions o each sou ce on he basis o diagnos ic a ios. Abb e ia ions PAHs: polycyclic a oma ic hyd oca bons; Ace: Acenaph- hene; Acy: Acenaph hylene; An : An h acene; Baa: Benzo [a]an h acene; Bap: Benzo [a]py ene; Bb : Benzo [b] luo an hene; Bk : Benzo [k] luo an hene; BghiP: Benzo [g.h.i]pe ylene; Ch y Ch ysene; Daa: Dibenzo [ah]an h acene, Fl : Fluo an hene; Flu: Fluo ene; Ind: Indeno [1,2,3-cd]py ene; Nap: Naph halene; Phe: Phen- an h ene; Py : Py ene; Dm: d y ma e . Compe ing in e es s The au ho s decla e ha hey ha e no compe ing in e es s. Au ho s' con ibu ions DP e alua ed he esul s and w o e he manusc ip . HR was he head o he esea ch g oupe, she designed his s udy and pa icipa ed in p epa a ion o he manusc ip . DM p epa ed g aphical pa o he manusc ip and he s a- is ical analysis. All o h ee au ho s pa icipa ed in Table 13: The PAHs alues in a ious ypes soils in a ious egions Region Soil ype PAHs Con en s (mg/kg dm) Li e a u e No way o es soils Σ16 PAHs < 006.2 - 010.0 Jensen e al., 2007,[27] Σ15 PAHs, excep Aus ia o es soils Naph halene 0.068 - 1.342 Weiss e al., 2000,[29] UK woodland soils Σ15 PAHs up o 4.850 Nam e al., 2008,[10] Swi ze land o es soils Σ16 PAHs 0.098 0.219 Bucheli e al., 2004,[41] Czech epublic o es soils Σ16 PAHs 2.000-30.000 Wilcke e al., 2007b,[40] No he n Ba a ia, Ge many o es soils Σ16 PAHs 0.644 19.919 K auss e al., 2000,[42] Valasske Mezi ici o es soils Σ16 PAHs 7.657 - 79.385 Placha e al Belgium indus ial soil Σ16 PAHs 2.00 - 300.000 Bakke e al., 2000,[43] Ge many i e bank soils Σ16 PAHs 12.200 - 31.200 Pies e al., 2008,[32] Beijing, China u ban soil Σ16 PAHs 0.220 - 27.830 Tang e al., 2005,[44] Nanjing, China u ban soil Σ16 PAHs 0.290 - 17.640 Yin e al., 2008,[11] Nanjing, China esiden ial a eas Σ16 PAHs 0.460 - 3.110 Yin e al., 2008,[11] Nanjing, China ag icul u al soil Σ16 PAHs 0.310 - 27.580 Yin e al., 2008,[11] Spain u ban soil Σ16 PAHs 0.340 - 6.060 Nadal e al., 2007,[45] Valasske Mezi ici u ban/ag icul u al soil Σ16 PAHs 0.861-10.840 (one anomalous alue 35.140) Placha e al Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 20 o 21 (page numbe no o ci a ion pu poses) designing o he s udy, in sample collec ing and da a e al- ua ion. MHR pa icipa ed in design o he manusc ip . All au ho s ha e ead and app o ed he inal manusc ip . Acknowledgemen s We acknowledge he inancial suppo o he esea ch p ojec INTERVI- RON 2BE6068 (The Minis y o Educa ion, You h and Spo , he Czech Republic). Re e ences 1. Liu X, Zhang G, Jones KC, Li X, Peng X, Qi S: Composi ional ac- iona ion o polycyclic a oma ic hyd oca bons (PAHs) in mosses (Hypnum plumae o mae WILS.) om he no he n slope o Nanling Moun ains, Sou h China. A mosphe ic En i on- men 2005, 39:5490-5499. 2. Maliszewska-Ko dybach B, Sm eczak B, Klimkowicz-Pawlas A, Te e- lak H: Moni o ing o he o al con en o polycyclic a oma ic hyd oca bons (PAHs) in a able soils in Poland. Chemosphe e 2008, 73:1284-1291. 3. Vila-Escalé M, Vegas-Vila úbia T, P a N: Release o polycyclic a oma ic compounds in o a Medi e anean c eek (Ca alo- nia, NE Spain) a e a o es i e. Wa e Resea ch 2007, 41:2171-2179. 4. Wang Z, Chen J, Qiao X, Yang P, Tian F, Juany L: Dis ibu ion and sou ces o polycyclic a oma ic hyd oca bons om u ban o u al soils: A case s udy in Dalian, China. Chemosphe e 2007, 68:965-971. 5. Holoubek I, Vokouno á Š, Komp es J: Pe sis en ní o ganické polu an y a mos éře a půdách, Еkání z půd. Och ana o zduší 2000, 3:4-19. 6. Kim EJ, Oh JE, Chány YS: E ec s o o es i e on he le el and dis ibu ion o PCDD/Fs and PAHs in soil. The Science o The To al En i onmen 2003, 311:177-189. 7. Oma NYMJ, Bin Abas MR, Ke uly KA, Tahi NM: Concen a ions o PAHs in a mosphe ic pa icles (PM-10) and oadside soil pa icles collec ed in Kuala Lumpu , Malaysia. A mosphe ic En i onmen 2002, 36:247-254. 8. Wong F, Ha ne b T, Liua QT, Diamonda ML: Using expe imen al and o es soils o in es iga e he up ake o polycyclic a o- ma ic hyd oca bons (PAHs) along an u ban- u al g adien . En i onmen al Pollu ion 2004, 129:387-398. 9. Chung MK, Hu R, Cheung KC, Wong MH: Pollu an s in Hong Kong soils: Polycyclic a oma ic hyd oca bons. Chemosphe e 2007, 67:464-470. 10. Nam JJ, Thomas GO, Jawa d FM, S einnes E, Gus a sson O, Jones KC: PAHs in backg ound soils om Wes e n Eu ope: In luence o a mosphe ic deposi ion and soil o ganic ma e . Chemos- phe 2008, 70:1596-1602. 11. Yin ChQ, Jiang X, Yang XL, Bian YR, Wang F: Polycyclic a oma ic hyd oca bons in soils in he icini y o Nanjing, China. Chem- osphe e 2008, 73:389-394. 12. Town o Valasske Mezi ici. P o ile o he own [h p:// www. alasskemezi ici.cz/en/1928/] 13. Benhabib K, Fau e P, Sa din M, Simonno MO: Cha ac e is ics o a solid coal a sampled om a con amina ed soil and o he o ganics ans e ed in o wa e . Fuel 2009. doi:10.1016/ j. uel.2009.06.009 14. B own DG, Gup a L, Kim TH, Moo-Young HK, Coleman AJ: Com- pa a i e assessmen o coal a s ob ained om 10 o me manu ac u ed gas plan si es in he Eas e n Uni ed S a es. Chemosphe e 2006, 65:1562-1569. 15. DEZA, membe o Ag o e G oup [h p://www.deza.cz/] 16. In eg o aný egis znečiš'o ání ži o ního p os ředí (IRZ) [h p://www.i z.cz/] 17. Scheye JM, Hipple KW: U ban Soil P ime . 2005 [h p:// soils.usda.go /use]. Uni ed S a es Depa men o Ag icul u e, Na u al Resou ces Conse a ion Se ice, Na ional Soil Su ey Cen e , Lin- coln, Neb aska 18. Lehmann A, S ah K: Na u e and Signi icance o An h opogenic U ban Soils. J Soils Sedimen s 2007, 7:247-260. 19. Tan Kim H: Soil sampling, p epa a ion and analysis. CRC P ess, Taylo and F ancis, Boca Ra on, Flo ida; 2005:623. 20. ISO 10381-4:2003 Soil quali y - Sampling - Pa 4: Guidance on he p ocedu e o in es iga ion o na u al, nea -na u al and cul i a ed si es. . 21. ISO 10381-5:2005 Soil quali y - Sampling - Pa 5: Guidance on he p ocedu e o he in es iga ion o u ban and indus- ial si es wi h ega d o soil con amina ion. . 22. In e na ional Con e ence on Ha moniza ion (ICH) o Technical Requi emen s o he Regis a ion o Pha maceu icals o Human Use: Valida ion o analy ical p ocedu es: de ini ions and e - minology. Gene a 1996. 23. EURACHEM/CITAC Guide CG 4, Quan i ying Unce ain y in Analy ical Measu emen . QUAM Second edi ion. 2000. 24. De Vos B, Le ens S, Muys B, Decke s JA: Walkley-Black analysis o o es soil o ganic ca bon: eco e y, limi a ions and unce ain y. Soil Use and Managemen 2007, 23:221-229. 25. Ai Quali y Guidelines. Second edi ion. WHO Regional O ice o Eu ope, Copenhagen, Denma k; 2000. 26. Do de ič DS, Šole ič TM: The con ibu ions o high- and low al i ude emission sou ces o he nea g ound concen a ions o ai pollu an s. A mosphe ic Resea ch 2008, 87:170-182. 27. Jensen H, Reimann C, Finne TE, O esen RT, A noldussen A: PAH- concen a ions and composi ions in he op 2 cm o o es soils along a 120 km long ansec h ough ag icul u al a eas, o es s and he ci y o Oslo, No way. En i onmen al Pollu ion 2007, 14:829-838. 28. PAHs: An Eco oxicological Pe spec i e. 2003:404. 29. Weiss P, Lo bee G, Scha S: Regional aspec s and s a is ical cha ac e isa ion o he load wi h semi ola ile o ganic com- pounds a emo e Aus ian o es si es. Chemosphe e 2000, 40:1159-1171. 30. E isman JW, D aaije s G: Deposi ion o o es in Eu ope: mos impo an ac o s in luencing d y deposi ion and models used o gene aliza ion. En i onmen al Pollu ion 2003, 124:379-388. 31. Ra ind a K, Sokhi R, Van G ieken R: A mosphe ic polycyclic a o- ma ic hyd oca bons: Sou ce a ibu ion, emission ac o s and egula ion. A mosphe ic En i onmen 2008, 42:2895-2921. 32. Pies C, Ho mann B, Pe owsky J, Yang Y, Te nes TA, Ho mann T: Cha ac e iza ion and sou ce iden i ica ion o polycyclic a o- ma ic hyd oca bons (PAHs) in i e bank soils. Chemosphe e 2008, 72:1594-1601. 33. Zhang HB, Luo YM, Wong MH, Zhao QG, Zhang GL: Dis ibu ions and Concen a ions o PAHs in Hong Kong Soils. En i onmen- al Pollu ion 2006, 141:107-114. 34. Wilcke W, Zech W: Polycyclic a oma ic hyd oca bons (PAHs) in o es loo s o he No he n Czech Moun ains. Zei sch i ü P lanzene näh ung und Bodenkunde 2007, 160:573-579. 35. P áško á L, Kubík L, Kři ánek J, Maje F, Malý S: Kon ola a moni- o ing cizo odých lá ek zemЕdЕlské půdЕ a s upech do půdy. Zp á a za ok 2006. Cen al Ins i u e o supe ising and Tes ing in Ag icul u e, B no; 2007. 36. Schönbuchne H, Guggenbe ge G, Pe e s K, Be gmann H, Zech W: Pa icle size dis ibu ion o PAH in he ai o a emo e no - way sp uce o es in no he n Ba a ia. Wa e , Ai and Soil Pollu- ion 2001, 128:355-367. 37. Koi ula TT, Salkinoja-Salonen M, Pel ola R, Roman schuk M: Py ene deg ada ion in o es humus mic ocosms wi h o wi hou pine and i s myco hizal ungus. En i on Qual 2004, 33:45-53. 38. Wes AW, Spa ling GP, Fel ham CW, Reynolds J: Mic obial ac i i y and su i al in soils d ied a di e en a es. Aus alian Jou nal o Soil Resea ch 1992, 30:209-222. 39. Van B ummelen TC, Ve weij RA, Wedzinga SA, Van Ges el CAM: En ichmen o polycyclic a oma ic hyd oca bons in o es soils nea blas u nace plan . Chemosphe e 1996, 32:293-314. 40. Wilcke W: Global pa e ns o polycyclic a oma ic hyd oca - bons (PAHs) in soil. Geode ma 2007, 141:157-166. 41. Bucheli TD, Blum F, Desaules A, Gus a sson O: Polycyclic a o- ma ic hyd oca bons, black ca bon, and molecula ma ke s in soils o Swi ze land. Chemosphe e 2004, 11:1061-1076. 42. K auss M, Wilcke W, Zech W: Polycyclic a oma ic hyd oca - bons and polychlo ina ed biphenyls in o es soils: dep h dis- ibu ion as indica o o di e en a e. En i onmen al Pollu ion 2000, 110:79-88. 43. Bakke MI, Casado B, Koe selman JW, Tolls J, Kollö el C: Polycyclic a oma ic hyd oca bons in soil and plan samples om he Publish wi h BioMed Cen al and e e y scien is can ead you wo k ee o cha ge "BioMed Cen al will be he mos signi ican de elopmen o dissemina ing he esul s o biomedical esea ch in ou li e ime." Si Paul Nu se, Cance Resea ch UK You esea ch pape s will be: a ailable ee o cha ge o he en i e biomedical communi y pee e iewed and published immedia ely upon accep ance ci ed in PubMed and a chi ed on PubMed Cen al you s — you keep he copy igh Submi you manusc ip he e: h p://www.biomedcen al.com/in o/publishing_ad .asp BioMedcen al Geochemical T ansac ions 2009, 10:12 h p://www.geochemical ansac ions.com/con en /10/1/12 Page 21 o 21 (page numbe no o ci a ion pu poses) icini y o an oil e ine y. The Science o The To al En i onmen 2000, 263:91-100. 44. Tang L, Tang XY, Zhu YG, Zheng MH, Miao QL: Con amina ion o polycyclic a oma ic hyd oca bons (PAHs) in u ban soils in Beijing, China. En i onmen In e na ional 2005, 31:822-828. 45. Nadal M, Schuhmache M, Domino JL: Le els o me als, PCBs, PCNs and PAHs in soils o a highly indus ialized chemical/ pe ochemical a ea: Tempo al end. Chemosphe e 2007, 66:267-276. 46. Fa a NJ, Ha ne T, Shoeib M, Swee man A, Jones KC: Field deploymen o hin ilm passi e ai sample s o pe sis en o ganic pollu an s: a s udy in he u ban a mosphe ic bound- a y laye . En i onmen al Science and Technology 2005, 39:28-42. 47. Tao S, Wang Y, Wu S, Liu S, Dou H, Liu Y, Chang L, Hu F, Xing B: Ve ical dis ibu ion o polycyclic a oma ic hyd oca bons in a mosphe ic bounda y laye o Beijing in win e . A mosphe ic En i onmen 2007, 41:9594-9602. 48. VymЕ al J, Plesnik M: Zp aco ání če nouhelného deh u a smoly. DEZA Valasske Mezi ici 1994:34-44. 49. Yunke MB, Macdonald RW, Vinga zan R, Mi chell RH, Goye e D, Syl es e S: PAHs in he F ase Ri e basin: a c i ical app aisal o PAH a ios as indica o s o PAH sou ce and composi ion. O ganic Geochemis y 2002, 33:489-515. 50. Ka soyiannis A, Te zi E, Cai QY: On he use o PAH molecula diagnos ic a ios in sewage sludge o he unde s anding o he PAH sou ces. Is his use app op ia e? Chemosphe e 2007, 69:1337-1339.