GEOLOGIJA 56/1, 087-096, Ljubljana 2013 doi:10.5474/geologija.2013.007
Organic compounds in the urban dusts in Celje area
Organske spojine v urbanih prahovih na območju Celja
Gorazd ŽIBRET
Geological survey of Slovenia, Dimi~eva ulica 14, SI - 1000 Ljubljana, Slovenia; e-mail:gorazd.zibret@geo-zs.si
Prejeto / Received 18. 4. 2013; Sprejeto / Accepted 18. 6. 2013
Key words: attic dust, household dust, street sediment, organic pollutants, Celje, Slovenia
Ključne besede: podstre{ni prah, hi{ni prah, cestni sediment, organske spojine, Celje, Slovenija
Abstract
This paper presents the results of the analysis of organic chemicals in different urban dusts. The aim of the research is preliminary evaluation of the presence of organic contaminants in household dust, attic dust and street sediment. Celje area has been chosen as a pilot study site due to availability of sampling materials from previous sampling campaigns. Samples have been tested to the presence of 120 organic compounds. Attic dust contains 98 different organic compounds or 82 % of all measured. Terpenoids, alkylbenzenes and different Polycyclic Aromatic Hydrocarbons (PAH's), as well as plasticizers, halogenated compounds (among them also PCB's) and pesticides (DDT and degradation products) can be found there. It also contains all of the in this study analysed US-EPA priority pollutants. Street dust contained 70 different organic chemicals (58 %), among them 14 priority pollutants. Traces of aliphatic organic compounds, PAH's, aldehydes and ketones, esters, and plasticizers are found there. House dust contains lowest number of organic compounds. Among 45 detected (38 % of total measured), 8 are priority pollutants. Aliphatic compounds, alkylbenzenes, aldehides, ketones, acids and PAH's can be found there. Current number of analysed samples, as well as only qualitative evaluations were made does not allow making any solid interpretation of obtained results in regarding to the potential sources of chemicals or potential environmental hazards. This study can thus be used only as a guideline for future studies of organic chemicals in urban dusts.
Izvleček
Na obmo~ju Celja je bilo do sedaj opravljenih veliko raziskav onesnaženja s strupenimi kovinami. Vendar pa je bilo opravljenih premalo raziskav v povezavi s tematiko onesnaženja z organskimi spojinami na tem obmo~ju. Zato je namen te raziskave preliminarno ugotoviti, katere organske spojine so prisotne v prahovih na tem obmo~ju. Zaradi bremen iz preteklosti lahko pri~akujemo tudi obremenjenost okolja na podro~ju onesnaženja z organskimi spojinami. Vzrokov je ve~, izpostavimo pa lahko poleg rastlinstva in mikrobnega delovanja, ki je naravni vir organskih spojin, potencialne antropogene vire, ki so: izhlapevanje spojin iz deponij katrana na obmo~ju stare Cinkarne (zaradi proizvodnje tehni~nega plina iz premoga v preteklosti), delovanje dana{nje kemi~ne, papirne in lesno-predelovalne industrije, promet in drugo izgorevanje fosilnih goriv, izhlapevanje spojin iz asfaltiranih povr{in in gradbenih materialov ter druge vire. V gospodinjstvih pa lahko k prej na{tetim virom dodamo tudi uporabo kemikalij (barvila, laki, topila ipd.) in proizvodov, ki vsebujejo kemikalije (pohi{tvo, gradbeni materiali, tekstil, plasti~ni izdelki ipd.), kajenje, kuhanje na plinu in ostale vire. V tej raziskavi smo analizirali vzorec podstre{nega prahu, ki kaže na „zgodovinsko" onesnaženje zraka, vzorec cestnega prahu, ki kaže na dana{nje stanje zraka in vzorec hi{nega prahu, ki kaže na morebitno izpostavljenost ljudi. Analiziranih je bilo 120 razli~nih organskih spojin po metodi plinske kromatografije in masne spektroskopije, od tega jih 17 spojin spada pod t.i. prioritetna onesnažila, ki so na seznamu ameri{ke agencije za okolje. Podstre{ni prah vsebuje najve~ razli~nih spojin (82 % od vseh analiziranih), od katerih so zastopane skoraj vse skupine (tabeli 1 in 2) organskih spojin. Najbolj zna~ilne skupine so: terpenoidi, alkilbenzeni in policikli~ni aromatski ogljikovodiki in produkti delnega razpada le-teh. Zanimivo je tudi, da podstre{ni prah vsebuje sledi DDT-ja (uporaba v kmetijstvu) in PCB-ja (industrija), ki sta oba že ve~ kot 40 let prepovedana, a njihove ostanke {e vedno lahko najdemo v njem. Cestni prah vsebuje 58 % vseh analiziranih spojin, od katerih so zna~ilne skupine: policikli~ni aromatski ogljikovodiki, al-dehidi in ketoni, etri, amini in plastifikatorji. Hi{ni prah vsebuje najmanj razli~nih spojin (38 % vseh analiziranih). V njem najdemo terpenoide, alkilbenzene, policikli~ne aromatske ogljikovodike, aldehide in ketone ter organske kisline. Od 17-ih analiziranih US-EPA prioritetnih polutantov, v podstre{nem prahu najdemo sledi prav vseh, v cestnem prahu 14 in v hi{nem prahu 8 razli~nih. Ker v tej raziskavi ne razpolagamo s koncentracijami, ampak le s prisotnostjo snovi, prav tako pa je vzorcev malo, pa {e ti so bili odvzeti zgolj na obmo~ju, kjer pri~akujemo najvi{jo stopnjo onesnaženja, ne moremo delati prav nobenih ocen, kak{ni so morebitni viri spojin in ali predstavljajo prisotnosti rakotvornih spojin tveganje za okolje in zdravje ljudi. Analiz organskih spojin je draga metoda, zato je dodana vrednost te raziskave v tem, da lahko sedaj bolje na~rtujemo morebitne nove raziskave organskih onesnažil v prahovih in okolju in ne „zapra-vljamo" denarja za analize spojin, katerih ne najdemo. S tem lahko zmanj{amo morebitne stro{ke. Avtor se zahvaljuje Radim Lana, ki je opravil analize, in Evi Francu (oba iz Če{kega geolo{kega zavoda, izpostava Brno), ki je kot vodja laboratorija omogo~ila kemijsko analizo.
Fig. 1. Pyrometallurgical waste deposit and tar creosote around past Zn smelting furnaces in Celje.
Introduction
Celje area is well known for its environmental contamination. In the past studies main focus has been put on the evaluation of toxic metals contamination in soil due to past smelting and ironworking activities (Frančiškovič-Eilinski et al., 2006; Leštan et al., 2003; Lobnik et al., 1989; Šajn, 2005; Zupan et al., 2000; Žibret, 2002, 2008; Žibret & Šajn, 2008). But few researches have been done regarding the evaluation of organic pollutant contamination in the area, and even existing studies are focused mainly on the presence of very limited list of organic pollutants in drinking water.
This article presents the results of the chemical analyses of urban dusts in the Celje area by the means of gas chromatography / mass spectrom-etry. The focus has been put on the detection of the presence of 120 different organic substances. Description of the research area gives the main reason why the Celje area needs such pilot study. Materials and methods chapter describes the sampled materials, samples preparation, samples handling and chemical analyses. In the Results chapter results are presented and evaluated in the Discussion chapter. Main conclusions are presented in the Summary chapter.
Description of the research area
Celje, the third biggest town in Slovenia with the inhabitants around 50.000, lies in Celje basin in central Slovenia. It is surrounded with the Sava folds hills on the south (up to 1200 m above sea level) and with the Periadriatic lineament hill range on the north (1100 m above sea level). On the east side there is Voglajna River valley and on the west side the open space of Savinja River valley dominates.
Mayor pollution from the past was caused by zinc smelting by Cinkarna Celje plant. In its 100-year history of operation (between 1870 and 1970) approximately 500.000 tons of raw zinc
has been produced (Žibret, 2008). On the peak of the production there has been 12 pyrometalurgi-cal furnaces operating. This resulted in high rate of environmental pollution, caused by airborne particle sedimentation on the wider area of Celje basin. The Zn smelting process required highly caloric burning material, which was produced by coal gasification process. Formation of brown-field, containing highly toxic pyrometallurgical waste and coal tar creosote (Fig. 1) around past furnaces is a direct follow-up of zinc production. There were also other possible sources of organic chemicals, like Štore ironworks, traffic, small furnaces for heating of houses, chemical, paper and wood processing industry, metal manufacturing, domestic use of chemicals and products containing chemicals. Taking into account organic pollutants in Celje area several possible sources can thus be identified:
-	Evaporation of volatile organic compounds from tar creosote in Celje brownfield area;
-	Emissions from traffic;
-	Past and present coal and other fossil fuel combustion for heating of houses and other purposes, including cooking with natural gas;
-	Intensive hop and other crops farming west from Celje area and substantial use of phytopharma-ceuticals;
-	Emissions from Celje industry, including chemical industry, as well as wood processing, paper industry and others;
-	Vaporisation of compounds from asphalt (tarred) surfaces and other construction materials;
-	Domestic indoor and outdoor uses of chemical products or products containing chemicals.
Since atmospheric dust particles can travel distances of several hundred km from their source to their deposition, regional influences to the composition of the urban dusts might also be mentioned here. Two coal-powered power stations exist in the vicinity of Celje. The first one is Šoštanj power station, located 21 km NW and the other one is Trbovlje-Hrastnik power station,
Fig. 2. The map of Celje area indicating the position of sampling points. HD - house dust sampling point; AD - attic dust sampling point; SD - street dust sampling point; BF - approximate area of pyrometallurgical slag and coal creosote deposit.
located 20 km SW. Cement factory is also located next to the aforementioned power plant. Mayor wind direction is SW wind. During the winter period, temperature inversion with fog is an important factor which influences the transportation of atmospheric particles.
Materials and methods
Three sampling materials have been chosen: attic dust, household dust and street sediment because of their availability from past studies (ŽIBRET, 2002; ŽIBRET & RoKAVEc, 2010). Positions of the samples are shown on Figure 2.
Attic dust has been sampled in the attics of old house in the vicinity of past Cinkarna Celje smelting plant and Celje brownfield where the highest Zn-Cd-Pb contamination has been detected (Šajn, 2005) and there is clear influence of Cinkarna Celje to the chemical composition of soil and attic dust detected. This sampling point also lies next to the busiest road in Celje (Mariborska Street). Attic dust is formed by the deposition of airborne particles. Being situated under the roof it is preserved from rain, heavy winds or sun's radiation, so it contains the record of past atmospheric pollution from the time the house was build. Its composition is not influenced by everyday activities of the inhabitants of the house (Balbanova et al., 2011; Baceva et al., 2011; Šajn, 2006 and others). Sample was taken from the wooden roof bearing trams using plastic brush. Special attention was put not to sample possible roof tiling dust, sand from walls or possible plant remains. Sample in this study was collected in September 2001 in a building constructed in the beginning of 20 century, as a part of the other project, which aim was to evaluate the extent of toxic metal contamination in Celje area (Žibret, 2002; Šajn, 2005).
Street dust is regarded as a sink of atmospheric dust in urban environments (AYRAULT et al., 2013). It shows the contamination with particulate matter in the period of past 6 - 12 months. The reason for this is that storm events remove only a minority of the particles, deposited on the road surface (Chiew et al., 1997; Malmquist, 1978) and during rain events its composition is changed in the sense that larger particles are washed up so smaller particles prevail (vaze & Chiew, 2002). Such dust cannot be removed by street sweeping, since street sweeper machines efficiently remove only particles larger than 0.25 mm, but they do not affect much of the particles below that size (Bender & Tarstreip, 1984). Therefore atmospheric deposit and pollutants build-up occurs on dry days and electrostatically bound to the pores in the asphalt or concrete in the form of street dust. Sample of street dust was brushed from the road surface with the hard plastic brush (Fig. 3) prior sweeping the road with the soft broom to remove sand particles. Approximately of 2 m2 of road has to be brushed to collect enough atmospheric deposit. Road was brushed on 10-15 places in the radius of 20 m around sampling point to eliminate possible small-scale sample composition fluctuations. Importance of studying the street dust lies in the fact, that re-mobilised street dust by traffic is a dominant source of inhalable particles in urban environments (Amato et al. 2009; Pina et al. 2000; Sutherland, 2003).
Household dust reflects ambient air pollution and pollution from other sources, indoor and outdoor (ABT et al., 2000; TONG, 1998). The importance of studying house dust lies in the fact that this is the material we are exposed daily. Its latency is between 1 to 3 months. Its composition depends on the size of the house, dwelling habits of the inhabit-
Fig. 3. Sampling of street dust sediment. After sweeping the surface with the soft broom to remove coarse particles, fine-grained dust were extracted from pores with the hard plastic brush.
ants, pet presence etc. Household dust sample was represented by three full vacuum cleaner bags from dwellings next to the sampling point. We sampled only bags, which were used for cleaning the interior of the houses or apartments. Bags, used for vacuuming of any construction works, paint jobs, pet droppings, cars or workshops were avoided. Conversation with the owner of the house helped to identify good samples. Samples of household dust and street sediment were taken in dry weather condition in the early spring 2009, as a part of the study of ŽIBRET & RoKAVEC (2010).
Laboratory preparation of the samples included drying on 303K until no weight loss is observed, and sieving. When particles coagulated into clods due to the presence of humidity, the aggregates were softly crushed in the ceramic mortar. Fraction under 0.125 mm represented material for chemical analysis. Special procedure was applied to household dust sample preparation to remove as much fibres as possible. The contest of the vacuum cleaner bag (coagulates of hair, dirt,
fibres etc...) was rubbed on the 1 mm sieve to extract finer particles (Fig. 4). Hair and other fibres and coarse particles were discarded. The remains were sieved with quick and strong hand shaking on 0.5 mm sieve, and after that the procedure was repeated with the 0.125 mm sieve. During this procedure majority of fibres were removed and only dry air deposit and possible soil particles remained.
Samples were stored in the dark and dry place in the air-sealed plastic containers prior chemical analyses, which were done in the Czech Geological survey, using gas chromatography and mass spec-trometry. Only qualitative measurements were made for screening purposes for 120 different organic compounds. Extraction, fractionation and analysis were done according to Czech geological survey procedures (Francu et al., 2010). The presence of certain chemicals was evaluated according to the presence of the peak on the chromatogram. However, no evaluation of the peak significance was made.
Fig. 4. Household dust preparation. Material was rubbed on the 1 mm sieve. Fibres (right) were discarded, remains (left) were sieved several times on 0.5 and 0.125 mm sieves to remove as much smaller fibres as possible.
Results
Table 1 shows the aggregated results - presence of chemicals among different groups of organic compounds. The presence of the peak on chromatograph, representing a specific substance, is indicated in table 2. Unfortunately, chromatography data system for the identification of the substances, as well as identification of their sources, was unavailable to the author of this article. This is why extensive literature search was performed in order to try to interpret results. Special emphasis was put on the identification of possible origin of a certain substance, and to determine possible industrial or domestic use of it. We did not provide data sources for each of the chemicals separately, because table 2 would be too large and would loose its clarity. Therefore we provide a list of data sources for uses and occurrence for chemicals in table 2, which are:
1.	Scientific books, chemical atlases and articles (Bryant et al., 2007; CCME, 2008; Harvey et al., 1991; Kavouras et al., 1998; Kingsbury et al., 1979; Melber, 2004; Tsapakis et al., 2002; U.S. EPA, 2006; US Public Health Service, 1995; Weschler & Nazaroff, 2008);
2.	Chemical safety information factsheets (Internet 1 and 2),
3.	Data from search engines of suppliers of chemicals (Internet 3 and 4)
4.	Information from on-line chemical databases (Internet 5 and 6) and for fragrance and food additives (Internet 7);
5.	If aforementioned information sources did not provided enough information for specific chemical, a search at google.com and duckduckgo.com search engines were performed.
Since there is not much scientific information about many of the analyzed organic chemicals in world literature, and even that is scattered in a vast amount of publications, also non-scientific sources of information were used to search for the specific chemical. Therefore provided information about the occurrence and use of chemicals can be incorrect or incomplete and this information must be therefore taken into account by knowing aforementioned fact.
A special emphasis was put on US-EPA priority pollutants list (Internet 8), which are regarded as high threat to the humans and environment. However, some studies revealed that also other chemicals can also be a similar environmental threat as US-EPA priority pollutants. When such study was found during literature search it is noted in the table 2, despite not indicated as being a priority pollutant.
Table 1 shows that attic dust is the most diverse "cocktail" of organic substances, containing 98 organic substances out of 120 analysed (82 %). It also contains all of the analysed priority pollutants and representatives of almost all of the analysed groups of organic chemicals. Among them the most abundant are terpenoids, alkylbenzenes and polycyclic aromatic hydrocarbons (PAH's). Street dust contains 70 of different organic compounds
Table 1. Analysed groups of organic compounds. Table shows total number of different compounds analysed in a specific group (TOT) and detected in attic dust (AD), household dust (HD) and street dust (SD).
, , . , TOT.
groups of chemicals anAL
Aliphatic compounds
Terpenoids and degradation products
Alkylbenzenes
Polycyclic aromatic hydrocarbons (PAH)s
Sulphur containing PAHs
Oxygen containing PAHs
Nitrogen containing PAHs
Oxygenated aromatic compounds
Alcohols and phenols
Aldehydes and ketones
Ethers
Amines
Acids
Esters
Plasticizers
Fragrances
Halogenated compounds
Pesticides and degradation products
Other compounds
5
17
8
51
7
4 2 3 2 3 1 1 2 2
5 3 2
1
1
AD HD SD
333 6 4
16
8
49 21
5 2
38
TOTAL
%
PRORITY POLLUTANTS ANALYSED
120
17
98 82
45 70
38 58
17 8 14
out of 120 analysed (58 %). PAH, aldehydes, ke-tones, ethers, amines and plasticizers are the most characteristic. Among 17 analysed priority pollutants, 14 were detected in street dust. House dust contains the fewest different organic compounds among three types of dusts - 45 compounds out of 120 analysed, which means 28 % of all analyzed. Terpenoids, alkylbenzenes, PAH's, aldehides and ketones, organic acids and other compounds can be found there. 8 out of 17 analysed priority pollutants were detected in house dust.
Discussion
With only few data available, the interpretation of the results certainly contains the speculations, at some extent. From the number of different chemicals present in dusts it can be concluded, that diversity of organic molecules is decreasing in the following order: attic dust > street dust > house dust. The same order is also when we take into account priority pollutants. Lower number of different chemicals found in street dust in comparison with attic dust can be attributed to the fact that street dust is exposed in comparison to attic dust is exposed to
Table 2. Organic compounds identified in environmental samples from Celje (Slovenia). AD - attic dust; HD - household dust; SS - street dust. US-EPA priority pollutants are indicated with italic underline letters.
occurrence & use
AD HD SS
Aliphatic compounds				
Homologues series of n-alkanes (C10				
to C30)a				
Series of various methylated		+	+	+
n-alkanesb				
n-alkylcyclohexanes with side chainsb	intermediate in industrial processes, unstable	+		
n-alkylcyclohexenesbc	intermediate in industrial processes, unstable		+	
Misc. alkyl cycloalkanesbc	naturally occurring molecules; chrysanthemic acid, prostoglandins, steroids			+
Terpenoids and degradation products				
D-Limoneneb	citrus, detergents, cosmetics, orange juice	+	+	+
Cymenesbc	cosmetic, food, medicine	+	+	+
3-Methoxy-p-cymeneb	wood industry, plant gradient, cumin, thyme	+		
(+)-4-Careneb	wood turpentine; paints, solvent, volatile oil	+	+	
Octahydro-4b,8-dimethyl-2-isopropylphenanthreneb	cigarette smoke, coal burning	+		
Cadaleneb	essential oil of high plants	+		
Calameneneb	essential oil	+		+
a-Cedreneb	cedar oil, spices	+	+	
a-Muurolene	essential oil, perfumes, medicines		+	
Longicycleneb	essential oil (Orchidacaea, Asparagales)	+		
Junipeneb	essential oil (Abies cilicica)	+		+
Ferruginolb	essential oil (Sequoia sempervirens), anti-tumour, anti-bacterial activity	+		
Squaleneb	lipid, produced by plants, animals, incl. humans, olive oil, cosmetics, vaccines	+	+	+
Selinaneb	enzymes, found in algae, plants and insects	+		
Isophyllocladeneb	essential oil of Araucaria excelsa	+		
Aromadendran ('2')	flavonoid (Pinus sibirica)	+		
ß-Patchoulane	terpene, extracted from Pogostemon cablin	+		
Alkylbenzenes				
5-Ethyl-m-xyleneb	wood, petrochemical, coke fuel, additive in gasoline	+		
Trimethylbenzenesb,c	coal tar, petroleum, mineral oils, gasoline additive, dyes, perfumes, scintilators	+	+	+
Tetramethylbenzenesb,c	toxic, curing agents, plastics, cross-linking agents, alkyd resins	+	+	+
Dimethylstyrenesb,c	flavour and fragrance agent; orchids Catasetum.	+		
Linear alkylbenzenes (Cx-benzenes)b,c	surfactants, detergents	+	+	
1-Methyl-4(1-methylpropyl)benzeneb	-	+		
2,4-diphenyl-4-methyl-2(E)-pentene	-	+		
4,4'-Diacetyldiphenylmethaneb	polyurethane foams	+	+	
Polycyclic aromatic hydrocarbons, PAH				
Naphtalene'	coal tar, heavy petroleum fractions, petroleum based fuels, coal, burning of	+	+	+
	wood and tobacco, indoor air pollutant			
Ethylnaphthaleneb	coal tar, heavy petroleum fractions (oil spills)			+
1-Methylnaphtaleneb	coal tar, heavy petroleum fractions (oil spills)	+	+	+
2-Methylnaphtaleneb	coal tar, heavy petroleum fractions (oil spills)	+	+	+
C2-Naphthalenesbc	coal tar, heavy petroleum fractions (oil spills)	+	+	+
C3-Naphthalenes	coal tar, heavy petroleum fractions (oil spills)	+	+	+
C4-Naphthalenes	coal tar, heavy petroleum fractions (oil spills)	+		+
2-Phenylnaphthaleneb	occurrence with PAH in sediments, decomposition of plastics, coal	+		+
Phenylmethylnephtalenesb,c	-	+		+
2,6-Diisopropylnaphthaleneb	pesticides, natural plant growth regulator	+	+	+
Biphenylb	organic compounds, plastics, coal tar, oil, natural gas, preservative (E230)	+	+	+
3- and 4-methylbiphenylb	naturally occurrence in cocoa, spicy odour, flavouring agent	+		+
C2-Biphenylsbc	organic compounds, plastics, emulsifiers, naturally occurrence in coal, crude oil and natural gas	+	+	+
1-Phenyl-1,3,3-trimethylindan	fragrance agent	+		+
Acenaphthylene'	coal tar	+		+
Acenaphtene'	coal tar	+		+
Fluorene'	coal tar	+	+	+
Methylfluorenesbc	coal liquefaction by-product	+		+
Dimethylfluoreneb	organic electroluminescent elements			+
1- and 2-phenylnaphthalenesb,c	plant lignans, found in organic sediments	+		+
Phenanthrenea	combustion by-product, cigarette smoke, coal burning	+	+	+
Anthracenea	coal tar, dyes, plastics, incomplete combustion of coal, gas or garbage	+		
2-Ethylanthracene	toxic to aquatic organisms	+		+
9-Phenylanthracene	component in crude oil, final stage of oil generation	+		
Methylphenanthrenesb,c	natural oil, coal-derived liquids, tar, traffic	+	+	+
Methylanthracenesb,c	diesel engines exhaust, crude oil component	+	+	+
Dimethylphenanthrenesb,c	wood combustion, motor vehicle exhaust, tars, coal-derived liquids, oxidation of resins	+	+	+
C3-Phenanthrenesbc
4H-Cyclopenta(def)phenanthreneb
Reteneb
Fluoranthene"
Pvrenea
Methylfluoranthenes/-pyrenesbc
o,p,m-Terphenylsbc
Benzo(ghi)fluorantheneb Chrysenea/Triphenyleneb
Benzo(a)anthracenea
Methylbenz(a)anthracenesbc
Cyclopenta(cd)pyreneb
Methylchrysenesbc
1,2'- and 2,2'-Binaphthylb
Benzo(x)fluoranthene (x=i.b.k)b-c
Benzo(a)pvrenea
Peryleneb
Indeno(1,2,3-cd)pyrene' Dibenzo(a,h)anthracene'
Benzo(g,h,i)perylenea
Benzo(b)chryseneb
Coroneneb
Dibenzopyrenesb,c
Indeno(1.2.3-fa)naphthacene
Oxygenated aromatic compounds
Benzanthroneb
Sulphur containing PAHs
Dibenzothiopheneb
Methyldibenzothiophene(s)
Dimethylbenzothiopheneb
C2-Dibenzothiophenesb,c Benzo(b)naphtho(1,2 or 2,1-d) thiopheneb
Mono- and dimethylbenzonaphthothi
ophenesb,c
Benzothieno(4,5-b)benzothiophene Oxygen containing PAHs
Dibenzofuranb
Methylbenzofuranesb,c Benzonaphthofuranb,c Benzobisbenzofuranesb,c
Nitrogen containing PAHs
Carbazoleb
Methylcarbazolesb,c
Oxygenated aromatic compounds 9-Fluorenolb Ditertbutylquinone Benzanthroneb
Alcohols and phenols
Butylated hydroxytoluene (BHT)b Di-tert-butylphenol
Aldehydes and ketones
Misc. n-aldehydesb,c
Misc. x-alkanonesb,c Diisobutyl ketoneb
Ethers
Dioctyl ether
Amines
Diphenylamineb
Acids
Misc. n-alkanoic acidsb,c
Benzoic acid
Esters
Isopropyl myristateb Methylpalmitate
cigarette smoke, coal burning, dyes, plastics, pesticides, garbage incineration, oil, oil marker
pyrolysis product of catechol (precursor chemical of pesticides, flavours
and fragrances), fuel component
coal tar fraction, resinous wood distillation
low-temperature combustion by-product, carcinogen
incomplete combustion of organic compounds, coal tar ?
fungus and mould growth prevention, sunscreen lotion component, pharmaceuticals, intermediate for many other chemicals tobacco smoke, fuel combustion
coal tar, electronic and optic cables, wood preservative, stable
coal tar, roasted coffee, smoked foods, automobile exhaust, intermediate
for other chemicals, carcinogen ?
gasoline engine exhaust
tobacco smoke, diesel engine emissions, carcinogen ?
tobacco smoke, incomplete combustion of fossil fuel, carcinogen
coal tar, diesel engine exhaust, wood combustion, highly carcinogenic
tobacco smoke, Rylene dyes, in-situ biogenic origin from organic matter
coal slurry, coal tar, tobacco smoke, gasoline engine exhaust
automobile exhaust, cigarette smoke, carcinogenic
incomplete combustion or pyrolysis of organic matter, fossil fuels
combustion, cigarette smoke
coal tar, airborne pollution (traffic)
hydrothermal mineral carpathite, gasoline exhaust
coal tar, forest fires, cigarette smoke
tobacco smoke
dyes, pyrotechnics industry-green and yellow colour smokes heavier fractions of petroleum
component of crude oil, occurrence in sedimentary rocks
component of crude oil, occurrence in sedimentary rocks, coal-derived
liquids
component of crude oil
product of crude-oil microbial degradation
product of crude-oil microbial degradation
coal tar, oil, insecticide, production of PVC, industrial bleaching and incineration
occurrence in coffee, flavouring agent burning of residential waste, coal tar oled diodes
coal tar; intermediate in synthesis of pharmaceuticals, agrochemicals, dyes, pigments, optoelectronics... coal tar, crude oil;
substance in coal
oxidant, polymerization catalyst
dyes, pyrotechnics
antioxidant (=E321), fuel additive, hydraulic fluid, jet fuel, rubber antioxidant in petrochemicals and plastics, aviation fuel
polyurethane and other construction materials production, plastics, essential oils
solvent, polymer precursor, pharmaceuticals, natural molecules solvent (leather, cleaning, paint, lack... )
lubricant , anti-static agent, electrical insulator, water repellent food
soap, food, drugs, rubber, dyes, perfumes
food preservative (E210), pharmaceutics, sunscreen, body wash... cosmetics
detergents, resins, plastics, lubricants, food
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+
Plasticizers
Diethvlphthalateb
Dibutyl phthalate (DBF)"
Di-iso-butylphthalateb
Bis(2-ethylhexyl)phthalate (DEHF)b
Phthalic anhydride
Fragrances
?-, ?-Muuroleneb
Geranylacetoneb
Hexahydrofarnesyl acetone
Halogenated compounds
Mixture of di- to hexachlorinated
biphenyls (FCB's)ab
Tetrachloro-m-xyleneb
Pesticides and degradation products o.p- and p.p-DDT Other compounds Octasulfur
cosmetics, detergents, sprays	+
solvent, additive to pesticides, repellents, adhesive, ink	+ PVC, PVC copolymers, footwear, jackets
PVC, capacitors, hydraulic fluid	+ plastics, paints, urethane polyester, insect repellent
herbs, spices, wood	+ perfumery, food (chocolate, marzipan) long-lasting fresh jasmine, celery odour
heat-transfer fluids, dielectric fluid, persistent pollutant, carcinogenic	+
pesticides & metabolites	+
phytopharmaceutical, pollutant	+
yellow sulphur powder	+
' Identified by comparison of GC and MS data with those of reference compounds b Identified by comparison of MS data with those of MS data bases (NIST98) c Mixtures of isomers/homologues
the ultraviolet light from sun produce photo degradation and oxidation of many of the compounds. Also other weather influences might change the composition of street dust. As the retention time of the street dust is estimated to be between 6 to 12 months, certain chemicals, which are banned today, are no longer found there, but they are preserved in attic dust (such as DDT and PCB for example). Lowest number of compounds in house dust can be explained that certain chemicals can be effectively removed by regular cleaning of homes in contaminated environments.
First group of organic chemicals of interest are terpenoids, which are dominantly the compounds, found in plants. Their origin is from wood remains, pollen and other plant remains. Majority of terpenoids are of natural origin. They are most abundant in attic dust, most probably because attic dust contains a lot of pollen or similar windblown organic material. Alkylbenzenes are also abundant in all types of dusts. Since alkylben-zenes are usually biodegradable, we assume that their presence in dusts do not pose increased long-term environmental or health risk.
But the focus of future studies might be on PAH's and other aromatic compounds, since the occurrence of this group of chemicals has the major potential to pose a health or environmental risk. Some of them are regarded also as priority pollutants. Literature search points out the source of PAH's are dominantly coal tar and by-products of incomplete combustion of all types of burning materials. From current dataset it is impossible to determine the source of PAH's in Celje. Traffic and burning of fossil fuels can be suspected to be responsible for their presence. But it can be speculated that vaporisation from tar at the Celje brownfield can also be an important source of PAH's in the attic and street dust, and to some extent also in house dust. It is interesting, that also short-lived PAH's are present in attic dust. Thus it can be suspected that a continuous source of such compounds exists in Celje. Regarding the the occurrence of PAH's indoors, it must be denoted
that beside outdoor sources also smoking, grilling of food, wood burning for heating (like fireplace indoors), vaporisation of petroleum products and burning of natural gas can all be possible indoor sources.
Aldehides and ketones, ethers, amines, organic acids, esters and fragrances are abundant natural molecules and usually do not pose increased risk at exposure to small quantities, so their occurrence will not be discussed here.
Another group which contains priority pollutants are plasticizers, and this group of chemicals might also be a focus of future studies. Street dust contains 4 among 5 chemicals from this group, attic dust 3 and house dust 1 representative. It can be speculated, that additives to construction materials can be a reason for plasticizer occurrences in urban atmosphere. House dust, contrary, contains no priority pollutant plasticizers. Among environmentally dangerous and carcinogenic pollutants, PCB's were found in attic dust, but not in street and house dust, which might indicate that PCB's are no longer emitted in Celje any more, but they were used at some point in the past. Last priority pollutant chemical is pesticide DDT and its degradation products. As at PCB case, they can be found only in attic dust, but not in street or house dust. This can be explained by the possible use of DDT containing insecticides for the hop and other crops production in the Celje area in the past, thus proving that attic dust is really a museum for atmospheric contamination in the area of interest, as being expressed by Davis & Gulson (2005). Our results also points out that no sources of DDT exist in Celje area today.
Conclusions
Attic dust, house dust and street dust samples from Celje area were analysed for the presence of 120 different organic substances using gas chro-matography and mass spectrometry. Attic dust contains 82 % of organic substances, among them all of the US-EPA priority pollutants. Terpenoids,
+
+
+
+
alkylbenzenes and PAH's are the most abundant. Street dust contains 58% of analysed organic chemicals. Most abundant groups of compounds are PAH's, aldehydes, ketones, ethers, amines and plasticizers. House dust contains the least different organic compounds - 38 % of all analysed. Ter-penoids, alkylbenzenes, PAH's, aldehides, ketones and organic acids can be found there. Among 17 analysed priority pollutants, all were detected in attic dust, 14 of them in street dust and 8 of them in house dust. Evaporation of organic compounds from Cinkarna brownfield, traffic and other types of fossil fuel combustion, use of certain chemical and natural products, construction, evaporation from tarred road surfaces, wood-processing and chemical industry, wood burning, as well as natural gas burning for cooking, smoking or food grilling can be suspected anthropogenical sources of detected organic chemicals.
Since no quantitative evaluation was made, this study must be used only as a guideline for possible further studies. Its main added value is that certain groups of chemicals are evaluated in street, attic and house dust, thus the results can point to the direction of future interests. Since analyses of organic compounds are expensive, this study can be very useful for reducing possible costs of future studies of organic pollutants. Moreover, an analysis of groundwater in the area around industrial waste deposit might be useful. Author recommendation is, that the most interesting groups of organic chemicals for the future studies of ambient dusts in Celje, as well as also in the other places, might be PAH's and plasticizers. Measuring actual concentrations of such organic compounds in different natural and anthropo-genical materials in Celje area might be an useful follow-up of this study.
Acknowledgments
This study was made within the scope of programme group "Mineral resources" (P1-0025), funded by the Slovenian Research Agency. Author would like to kindly acknowledge the gratitude to the Radim Lana for chemical analyses, who was at the time when the chemical analysis were done employed at the Czech Geological Survey in Brno, and to Eva Francu, who kindly allowed to conduct the analyses in the laboratory she was in charge for.
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