Title Prostorna i vremenska raspodjela policikličkih aromatskih ugljikovodika u zraku Title (english) Spatial and temporal distribution of polycyclic aromatic hydrocarbons in the air Author Ivana Jakovljević Mentor Gordana Pehnec (mentor)Mentor Vesna Tomašić (mentor)Committee member Ana Lončarić Božić (predsjednik povjerenstva)Committee member Marija Vuković Domanovac (član povjerenstva)Committee member Sanda Rončević (član povjerenstva)Granter University of Zagreb Defense date and country 2017-12-12, Croatia Scientific / art field, TECHNICAL SCIENCES Universal decimal classificationUDC ) 66 - Chemical technology. Chemical and related industries 502/504 - Environmental science. Conservation of natural resources. Threats to the environment and protection against them Abstract Policiklički aromatski ugljikovodici (PAU) su organski spojevi koji se sastoje od dva ili više međusobno povezana aromatska prstena. Najpoznatiji i najviše proučavan PAU je benzo[a]piren (BaP) koji se često koristi kao indikator za karcinogenu aktivnost onečišćenja u okolišu. BaP nije i najzastupljeniji spoj, ali se uvijek javlja ukoliko su PAU prisutni. U atmosferi PAU mogu biti prisutni u plinovitoj fazi te vezani na lebdeće čestice. Dosadašnja istraživanja pokazala su da su PAU s dva ili tri aromatska prstena postojani u plinovitoj fazi te njihova koncentracija u zraku raste s porastom temperature, dok se PAU s više aromatskih prstenova nalaze u zraku uglavnom vezani na lebdeće čestice. PAU nastaju kao posljedica prirodnih procesa kao što su karbonizacija, šumski požari ili vulkanske erupcije. Nastaju i kao produkt spaljivanja otpada i raznih plastičnih masa u nedopuštenim i nekontroliranim uvjetima ili pirolizom organskih tvari te tijekom raznih industrijskih procesa (proizvodnja ugljena, sirove nafte, teških i lakih metala). Također su prisutni u ispušnim plinovima automobila te u dimu cigarete. Uzorkovanje je provedeno referentnim sakupljačima s malim protokom zraka
(55 m^3) tijekom 24±1 sata kroz filtarski papir od kvarcnih vlakana. Na jednom urbanom mjernom mjestu (A) sakupljani su uzorci frakcija lebdećih čestica PM10, PM2.5 i PM1, dok je na drugim urbanim i ruralnim lokacijama sakupljana PM10 frakcija lebdećih čestica. Na urbanim lokacijama uzorkovanje se provodilo svakodnevno tijekom cijele kalendarske godine, dok su na ostalim lokacijama uzorci sakupljani najmanje 30 dana tijekom sezone. Analiza PAU-a provedena je tekućinskom kromatografijom visoke djelotvornosti (HPLC) s fluoroscentnim detektorom promjenjivih valnih duljina ekscitacije i emisije. Određivani su sljedeći PAU-i: fluoranten (Flu), piren (Pir), benzo[a]antracen (BaA), krizen (Kri), benzo[e]piren (BeP), benzo[b]fluoranten (BbF), benzo[k]fluoranten (BkF), benzo[a]piren (BaP), dibenzo[ah]antracen (DahA), indeno[1,2,3-cd]piren (IP) i benzo[ghi]perilen (BghiP). Masene koncentracije PAU-a u sve tri frakcije mjerenja (PM10, PM2,5 i PM1) pokazuju sezonske varijacije s najnižim vrijednostima tijekom ljeta, a najvišim tijekom zimskog razdoblja godine. Na svim urbanim lokacijama te na urbano-industrijskoj lokaciji najvišu vrijednost tijekom svih godišnjih doba imao je BghiP, a najnižu DahA. Najviše vrijednosti masenih koncentracija PAU-a zimi izmjerene su na mjernom mjestu u planinskom području s drvnom industrijom. Regresijska i faktorska analiza pokazala je da su na svim mjernim mjestima dominantni izvori onečišćenja zraka PAU-ima su ispušni plinovi motornih vozila, izgaranje drva, trave i otpada tijekom proljeća i ljeta te izgaranje drva u kućnim ložištima tijekom jeseni i zime. Toksična ekvivalentna koncentracija bila je viša u hladnijem razdoblju mjerenja, dok je relativni karcinogeni potencijal bio viši u toplijem dijelu godine. Nađena je statistički značajna negativna korelacija između PAU-a i ozona te PAU-a i temperature. Pozitivna korelacija nađena je između PAU-a i SO2, CO i vlage. Odnosi pojedinih PAU između PM10 i PM2.5 te PM1 i PM2.5 frakcija lebdećih čestica ispitani su regresijskom analizom te su pokazali da su PAU-i sadržani uglavnom u česticama manjega aerodinamičkoga promjera PM2.5 i PM1 tijekom svih godišnjih doba, što dodatno potvrđuje njihovo štetno djelovanje na zdravlje ljudi.
Abstract (english) Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds consisting of two or more benzene rings. Benzo(a)pyrene is the most commonly measured PAH and is used as an indicator of carcinogenic hazard in polluted environments. BaP is not always found in abundance, but it always occurs when PAHs are present. In the atmosphere, PAHs can be present in the gaseous phase or bounded to particulate matter. Previous studies have shown that PAHs with two or three benzene rings are stable in the gas phase and their concentration in the air increases with temperature, while PAHs with more aromatic rings mostly bond to particulate matter. PAHs are products of natural processes such as carbonation, large forest fires or volcanic eruptions. They are products of waste incineration, pyrolysis of organic matter and a variety of industrial processes (coal, crude oil, heavy and light metal). They are also present in car exhausts and cigarette smoke. Daily samples of particle fractions were collected 24 ± 1 hour by a reference sampler on quartz filter. At one measuring site (A), daily samples of PM10, PM2.5 and PM1 particle matter were collected throughout the entire calendar year, while at the other urban and rural locations only PM10 particulate matter was collected only 30 days during one season. PAH analysis was carried out using high performance liquid chromatography (HPLC) with fluorescence detection and changeable excitation and emission wavelength. Samples were analysed for the following PAHs: fluoranthene (Flu), pyrene (Pir), benzo [a] anthracene (BaA), chrysene (Kri), benzo [e] pyrene (BeP), benzo [b] fluoranthene (BbF), benzo [k ] fluoranthene (BkF), benzo [a] pyrene (BaP), dibenzo [ah] anthracene (DahA), indeno [1,2,3-cd] pyrene (IP) and benzo [ghi] perylene (BghiP). Mass concentrations of PAHs bounded to PM10, PM2.5 and PM1 showed seasonal variations with the lowest values in summer and the highest during the winter period of the year. Urban locations had higher concentrations of PAHs in the air in comparison to rural measuring sites, because they were dominated by different pollutions (car exhaust, combustion of wood or other fossil fuels, etc.). At all urban locations and at the urban-industrial location, the highest value mass concentration had BghiP and the lowest value mass concentration had DahA in all seasons. The highest values mass concentration of PAH in winter were measured at mountainous area with wood industry. Regression and factor analysis showed that the dominant source at all of the measuring sites site were car exhaust, wood, grass and waste combustion during spring and summer, wood combustion in households during autumn and winter. Total carcinogenic activity was higher in the cold measurement period at all of the sites, while the relative potency factors were higher during the warmer period of the year. Negative correlations were found between PAH and ozone and PAH and temperature. Positive correlations were found between PAH and SO2 and CO and humidity. The relationship between the mass concentrations of PAHs in the PM10 and PM2.5 particle, between PM1 and PM2.5 fraction particle matter were tested with regression analysis. It has been found that most PAHs are present in the fraction of PM2.5 and PM1 during all seasons, which implies that they can have adverse effect on human health.
Keywords
BaP
HPLC
lebdeće čestice
PAU
prostorna raspodjela
sezonska varijacija
ukupna toksična ekvivalentna koncentracija
Keywords (english)
BaP
HPLC
particle matter
PAH
spatial variation
seasonal variation
total carcinogenic activity
Language croatian URN:NBN urn:nbn:hr:149:047781 Promotion 2017 Project Number: 022-0222882-2338 Study programme Title: Engineering Chemistry - Doctoral Course Type of resource Text Extent 182 str. ; 30 cm File origin Born digital Access conditions Open access Terms of use Created on 2023-12-06 10:03:17
