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Journal of Environmental Sciences
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Aerosol organik primer dan sekunder di situs perkotaan / industri: Sumber,

implikasi kesehatan dan peran pembakaran sampah yang diperkaya plastik
Panagiotis Georgios Kanellopoulos 1 , Eleni Verouti 1 , Eirini Chrysochou,

Konstantinos Koukoulakis, Evangelos Bakeas ∗
Universitas Nasional dan Kapodistrian Athena, Laboratorium Kimia Analitik, Departemen Kimia, Zografou, GR-15784, Yunani
articleinfo Pendahuluan
Sejarah artikel: Diterima 5 April Airborne particulate matter (PM), juga dikenal sebagai aerosol
2020 Revisi 10 Juni 2020 Diterima
atmosfer, terdiri dari partikel tersuspensi ke atmosfer dengan berbagai diameter
11 Juni Juni 2020
aerodinamik (dari nm ke μm). Emisi PM adalah hasil dari berbagai kegiatan alami dan
antropogenik seperti, proses pembakaran, kegiatan industri, penangguhan debu tanah dan
Kata kunci: Aerosol organik primer (POA) Aerosol transformasi senyawa fase gas, ( Ghosh et al., 2018 ) yang menyebabkan dampak parah
organik sekunder (SOA) Emisi pembakaran sampah
plastik. GC / MS. SumberPCApembakaran yang pada kesehatan manusia ( Anderson et al., 2012 ; Kim et al., 2015 ) dan iklim
mpulkan dari lokasi perkotaan / industri di dekat Athena, tempat aktivitastidak terkendali terjadi. PAH,
carboxylic, hydroxycarboxylic dan asam aromatik, pelacak dari oksidasi BVOC, pelacak pembakaran biomassa Penulis yang sesuai.
entukan. PAH, asam monokarboksilat, pelacak pembakaran biomassa dan bisphenol A meningkat selama musim Alamat email: bakeas@chem.uoa.gr (E. Bakeas). 1
in, sementara pelacak BSOA, asam dicarboxylic- dan hidroksikarboksilat selama musim panas. Mengenai asam
Keduanya berkontribusi sama untuk artikel ini.
sumber dan mekanisme pembentukan diindikasikan sebagai asam benzoat, phthalic dan trimellitic memuncak
( Lohmann dan Feichter, 2005 ; Myhre et al., 2013 ; Rosenfeld et al., 2014 ). Fraksi
s sedangkan p -toluic, isophthalic dan terephthalic lebih berlimpah selama musim gugur / musim dingin. Benzo
ogenik setara pyrene, karsinogenik dan aktivitas mutagenik dihitung menunjukkan peningkatan yang signifikan organik
( PM, yang sering disebut sebagai aerosol organik (OA), mengandung ribuan
senyawa
ulan-bulan yang lebih dingin. Asam palmitat, suksinat dan malat adalah asam monokarboksilat, dicarboxylic, dan yang menyumbang 20% -90% dari total massa aerosol halus, dengan dampak
ng paling banyak selama periode pengambilan sampel keseluruhan. Oksidasi isoprena merupakan kontributor parah pada iklim global / regional, kimia atmosfer dan kesehatan masyarakat (
hadap BSOA karena senyawa isoprena-SOA dua kali lebih banyak daripada pinene-SOA (masing-masing 13,4 Kanakidou et al., 2005 ; Pöschl, 2005 ; Jimenez et al., 2009 ; Fu et al., 2010 ; Gilardoni,
9 ng / m 3 ). Ozon memiliki dampak signifikan pada pembentukan banyak senyawa yang dipelajari 2017 yang ; Shrivastava et al., 2017 ). OA dapat dipancarkan ke atmosfer secara langsung
(Aerosol organik primer - POA) ( De Gouw dan Jimenez, 2009 ) atau dibentuk melalui
asi signifikan dengan: isoprena-SOA ( r = 0,77), asam hidrokarboksilat ( r = 0,69), pinene-SOA ( r = 0,63), asam
0,58 ), dan jumlah asam ftalat, benzoat, dan trimelitat ( r = 0,44). PCA menunjukkan lima faktor yang dapat berbagai proses atmosfer oksidasi senyawa organik yang mudah menguap (aerosol
r termasuk pembakaran limbah yang diperkaya plastik (30,8%), oksidasi asam lemak tak jenuh (23,0%), organik misi sekunder - SOA) ( Hallquist et al. , 2009 ).
masak (9,2%), pembakaran biomassa (7,7%) dan oksidasi VOC ( 5,8%). Hasilnya menyoroti kontribusi signifikan Sumber POA meliputi pembakaran bahan bakar biomassa / fosil, tanaman
pembakaran yang tidak terkendali terhadap degradasi kualitas udara secara keseluruhan. yang lebih tinggi dan debu tanah ( Simoneit et al., 1999 ; De Gouw dan Jimenez, 2009 ;
Zheng
© 2020 Diterbitkan oleh Elsevier et al.,
BV atas nama2014 ; Kang
Pusat et al.,
Penelitian 2018
untuk ). Lingkungan
Ilmu Di lingkungan perkotaan,
Hidup, Akademimisalnya, meskipun
Ilmu Pengetahuan
Cina. emisi lalu lintas adalah POA dasar
https://doi.org/10.1016/j.jes.2020.06.012 1001-0742 / © 2020 Diterbitkan oleh Elsevier BV atas nama The Research Center for Ilmu Lingkungan Hidup, Akademi Ilmu Pengetahuan
Tiongkok.
Jurnal Ilmu Lingkungan 99 (2021) 222-238
PG Kanellopoulos, E. Verouti dan E. Chrysochou et al. / Jurnal Ilmu Lingkungan 99 (2021) 222-238 223
sumber, kontribusi pembakaran biomassa dan OA non-fosil juga signifikan dan perlu dan gas anorganik atmosfer ( Downard et al., 2015 ). Sumber SOA juga berganda dan
perhatian yang tepat ( Huang et al., 2019 ). Kontributor penting lainnya, tetapi diabaikan,
termasuk reaksi fotokimiawi senyawa organik volatil biogenik dan antropogenik
POA adalah praktik pembakaran limbah terbuka. Di Cina, 22% dari totalPM (BVOCs
10
dan AVOCs) dengan menjadi sumber dominan dalam skala global ( Heald et
emisidikaitkan dengan kegiatan pembakaran limbah domestik terbuka ( Wiedinmyer et al., 2008 ). Di antara BVOCs, isoprena adalah yang paling melimpah dengan emisi
global tahunan sekitar 600 Tg / tahun ( Guenther et al., 2006 ) sedangkan SOA turunan
al., 2014 ). Selain itu, Downard et al. (2015) menyoroti pentingnya karakterisasi kimia
dari emisi parsial dari pembakaran ban yang tidak terkontrol karena mereka mengamati isoprena diperkirakan mencapai 70% dari total SOA ( Heald et al., 2008 ). Dalam
lingkungan perkotaan, VOC semi-volatile dan menengah bertanggung jawab untuk
pengayaan yang signifikan pada tingkat PM 2.5 , hidrokarbon aromatik polisiklik (PAH)
pembentukan SOA ( Robinson et al., 2007 ). Sebagian besar senyawa SOA mengandung 1.1. Deskripsi situs
gugus fungsi polar dalam molekulnya seperti karbonil, hidroksil, dan karboksil.
Senyawa-senyawa ini bersama-sama dengan akun POA polar untuk sebagian besar Kotamadya Aspropirgos dengan 30.251 penduduk berdasarkan sensus 2011,
aerosol organik (40% -80%) ( Jaffrezo et al., 2005 ; Ho et al., 2015 ). terletak di Dataran Thriassion sekitar 20 km sebelah barat Athena - ibukota Yunani- dan
Dalam hal ini, identifikasi konten OA dan sumber emisinya adalah masalah 3 km sebelah timur Eleusis, kawasan industri terbesar di Yunani ( Gambar 1 ). Bagian
besar terutama di zona perkotaan dan industri, seperti lokasi Aspropirgos yang dipelajari timur laut kotamadya ditutupi oleh massif pegunungan Parnesian sementara tenggara
dengan ini, untuk mengevaluasi kualitas udara dan posisi. dampak kesehatan sementara oleh gunung berbatu Poikilo. Pegunungan Parnesia sebagian besar ditandai oleh hutan
dari paparan PM sehubungan dengan penerapan kebijakan lingkungan dan strategi pohon cemara Yunani, Abies cephalonica, hutan konifer dan scrub macchia. Di dalam
mitigasi. Dalam kedekatan kualitas udara Yunani, beberapa penelitian telah dilakukan di area Aspropirgos, lebih dari 300 industri terletak termasuk industri kayu, karet, plastik
lokasi yang berbeda sepanjang tahun mengenai distribusi spasial dan temporal dari dan kimia, pengilangan dan proses metalurgi. Tekanan serius lain terhadap kualitas udara
polusi partikulat di Wilayah Greater Athens ( Pateraki et al., 2013 ), PAHs dan logam di daerah tersebut terkait dengan pengoperasian beberapa tempat pembuangan akhir yang
berat terikat kePM 10 partikeldi Athena ( Mantis et al., 2005 ; Valavanidis et al., 2006 legal dan ilegal dan khususnya kegiatan pembakaran yang tidak terkontrol secara terus
dan Volos ( Manoli et al., 2017 ), sebuah studi elemen jejak dua tahun di Eleusis, sebuah menerus di mana bahan bakar termasuk limbah rumah tangga, plastik, ban, elektronik
situs industri di dekatnya Athena ( Koukoulakis et al., 2019 ), konsentrasi fase gas dan dll. ( Koukoulakis et al., 2019 ).
partikel PAH, PCB, PCDD / Fs dan hidrokarbon alifatik di atmosfer Athena ( Titik pengambilan sampel terletak di distrik Aspropirgos antara pusat kota dan
Mandalakis et al., 2002 ) dan logam terikat partikel di Aspropirgos ( Pasias et al., 2013 zona industri dan 2 km dari kilang minyak. Pengambilan sampel partikel dilakukan di
2014 ). Di Thessaloniki, kota Yunani terbesar kedua, dampak krisis ekonomi pada atap gedung sekitar 4 m dari tanah. Secara total, 56 sampel dikumpulkan selama 4
kualitas udara disorot, karena peningkatan 30% dariPMambien 2.5 tingkatdan periode musiman, dari musim panas 2018 hingga musim semi 2019. Setiap musim
peningkatan 2-5 kali lipat pelacak pembakaran biomassa telah diamati selama kampanye termasuk 14 sampel dan 1 filter kosong. Pengambilan sampel dilakukan dari 6/6/18
musim dingin ( Saffari et al., 2013 ). Selain itu, di lokasi yang sama kelas yang berbeda hingga 19/6/18 (musim panas), dari 29/10/18 hingga 11/11/18 (musim gugur), dari
dari senyawa organik fase parsial telah dipelajari termasuk PAH, asam dikarboksilat, 21/12/18 hingga 3/1/19 (musim dingin) dan dari 19/4/19 hingga 2/5/19 (musim semi).
gula / gula anhidrida, alkilfenol, ester phtha- terlambat dll. ( Salapasidou et al., 2011 Sampel aerosol harian dikumpulkan pada filter serat kuarsa (diameter 47 mm)
Manoli et al., 2017 ; Balla et al., 2018 ). menggunakan volume sampler rendah (LVS16, Umwelttechnik MCZ GmbH, Jerman)
pada laju aliran 38,3 L / mnt selama 24 jam. Protokol EN12341 diterapkan untuk
Dalam karya ini, 47 senyawa organik dari 8 kelas dan bisphenol A yang
prosedur pengambilan sampel dan penentuan gravimetri massa partikel ( EN 12341,
berbeda telah diidentifikasi dan diukur dalamPM 10 sampelselama penelitian satu tahun 2014 ). Filter disimpan pada -21 °C sampai analisis.
di Aspropirgos, zona perkotaan / industri di dekat Athena, di mana kegiatan pembakaran
yang tidak terkontrol sering dilakukan. Senyawa yang diteliti meliputi PAH, asam
dikarboksilat (DCA), asam monokarboksilat (MCA), asam aromatik (AA), asam 1.2. Analisis
hidroksikarboksilat (HCA), pelacak pembakaran biomassa (BBT) dan produk oksidasi
isoprena dan pinena (ISOA & PSOA). Tren laut dari masing-masing kelompok dibahas Setelah pengambilan sampel, filter dipotong menjadi dua bagian simetris.
dan sumber-sumbernya disesuaikan dengan penggunaan rasio diagnostik molekuler dan Bagian pertama digunakan untuk analisis PAH sedangkan bagian kedua digunakan untuk
analisis komponen utama (PCA). Risiko menghirup kanker juga diperkirakan. penentuan spesies yang teroksigenasi.
Sepengetahuan kami, ini adalah studi inklusif mengenai karakterisasi kimiawi aerosol Prosedur berikut dilakukan untuk analisis PAH: Sebelum ekstraksi, sampel
organik atmosfer dan yang pertama memberikan pemantauan sejumlah besar senyawa,
dibubuhi 20 μL standar internal (1,0 μg / mL) (campuran fenantrena D10 dan perilen
terutama dan yang dipancarkan sekunder, di atmosfer zona perkotaan / industri di dekat
D12, Supelco). Filter diekstraksi dengan 30 mL diklorometana (Carlo Erba ) dalam
Athena.
Gbr. 1 - Situs pengambilan rendaman ultrasonik (Ultrasonic LC 130H, Elma, Jerman) selama 14 menit. Prosedur
sampel. ekstraksi dilakukan di triplicate. Ekstrak yang diperoleh digabungkan dan dipekatkan
dalam volume menggunakan rotary evaporator (Rotavapor R-210, Buchi, Switzerland)
pada28 suhu°C hampir 2–3 mL. Kemudian, perubahan pelarut adalah per
1. Bahan dan metode
224 PG Kanellopoulos, E. Verouti dan E. Chrysochou et al. / Jurnal Ilmu Lingkungan 99 (2021) 222-238
dibentuk dengan penambahan 10 mL heksana (Macron Fine Chemi- cals ) . Larutan Kondensasi lebih lanjut terjadi dengan uap nitrogen yang lembut sampai kering.
dipekatkan lagi menjadi 2-3 mL dan penambahan kedua 5 mL heksana dibuat. Akhirnya,
Langkah pertama dari prosedur derivatisasi dimulai dengan penambahan 60 μLlarutan
larutan terkonsentrasi menggunakan evaporator hingga hampir 2 mL. Setelah dipanaskan O-methylhydroxylamine hidroklorida (MHA) (Sigma Aldrich, 1 mg / mL, di
prekonsentrasi dan perubahan pelarut diikuti langkah pemurnian.30 cm × Kromatografi
ACN). Reaksi senyawa karbonil dengan MHA berlangsung selama 60 menit pada 70 °C
kolom kaca1 cm digunakan. Kolom itu dikemas dengan 1 g natrium sulfat anhidrat dan 1 bak air. Langkah kedua meliputi metilasi asam karboksilat menjadi metil ester.
dalam
g silika gel (Sigma Aldrich ) . Awalnya dan sebelum pengambilan sampel kolom
Hal ini dicapai dengan menambahkan 12 μL dari (Trimethylsi- LYL) diazometana
diaktifkan dengan penambahan 10 mL heksana. Setelah ini sampel (hampir 2 mL)
(TMSD) (Acros Organics) dan 8 μLmetanol. Kemudian, vial dibiarkan dalam bak
ditempatkan di bagian atas kolom. Elusi dilakukan dengan menggunakan 2 mL heksana
(dalam rangkap dua dan setelah pembilasan labu evaporator berputar) dan kemudianultrasonik
10 selama 20 menit. Fol- melenguh ini, 245 μL dari N, O-bis (trimetilsilil) -
trifluoroacetamide (BSTFA) dengan 1% trimetilklorosilan (TMCS) (TCI Kimia) kami
mL campuran CH 2 Cl 2 : n-heksana 3: 2. Fraksi yang dielusi diuapkan di bawah aliran
nitrogen dan akhirnya disesuaikan menjadi 1 mL. menambahkan untuk mengubah gugus hidroksil dari spesies ke turunan eter
Mengenai paruh kedua filter, pra-perlakukan dan 3-langkah prosedur trimethylsilyl mereka . Selain itu, 50 μL dari dine pyri- ditambahkan. Reaksi dilakukan
dalam oven selama 60 menit pada 70 °C Setelah pendinginan sampai suhu kamar, 50
derivatisasi berikutnya berada di tempat lain ( Flores dan Doskey, 2015 ). Secara singkat
dan dengan sedikit modifikasi, filter diekstraksi 3 kali dengan 30 mL (1: Ldari 1) tetra cosane d-50 (Sigma Aldrich, 30 μg / mL, di DCM) ditambahkan ke setiap
diklorometana / metanol dalam rendaman ultrasonik selama 20 menit. Sebelum sampel sebagai standar internal. GC / MS (6890N / 5975B, Ag-ilent Technologies, USA)
ekstraksi, 5 μLasam ketopinic (KPA) (Sigma Aldrich, 5 μg
digunakan untuk kedua analisis. Instrumen GC dilengkapi dengan injektor split / splitless
/ mL, di MeOH)
ditambahkan sebagai standar pengganti. Juga 5 μL dan- kolom HP-5ms [5% - (fenil) -methylpolysiloxane] (Agilent J&W GC Column,
μL dari meso
dari KPA dan 5
Agilent Technologies, USA). Helium dengan kemurnian tinggi adalah gas pembawa
Erythritol (Sigma Aldrich, 5 μg / mL, di MeOH) yang ditambahkan sebagai standar
dengan kecepatan 1,5 mL / menit. Mode pulsed split-less digunakan untuk injeksi dan
pengganti dalam filter kosong untuk evaluasi pemulihan. Ekstrak gabungan disaring
suhu injektor diatur pada 280 °C.
melalui pipet Pasteur dan dipekatkan pada hampir 4 mL dengan rotary evaporator.
Untuk analisis PAH program suhu oven GC adalah: 65 °C (tahan malat, asam suberat, asam 3-hidroksiglutarat dan levoglucosan. Batas deteksi berkisar
selama 1 menit) hingga 320 °C pada 15 °C / menit dengan tahan isotermal akhir selama antara 0,16 ng / m 3 (asam suberat) hingga 0,62 ng / m 3 (asam palmitat) dan pemulihan
3 menit, sedangkan untuk spesies organik teroksigenasi adalah: 84 °C (tahan selama 1 bervariasi dari 68% (asam pinonat) hingga 127% (asam stearat).
menit) hingga 200 °C pada4 suhu°C / menit, tahan selama 2 menit, kemudian ke 300 Fragmen ionik yang digunakan dan waktu retensi senyawa autentik disajikan
°C pada 10 °C / menit dengan penahanan isotermal akhir selama 15 menit. Dalam pada Tabel S1 dan S2 . Pada Tabel S3 , data identifikasi senyawa dengan standar yang
kedua kasus, suhu sumber masuk dan MS280 °C dan 230 °masing-masingC. Mode tidak tersedia dan referensi terkait disajikan. Filter kosong diperlakukan sebagai sampel
pemantauan ion yang dipilih (SIM) digunakan untuk kuantifikasi analit. nyata menggunakan prosedur yang sama. Jika perlu, data dikoreksi dengan tepat untuk
Prosedur penentuan PAH divalidasi menggunakan Campuran bidang kosong tetapi tidak untuk pemulihan.
Hidrokarbon Aromatik Polynu Clear (Supelco), solusi standar dari senyawa yang diteliti Parameter meteorologi (T, RH) dan gas anorganik (O 3 , NO x dan SO 2 )
termasuk naphthalene (NAP), acenaphthylene (ACY), acenaphthene (ACE), fluoren diukur dari Biro Lingkungan Kota Aspropirgos, di stasiun yang sangat dekat dengan
(FLU), phenanthrene ( PHE), anthracene (ANTH), fluoranthene (FTL), pyrene (PYR), lokasi pengambilan sampel seperti yang dijelaskan oleh Mavrakis et al. (2008) .
chry- sene (CHR), benzo [a] antrasena (BaA), benzo [b, k] fluoranthenes (BbkF), benzo
[a] pirena (BaP), indeno [1,2,3 cd] pyrene (IPY),
dibenzo [a, h] anthracene (DBA) dan benzo [ghi] perylene (BPE). Batas deteksi (DL)1.3. Analisis statistik
dari PAH yang diteliti berkisar antara 0,0 0 02 (ANTH dan DBA) hingga 0,002 (FLT
3
dan PYR) ng / m . Pemulihan bervariasi dari 82% (FLU) hingga 117% (CHR). IBM SPSS statistics 24 digunakan untuk analisis statistik data. Uji Spearman
Sebagian besar senyawa organik teroksigenasi diidentifikasi dan diukur diterapkan untuk analisis korelasi, analisis komponen utama (PCA) untuk pembagian
sumber dan uji Mann Whitney untuk memeriksa kemungkinan perbedaan antara periode
menggunakan standar referensi yang tersedia. Secara khusus, asam karboksilat termasuk
pengambilan sampel. Perbedaan yang signifikan antara parameter yang diteliti
suksinat (diC4), glutarat (diC5), adipat (diC6), pimelic (diC7), suberic (diC8), azelaic
ditunjukkan dengan nilai p < 0,05 (tingkat kepercayaan 95%).
(diC9) dan asam sebacic (diC10), asam monokarboksilat termasuk laurat (C12), ), myris-
tic (C14), palmitic (C16), margaric (C17), stearic (C18), oleic (C18: 1) dan arachidic
(C20), asam aromatik termasuk benzoat (BEN), p-toluic (TOL) , phthalic (PHTHA),
2. Hasil dan diskusi
isophthalic (iPHTHA), terephthalic (tPHTHA) dan trimellitic (TRIM) telah dibeli dari
Sigma Aldrich. Pelacak SOA Pinene termasuk asam pinonat (PNA), asam 3-
hidroksiglutarat (3HGA) (Sigma Aldrich) dan asam pinat (PA) (Chiron). Pelacak SOA Konsentrasi PM 10 dan spesies organik yang diukur disajikan pada Tabel 1 ,
isoprena 2-methylerythritol (MTL1) dibeli dari Sigma Aldrich. Asam hidroksikarboksilat
sedangkan pada Gambar. 2 tren musiman PM 10 dan kelas senyawa organik
termasuk asam malat (MAL), sitrat (CIT) dan tartarat (TART) diperoleh dari ditampilkan.
TCI Perlu dicatat bahwa NAP, ACY dan ACE dikeluarkan dari hasil dan diskusi
Chemicals dan Sigma Aldrich. Akhirnya, levoglucosan (LEV) dan bisphenol A (BPA) karena terdeteksi dalam kurang dari 10% dari total sampel.
dibeli dari Sigma Aldrich. Terlepas dari senyawa yang disebutkan di atas, lima
komponen lain, yang standar otentik mereka tidak tersedia, diidentifikasi menggunakan
data MS dari literatur dan dengan bantuan perpustakaan NIST ( Mologousi dan Bakeas,2.1. PM 10 konsentrasi
2016 ). Kuantifikasi dilakukan menggunakan faktor respons GC / MS dari standar yang
tersedia. Sebagai contoh, 2-methylthreitol (MTL2), 2-methylglyceric acid (2MGA), 3-
PM 10 periode bervariasi konsentrasi diukur dalam seluruh sampel 8,5-129 μg / m
3
methyl-1,2,3-butanetricarboxylic acid (3MBTCA), 2- hydrohydglglutaric acid (2HGA)
dengan
dan mannosan (MAN) dikuantifikasi menggunakan faktor respons 2-metiltriritritol, asam nilai rata-rata
PG Kanellopoulos, E. Verouti dan E. Chrysochou et al. / Jurnal Ilmu Lingkungan 99 (2021) 222-238 225
Tabel 1 - Konsentrasi PM 10 ( μg / m 3 ), senyawa organik (ng / m 3 ), gas anorganik ( μg / m 3 ) dan parameter meteorologi ( T, RH) selama setiap periode sampling.
Spesies Autumn Summer Musim Dingin Musim Semi Semua Sampel (n = 56)
Rata-rata ± SD Rata-rata ± SD (kisaran)
3)
CPM 10 (μg / m 19,1 ± 8,2 58,6 ± 18,9 35,6 ± 16,1 76,3 ± 35,0 47,4 ± 30,6 (8,5-129) PAH (ng / m 3) FLU 0,004 ± 0,01 0,006 ± 0,005 0,02 ± 0,01 0,02 ± 0,02 0,01 ± 0,01 (BDL-
0.05) PHE 0,02 ± 0,01 0,07 ± 0,03 0,14 ± 0,08 0,04 ± 0,02 0,07 ± 0,06 (BDL-0.25) ANT ND 0,07 ± 0,007 0,04 ± 0,03 ND 0,03 ± 0,03 (BDL-0,08) FLT 0,01 ± 0,01 0,49 ± 0,28 0,34
± 0,17 0,15 ± 0,09 0,25 ± 0,25 (BDL-1,1) PYR 0,005 ± 0,006 0,53 ± 0,33 0,38 ± 0,22 0,14 ± 0,09 0,26 ± 0,28 (BDL-1.2) CHR 0,01 ± 0,02 2,6 ± 1,9 1,3 ± 1,2 0,37 ± 0,25 1,1 ± 1,5
(BDL-6,4) baa 0,12 ± 0,14 2,2 ± 1,3 1,7 ± 1,3 0,61 ± 0,40 1,2 ± 1,2 (BDL-4.4) BbkF 0.15 ± 0.13 6.1 ± 3.2 4.8 ± 2.9 1.9 ± 1.4 3.2 ± 3.2 (BDL-11.0) BaP 0.09 ± 0.12 3.6 ± 2.6 1.7 ±
1.5 0.43 ± 0.37 1.4 ± 2.0 (BDL-8.4) IPY 0.06 ± 0.05 2.1 ± 1.2 0.60 ± 0,33 0,45 ± 0,42 0,79 ± 1,0 (BDL-3,9) DBA 0,05 ± 0,06 0,47 ± 0,20 0,29 ± 0,17 0,12 ± 0,09 0,23 ± 0,21 (BDL-
0,88) BPE 0,08 ± 0,07 2,4 ± 1,2 1,8 ± 0 .95 0,75 ± 0,70 1.2 ± 1.2 (BDL-4.3)
PAH 0.60 ± 0.48 20.6 ± 11.8 13.0 ± 8.4 5.0 ± 3.6 9.8 ± 10.6 (0.01-41.1) 3
13 MCA (ng / m ) C12 5.6 ± 4.0 11.9 ± 3.1 7.3 ± 5,4 5,6 ± 4,1 7,6 ± 4,9 (0,50-17,9) C14 4,4 ± 3,1 16,2 ± 5,9
8,4 ± 3,3 6,4 ± 5,6 8,8 ± 6,4 (0,43-24,2) C16 43,0 ± 26,2 67,1 ± 23,8 62,4 ± 40,5 51,7 ± 33,8 56,0 ± 32,3 (8.5-166) C17 2.8 ± 1.2 6.7 ± 4.9 4.3 ± 3.5 3.1 ± 2.8 4.2 ± 3.4 (0.65-19.6)
C18 20.7 ± 14.8 26.8 ± 7.6 36.3 ± 22.2 20.3 ± 11.4 26.0 ± 16.0 (2.9-89.5) C18: 1 1.1 ± 0.74 5.5 ± 4.8 2.3 ± 1.3 5.2 ± 3.2 3.5 ± 3.4 (BDL-16.7) C20 1.4 ± 1.1 4.4 ± 2.4 2.8 ± 1.1 3.2
± 1.6 3.0 ± 1.9 (BDL-8.4)
3
MCA 78.9 ± 46.4 139 ± 40.6 123 ± 70.6 95.7 ± 53.0 109 ± 57.8 (25.9-297) DCA (ng / m ) diC4 37.0 ± 20.8 22.7 ± 13.3 15.4 ± 12.1 27.0 ± 12.0 25.5 ± 16.6 (4.7-85.4) diC5 12.0 ± 10.7
8.1 ± 3.4 7.1 ± 5.9 8,5 ± 3,5 8,9 ± 6,7 (2,2-43,4) diC6 24,1 ± 21,3 10,0 ± 4,8 10,2 ± 7,1 15,2 ± 7,8 14,9 ± 13,1 (3,1-83,0) diC7 5,8 ± 4,7 3,5 ± 3,4 2,9 ± 1,8 4,2 ± 3,5 4,1 ± 3,6 (0,69 -
16.5) diC8 6.2 ± 5.0 2.6 ± 1.9 2.1 ± 1.9 4.7 ± 2.6 3.9 ± 3.5 (BDL-19.1) diC9 25.9 ± 14.6 13.5 ± 7.7 9.7 ± 7.3 20.0 ± 13.0 17.2 ± 12.5 (0.98-55.1) diC10 3.7 ± 2.9 1.0 ± 1.0 0.97 ±
0.65 2.2 ± 0.81 2.0 ± 1.9 (BDL-10.7) LMWdca 73.2 ± 50.8 40.8 ± 20.2 32.7 ± 24.7 50.8 ± 22.7 49.4 ± 34.7 (10.3-212) HMWdca 41.6 ± 25.7 20.7 ± 12.5 15.7 ± 11.0 31.1 ± 17.8
27.3 ± 19.9 (2.4-101)
DCA 115 ± 75,1 61,5 ± 31,4 48,4 ± 34,0 81,9 ± 33,7 76,7 ± 52,4 (18,4-313) AA (ng / m 3) BEN 10,2 ± 6,3 4,6 ± 4,2 2,9 ± 2,3 7,2 ± 5,3 6,2 ± 5,4 (BDL-21,9) TOL 0,93 ± 0.62 2.0 ±
0.65 2.3 ± 1.7 1.4 ± 0.85 1.6 ± 1.1 (BDL-7.9) PHTHA 32.7 ± 22.2 23.1 ± 15.8 20.1 ± 15.8 29.3 ± 11.3 26.3 ± 17.0 (7.7-90.5) tPHTHA 20.0 ± 12.4 54.9 ± 27.7 42.2 ± 21.3 34.1 ±
32,5 37,7 ± 27,2 (1,9-118) iPHTHA 1,3 ± 0,93 4,6 ± 2,2 4,2 ± 1,9 2,6 ± 1,6 3,1 ± 2,1 (BDL-10,0) TRIM 5,1 ± 4,0 1,9 ± 1,1 1,4 ± 0,85 2,7 ± 0,98 2,8 ± 2,5 (0.52- 14.4)
3
AA 70.1 ± 29.9 91.1 ± 31.1 73.1 ± 35.5 77.2 ± 37.1 77.8 ± 33.6 (23.7-163) HCA (ng / m ) MAL 8.2 ± 3.1 2.1 ± 0.54 1.0 ± 1.0 2.4 ± 2.3 3.8 ± 3.6 (BD L-17.4) 2-HGA 2.9 ± 0.96 1.9 ±
0.89 1.1 ± 0.52 2.3 ± 0.71 2.0 ± 1.0 (0.31-4.6) TAR 1.7 ± 1.5 0.74 ± 1.2 0.77 ± 0.83 1.3 ± 1.3 1.0 ± 1.2 (BDL-5.8) CIT 3.1 ± 1.3 1.5 ± 0.78 0.85 ± 0.40 2.7 ± 0.34 2.0 ± 1.2 (BDL-
3
5.9) HCA 15.9 ± 5.4 5.9 ± 2.0 3.7 ± 1.8 8.8 ± 3.2 8.9 ± 5.9 (1.4-31.9) PSOA (ng / m ) PA 1.2 ± 0.62 0.47 ± 0.44 0.36 ± 0.31 0.89 ± 0.27 0.72 ± 0.53 (BDL-2.6) PNA 1.4 ± 0.97
0.67 ± 0.26 0.62 ± 0.38 1.1 ± 0.65 0.93 ± 0.69 (BDL-3.4) 3HGA 3.4 ± 1.3 2.1 ± 0.84 1.8 ± 1.1 2.1 ± 0,53 2,3 ± 1,1 (BDL-7.2) 3MBTCA 2,9 ± 0,87 1,8 ± 0,53 1,6 ± 0,48 2,3 ± 0,57
3
2,1 ± 0,83 (BDL-4,9) PSOA 8,8 ± 3,6 5,0 ± 1,8 4,4 ± 1,9 6,4 ± 1,9 6,1 ± 2,9 (0,61- 18.1) ISOA (ng / m ) MTL1 17.4 ± 10.2 3.1 ± 0.62 2.4 ± 0.91 8.1 ± 4.1 7.7 ± 8.1 (1.3-44.1)
MTL2 8.1 ± 3.7 1.3 ± 0.24 1.0 ± 0.35 3.4 ± 2.1 3.4 ± 3.5 (0.68-17.3 ) 2MGA 3.0 ± 0.88 1.7 ± 0.60 1.8 ± 1.3 2.3 ± 0.73 2.2 ± 1.0 (0.42-5.3)
3
ISOA 28.5 ± 14.7 6.1 ± 1.3 5.2 ± 2.1 13.7 ± 6.9 13.4 ± 12.3 (2.8-66.7) BSOA 37.3 ± 17.8 11.1 ± 2.3 9,5 ± 3,8 20,1 ± 6,9 19,5 ± 14,7 (4.1-80.6) BBT (ng / m ) LEV 50.9 ± 40.2
363 ± 237 330 ± 193 39.2 ± 28.9 196 ± 215 (2.8-861) MAN 5.6 ± 4.7 38.2 ± 37.1 31.6 ± 28.6 4.0 ± 2.9 20.0 ± 27.5 ( BDL-128) BBT 56.5 ± 44.3 401 ± 272 362 ± 219 43.2 ± 31.5
3
216 ± 241 (3.0-989) Senyawa lain (ng / m ) BPA 0,37 ± 0,29 3.1 ± 2,5 2,3 ± 1,7 0,97 ± 0,96 1,7 ± 1,9 (1,9 BDL-9.5) Parameter meteorologi dan gas anorganik T ( °C) 26.6 ±
3
2.0 12.5 ± 2.2 9.9 ± 2.3 17.2 ± 2.4 16.5 ± 6.8 RH (%) 51.7 ± 14.1 68.1 ± 3.5 66.9 ± 9.0 57.0 ± 8.0 60.8 ± 11.6 O 3 ( μg / m ) 53.7 ± 15.1 18.7 ± 7.6 21.2 ± 12.9 27.7 ± 9.9 30.3 ±
3
18.1 NO x ( μg / m 3 ) 60.0 ± 23.3 107 ± 59.7 97.7 ± 47.6 66.4 ± 22.6 83.022.5 83.0 ±± 70.5 SO 2 ( μg / m ) 6.0 ± 3.4 3.8 ± 2.5 7.3 ± 4.9 5.8 ± 1.8 5.7 ± 3.5
BbkF: Jumlah benzo [b] fluoranthene dan benzo [k] fluoranthene; ND: Tidak terdeteksi; BDL: Di bawah batas deteksi; BSOA: Jumlah SOA isoprene dan pelacak SOA pinene.
226 PG Kanellopoulos, E. Verouti dan E. Chrysochou et al. / Jurnal Ilmu Lingkungan 99 (2021) 222-238
Gambar. 2 - Tren musiman PM 10 ( μg / m 3 ) dan kelas senyawa organik (ng / m 3 ). Selanjutnya, ∗ mengacu pada outlier dan o mengacu pada nilai di atas kuartil ke-3.
47,4 ± 30,6 μg / m 3 ( Tabel 1 ). Seperti yang jelas dari Gambar 2 , konsentrasi

Yin et al., 2014 ; Xu et al., 2017 ), sebanding dengan 49.2 ± 7.2 μg / m 3 yang diukur di
terendah diamati selama musim panas sementara levelnya meningkat secara signifikan (
Limassol, Siprus ( Pikridas et al., 2018 ) dan dengan 48 μg / m 3 dilaporkan di
p < 0,05) selama musim gugur. Konsentrasi PM rata-rata tertinggi diukur selama musim
Barcelona, Spanyol ( Pérez et al., 2008 ) dan lebih tinggi dari 27,0 μg / m 3 yang diukur di
semi (76,3 ± 35,0 μg / m ) dan dapat dijelaskan dari peristiwa pengangkutan debu yang
3
Elche, Spanyol ( Galindo et al., 2019 ), 39 μg / m 3 dilaporkan di Bern, Swiss (
terjadi selama setengah hari dari periode pengambilan sampel. Peristiwa debu seperti itu
Barmpadimos et al., 2011 ) dan 25,7 μg / m 3 diukur di lokasi perkotaan di Rotterdam,
biasa terjadi di wilayah Mediterania Timur dan mempengaruhi tingkat PM 10 di banyak
kota tanpa memandang musim ( Pikridas et al., 2018 ). Curah hujan musim dingin dapatBelanda ( Keuken et al., 2011 ). Di Yunani,PMrata-rata yang lebih tinggi 10
konsentrasitelah diamati di lokasi industri-perkotaan di Thessaloniki selama musim
menjelaskan penurunanPM 10 batas konsentrasi harian50 μg / m selama periode musim
3
dingin dan periode akhir (masing-masing 69 dan 58 μg / m 3 ) ( Terzi et al., 2010 ).

dingin. Mengenai ( EU, 2008/50 / EC), 23 pelanggaran diamati (41% dari total sampel)
dari musim gugur ke musim semi. Tidak ada pelanggaran diamati selama musim panas.
Dalam Eleusis, yang dekat dengan lokasi pengambilan sampel penelitian ini,PM 10
konsentrasi
Tingkat PMrata-rata yang dicatat dalam penelitian ini dibandingkan
10
dengan kota-kota lain di dunia dan ditemukan lebih rendah daripada yang dilaporkan di ditemukan sama dengan 67,7 μg / m dari Januari 2005-Maret 2006 ( Razos dan
3
Wuhan (122 ± 75 μg / m ) dan Chengdu (kisaran antara 85-166 μg / m ) dari Cina ( Christides, 2010 ) tetapi sekitar satu dekade kemudian nilai berkurang menjadi 39 dan 40
3 3
μg / m 3 masing-masing untuk tahun 2016 dan 2017 ( Koukoulakis et al., 2019 ). PAHLebihdengan berat molekul lebih tinggi ini dapat dijelaskan oleh peningkatan volatilitas
PAH dengan berat molekul rendah dan menengah yang menghasilkan partisi antara fase
rendah PM 10 konsentrasi telah diamati di situs industri Volos sama untuk 31 dan 33 μ
3
gas dan partikel ( Jamhari et al., 2014 ). Persentase tersebut sering menunjukkan proses
m selama kampanye dua tahun (Manoliet al., 2017). suhu tinggi sebagai sumber ( Tobiszewski dan Namie ́snik, 2012 ). Jumlah BbkF adalah
konstituen paling banyak dari PAH dengan konsentrasi rata-rata 3,2 ± 3,2 ng / m 3
2.2. Hidrokarbon aromatik polisiklik (PAH) selama periode sampel keseluruhan memberikan kontribusi hingga 38,4% dari total PAH
( Gambar 3 ). BbF juga merupakan PAH yang paling melimpah di kota Brasil, Sao
PAH merupakan kelompok besar senyawa organik yang dihasilkan dari pembakaran zat- menyumbang 12% dari total PM 10- PAH yang terikat ( Pereira et al., 2017 ), di
Paulo,
zat berkarbon yang tidak lengkap. Meskipun PAH dapat dipancarkan secara alami ke India, selama periode musim dingin ( Fu et al. , 2010 ) while BbkF accounted
Chennai,
atmosfer, sumber yang dominan adalah kegiatan antropogenik, dengan banyak sumber for approximately 20% of the total PAH in 3 site in Tangshan ( Shi et al., 2009 ). In our
terpisah berkontribusi terhadap total konsentrasi PAH, termasuk pemanasan domestik,
study, BaP was the second most abundant PAH with concentrations vary- ing from BDL
emisi kendaraan, kilang, pembangkit listrik, pembakaran sampah yang tidak terkendali, 3
to 8.4 ng/m contributing from 8.7% to 17.5% of the total PAH concentrations ( Fig. 3 ),
kecelakaan. kebakaran, merokok dll. ( Mantis et al., 20 05 ; Srogi, 20 07 ; Katsoyiannis 3
et al., 2011 ). PAH adalah masalah besar karena lingkungan mereka di mana-mana withdanthe highest average concentration measured during autumn (3.6 ± 2.6 ng/m ).
BaP levels are considered relatively high taking into account the annual average target
efek buruknya terhadap kesehatan manusia ( Kim et al., 2013 ; dan referensi di dalam).
3
Khususnya, baru-baru ini, BaP telah diklasifikasikan oleh IARC sebagai karsinogen value
bagi of PM 10 -bound BaP (1 ng/m ) according to the 4th Daughter Directive
(Directive, 20 04/107/EC) ( EC, 20 05 ). BaP levels presented in this work are among the
manusia ( IARC, 2012 ). Dalam pekerjaan ini, konsentrasi bervariasi dari 0,01 hingga
41,1 ng / m 3 , selama 13 periode pengambilan sampelPAH keseluruhan, dengan highest
nilai reported for Greek cities. For example, in Thessaloniki, average values for cold
3 and warm period were 0.12 ± 0.11 and 0.86 ± 0.43, respectively
median 9,8 ng / m ( Tabel 1 ) yang lebih tinggi daripada yang dihitung pada Eleusis (
Source estimation of PAH emissions can be achieved through molecular
PAH = 7,9 ng / m 3 ) ( Mantis et al., 2005 ) dan kota-kota Yunani lainnya seperti, Volosdiagnostic
( ratios (DRs) analysis. However, ratios should be used with caution as PAH
3
12 PAH = 3.34 dan 6.46 ng / m ) ( Manoli et al., 2017 ), Spata ( 14 PAH = 3.08 ng / m components may differ in reactivity and atmospheric residence times ( Katsoyiannis et
al., 2011 ). Table 2 shows the selected DRs calculated for each season and for the whole
dan Koropi ( 14 PAH = 3,21 ng / m 3 ) ( Vasilakos et al., 2007 ) tetapi secara signifikan
period. The ratio of COMBPAH/ PAH reveals combustion sources when close to 1 (
lebih rendah daripada yang dilaporkan
Ravindra et al., 2008 ). In this study the average ratio was 0.91 ± 0.07 with a decreasing
trend during summer suggesting strong pyrogenic source contributions. The average
FLT/(FLT + PYR) ratio was found to be 0.55 during the whole sampling period
indicating pyrogenic emissions ( Katsoyiannis et al., 2011 ). Particularly, during summer
and spring the ratio exceeded the value of 0.5 revealing grass/wood/coal combustion.
During the cold months, values were 0.49 for autumn and 0.48 for winter suggesting
influences from fossil fuel combus- tions. However, ratios were very close to 0.5 which
shows mixed combustion sources ( De La Torre-Roche et al., 2009 ). The ratio of
BaA/(BaA + CHR) was measured over 0.35 during the entire sampling campaign
which shows the clear dominance of pyrogenic sources ( Katsoyiannis et al., 2011 ).
Same pyrogenic sources were also indicated from the IPY/(IPY + BPE) ratio which was
in the range of 0.2–0.5 which attributes to petroleum combustion ( Yunker et al., 2002 ).
The ratio of ANT/(ANT + PHE) was calculated only for the cold months (0.51 and 0.23
for autumn and winter, respectively) and found over 0.1 which reflects pyrogenic
sources. ANT was found below detection limits during the warm months; thus, the latter
ratio wasn't calculated. In addition, ANT experiences faster photodegradation than PHE
and therefore has different chemical behavior ( Czaplicka et al., 2019 ). The above ratios
mostly attribute to combustion sources of various materials although petrochem- ical
activities are present near the sampling area. The DRs presented here are parallel with
those reported for other Greek cities ( Mantis et al., 2005 ) which also suggest effects
from pyrogenic sources, however seasonal variability wasn't observed in this work which
highlights the serious influence of combustion processes.
Gambar. 3 -- Ratarata profil PAH selama setiap periode sampling.
2.2.1. PAH health implications

The aerosol carcinogenicity can be quantified by applying the Benzo[a]pyrene-
di Tianjin dan Tangshan ( 14 PAH = 116 dan 17 PAH = 244 ng / m , masing-masing) ( equivalent carcinogenic power (BaPE) parameter. This parameter refers to all
3
3
Shi et al., 2009 , 2010 ). Variasi musiman diamati dengan konsentrasi rata-rata tertinggi carcinogenic PAH instead of BaP alone with values over 1.0 ng/m indicate an increased
3
yang diukur selama periode musim gugur (20,6 ± 11,8 ng / m ) dan terendah selama cancer risk ( Pereira et al., 2017 ). BaP equivalent (BaPE) is calculated using the
3 following equation Eq. (1) ( Yassaa et al., 2001 ; Vasconcellos et al., 2011 ):
musim panas (0,60 ± 0,48 ng / m ). Setiap PAH menunjukkan konsentrasi yang lebih
tinggi secara signifikan ( p < 0,05) selama periode dingin (musim gugur dan musim BaPE = ( [ BaA ] × 0 . 06 ) + ( [ BbkF ] ) × 0 . 07) + ( [ BaP ] × 1 ) + ( [ DBA ]
dingin) daripada selama periode hangat (musim semi dan musim panas) dengan
konsentrasi PAH rata-rata enam kali lebih tinggi selama periode dingin (16,8 ± 10,8 ×0 . 6 + ( [ IPY ] × 0 . 08 ) (1)
dibandingkan 2,8 ± 3,4 ng / m 3 ). Perbedaan seperti itu dapat dijelaskan oleh sumber
BaPE average seasonal values were respectively equal to 0.14 ± 0.15, 4.6 ± 3.0,
emisi langsung yang diperluas (pembakaran bahan bakar fosil, pembakaran biomassa, 3
2.3 ± 1.8, 0.71 ± 0.57 ng/m for summer, autumn, winter and spring. Temporal
dll.) Dan dengan peningkatan kondensasi PAH dalam aerosol karena suhu yang lebih
rendah ( Pereira et al., 2017 ). Selain itu, peningkatan radiasi matahari musim panas dan variations of BaPE are shown in Fig. 4 . About 46.4% of BaPE values exceeded the
3
oksidan atmosfer mendukung degradasi PAH ( Finardi et al., 2017 ). Variasi serupa telah described limit of 1 ng/m , while 100% of autumn and 71.4% of winter values exceeded
diamati dalam penelitian lain ( Brown et al., 2013 ; Manoli et al., 2017 ; Pereira et al., the above limit showing the severe impacts of primary emissions during the cold months.
2017 ; Finardi et al., 2017 ). Seperti yang jelas dari ( Gbr. 3 ), 5-6 cincin PAH adalah However, during summer no threshold exceedances were observed during summer.
spesies yang paling melimpah terhitung untuk 64% -72% dari PAH. Kelimpahan tinggi
The carcinogenic and mutagenic potential of particle bound- PAH (BaP-TEQ
and BaP-MEQ) can be estimated through the follow-
PG Kanellopoulos, E. Verouti and E. Chrysochou et al. / Journal of Environmental Sciences 99 (2021) 222–238 227
( Manoli et al., 2016 ). In the harbor of Volos, during 2015, BaP was calculated at 0.60 ±
0.98 ng/m 3 ( Manoli et al., 2017 ) while in Eleusis, mean concentration was 0.71 ng/m 3
(November 2001–June 2002 ) ( Mantis et al., 2005 ). Comparable BaP levels were
calculated in an urban site of Riyadh, Saudi Arabia (3.19 ng/m 3 ) ( Bian et al., 2016 ) but
much higher concentrations were measured in Donghe, China during a 4-season
3
campaign with average concentrations of 6.2, 17.0, 11.6 and 1.5 ng/m during autumn,
winter, spring and summer, respectively ( Wang et al., 2011 ).
228 PG Kanellopoulos, E. Verouti and E. Chrysochou et al. / Journal of Environmental Sciences 99 (2021) 222–238
Table 2 – Mean diagnostic ratios of selected PAH during each season and for the entire sampling period.
Ratio Summer Autumn Winter Spring All samples
COMBPAH/ PAH 0.81 ± 0.18 0.93 ± 0.01 0.92 ± 0.03 0.94 ± 0.02 0.91 ± 0.07 FLT/(FLT + PYR) 0.70 ± 0.23 0.49 ± 0.03 0.48 ± 0.03 0.52 ± 0.03 0.55 ±
0.14 BaA/(BaA + CHR) 0.90 ± 0.19 0.49 ± 0.06 0.58 ± 0.05 0.62 ± 0.11 0.65 ± 0.19 IPY/(IPY + BPE) 0.39 ± 0.21 0.45 ± 0.07
0.26 ± 0.04 0.38 ± 0.05 0.37 ± 0.13 ANT/(ANT + PHE) ∗ - 0.51 ± 0.09 0.23 ± 0.23 - 0.37 ± 0.22
COMBPAH: Sum of FLT + PYR + BaA + CHR + BbkF + BaP + IPY + BPE ∗ This ratio was calculated only for the two seasons as
ANT was found below detection limits during summer and spring.
Fig. 4 – Temporal variations of BaPE (ng/m 3 ).
ing Eqs. (2) and (3) ( Jung et al., 2010 ; Pereira et al., 2017 ):
( BaP − TEQ ) = ( [ BaA ] × 0 . 1 ) + ( [ Chr ] × 0 . 01 ) + ( [ BbkF ] × 0 . 1 )

+ ( [ BaP ] × 1 ) + ( [ IPY ] × 0 . 1 ) + ( [ DBA ] × 5 ) + (
[ BPE ] × 0 . 01 ) (2)
( BaP − MEQ ) = ( [ BaA ] × 0 . 082 ) + ( [ Chr ] × 0 . 017 ) + ( [ BbF ] × 0 . 25 )BaP-TEQ with highest average values during autumn (5.7 ± 3.7 ng/m 3 ) and winter (2.9
+ ( [ BkF ] × 0 . 11 ) + ( [ BaP ] × 1 ) + ( [ IPY ] × 0 . 31 + ( 2.1 ng/m 3 ). As it is clear, the carcinogenic and mutagenic potencies of the aerosols are
drastically increased during the colder months.
[ DBA ] × 0 . 29 ) + ( [ BPE ] × 0 . 19 ) (3)
It should be noted that as separation of BbK and BfK couldn't2.3.

beMonocarboxylic acids (MCA)
achieved, BbkF was calculated with the coefficient of BkF, as a result ( BaP − MEQ ) is
slightly underestimated. DBA was the highest contributor to the total Bap-TEQ Monocarboxylic acids consist a group of compounds, known also as
measured (approximately 42%), followed by BAP (approximately 39%), whereas BAP- fatty acids, with numerous primary emissions sources. These sources can be both natural
MEQ was mainly contributed by BAP (51%) which is in agreement with and theanthropogenic such as biomass burning, fossil fuel combustion, vehicular exhaust,
contributions described by ( Pereira et al., 2017 ). BaP-TEQ values are illustrated in vege-
Fig. tative emissions and cooking ( Schauer et al., 1999 ; Fraser et al., 2003 ; Rogge et
5 and their seasonal average values were 0.36 ± 0.35, 7.0 ± 3.9, 3.8 ± 2.4 and 1.3 ±al., 1.02006 ; Oliveira et al., 2007 ; Guo et al.,
for summer, autumn, winter and spring, respectively. Significant increase of BaP- TEQ Fig. 5 – Carcinogenic (BaP-TEQ, ng/m 3 ) and mutagenic (BaP-MEQ, ng/m 3 ) potency of PM
10 during each
values have also been observed in Thessaloniki, Greece, but they were much lower (1.5
and 1.4 ng/m ) than those presented in this study ( Manoli et al., 2016 ). Different sampling period.
3
seasonal patterns were observed in Venice-Mestre, Italy where highest values were
3 3 3
found in winter (3.6 ng/m ) followed by spring (2.8 ng/m ) and autumn (1.7 ng/m ) (
2015 ; Ho et al., 2015 ). Total measured MCA ranged from 25.9 to 297 ng/m 3 , with the
Masiol et al., 2012 ). BaP-MEQ values showed parallel seasonal trends with those of
3 MCA
highest average concentration observed during autumn (139 ± 40.6 ng/m ) ( Table 2 concentrations reported in this study are much lower compared to other urban
3 3
sites, eg 137–3306 ng/m in Beijing, 40.5–1448 ng/m in Chennai, although more
Fig. 2 ). Concentra- tions remained on the same levels also during wintertime but were
significantly ( p < 0.05) decreased during spring and especially summer (78.9 ± monocarboxylic
46.4 acids were quantified ( Fu et al., 2010 ; Ren et al., 2016 ). Comparable
3
ng/m ) indicating that anthropogenic emissions are more important contributors to were observed in Morogoro, Tanzania during wet (102.0 ± 43.8 ng/m 3 ) and dry
levels
aerosol MCA than biogenic ones. Differently, in Chennai of tropical India, MCA seasons
pre- (117.2 ± 72.4 ng/m 3 ) ( Mkoma and Kawamura, 2013 ). Source estimation can
sented higher concentrations during summer due to microbial sources which beare achieved by calculating the ratio of C18/C16. Values lower than 0.25 are attributed to
increased with higher temperature and humidity ( Fu et al., 2010 ). However, in smoke, foliar vegetation combustion and waxy leaf surface abrasions; ratios
wood
Beijing, China MCA showed similar seasonal trends with highest average between 0.25–0.5 are achieved for traffic emissions, such as car/diesels truck exhausts
concentrations observed during the cold seasons ( Huang et al., 2006 ). The most while values in the interval 0.5–1 refer to paved/unpaved road dust and cooking (
abundant MCA component was C16, followed by C18 in each of the sampling periods. Rogge et al., 2006 ; Ren et al., 2016 ). The ratio of C18/C16 in our study presented aver-
This finding is consistent with most studies that also refer to the C16 predominance
age (value of 0.45, 0.41, 0.57 and 0.41 for summer, autumn, winter
Oliveira et al., 2007 ; Fu et al., 2010 ; Mkoma and Kawamura, 2013 ; Guo et al., 2015
Table 3 – Diagnostic ratios of selected carboxylic acids, biogenic secondary organic aerosol compounds and biomass burning tracers.
Ratio Summer Autumn Winter Spring All samples
C18/C16 0.45 ± 0.10 0.41 ± 0.05 0.57 ± 0.09 0.41 ± 0.08 0.46 ± 0.11 C18:1/C18 0.08 ± 0.07 0.21 ± 0.19 0.11 ± 0.15 0.37 ± 0.31
0.19 ± 0.23 diC6/diC9 0.85 ± 0.27 0.89 ± 0.42 1.8 ± 1.9 0.94 ± 0.47 1.1 ± 1.1 PHTHA/diC9 1.5 ± 1.3 1.9 ± 0.88 3.2 ± 2.7 2.0 ±
1.3 2.2 ± 1.8 MAL/diC4 0.25 ± 0.09 0.11 ± 0.06 0.06 ± 0.03 0.08 ± 0.05 0.14 ± 0.10 (PA + PNA)/3MBTCA 0.84 ± 0.28 0.63 ±
0.28 0.77 ± 0.55 0.79 ± 0.20 0.76 ± 0.35 MLT1/MTL2 2.1 ± 0.28 2.5 ± 0.27 2.2 ± 0.37 2.5 ± 0.57 2.3 ± 0.42 (MTLs)/2MGA 8.1
± 2.5 2.8 ± 0.72 2.7 ± 1.9 4.8 ± 1.6 4.6 ± 2.8 LEV/MAN 10.1 ± 3.4 12.1 ± 8.3 15.1 ± 11.1 10.0 ± 1.6 11.8 ± 7.3
MTLs = MTL1 + MTL2
and spring respectively ( Table 3 ), suggesting vehicle emissions appear to be the main
MCA contributor. The ratio of C18:1/C18 is often used to determine aerosol aging
levels, with lower value corresponding to more aged aerosols ( Cao et al., 2017 ). The
double bond in the C18:1 molecule increases its reactivity with the atmospheric oxidants,
such as O 3 and OH radicals, compared to stearic acid ( Deshmukh et al., 2019 ). The
seasonal average ratios are shown in Table 3 . It is clear that the ratio is increased when
direct emissions are more intense, during autumn and winter. However, the highest
average ratio was observed during spring (0.37 ± 0.31), possibly due to the dust
transports events which loaded the aerosols with fresh particles from soil and/or road
suspension. Similar finding has been reported recently, in New Delhi, where C18:1/C18
ratios reached their maximum concentrations during dust storm events ( Kang et al.,
2016 ).
2.4. Dicarboxylic acids (DCA)
Dicarboxylic acids consist a group of compounds with abound- eting al., 2015 ) but in Vavihill, Sweeden only the C7-C9 DCA presented parallel variation
presence, which have been detected in urban, suburban, rural, remote marine and Arctic
( Hyder et al., 2012 ). However, in two sites of Hong Kong (urban/roadside and rural)
aerosols ( Legrand et al., 2007 ; Ho et al., 2011 ; Fu et al., 2013 ; Mkoma wintertime and values of DCA were significantly higher than those of summer ( Ho et al.,
Kawamura, 2013 ; Pietrogrande et al., 2014 ). Their increased polarities, low-vapor 2011 ).
pressures and hygroscopic properties make DCA act as cloud condensation nuclei (CCN) Fig. 6 – Mean DCA profile during each sampling season.
and thus affect the global climate ( Kawamura and Bikkina, 2016 , and references
therein). Moreover, effects on human health due to short- and long-term exposure to
DCA have been reported. These include eye,nose and skin irrita- tion, asthma and lung
damage ( Parmar, 2014 ). DCA origin can be both primary and secondary. Biomass and In Fig. 6 the mean DCA profile during each sampling period is presented.
plastic enriched waste burning appear to significantly increase DCA levels of the atmo- Succicic acid was the most abundant followed by azelaic and adipic acids. In most
sphere ( Kumar et al., 2015 ; Cao et al., 2017 ), while many secondary sources are studies, succinic acid has been reported as the most abundant DCA, such as in two sites
reported. In particular, DCA from 4 to 7 carbon numbers are formed by the oxidation of Po Valley, Italy, in six 6 of Pearl Delta River, China, in two sites of Oporto, Portugal
of anthropogenic and biogenic olefins, such as cyclopentene, cyclohexene, cycloheptene, and Copenhagen, Denmark ( Oliveira et al., 2007 ; Pietrogrande et al., 2014 ; Zhao et al.,
2014 ). On the other hand, in Chengdu and Vavihill azelaic acid was the most abundant
1-methylcyclohexe, α/ β-farnesene, limonene etc ( Gao et al., 2004 ; Rossignol et al.,
( Hyder et al., 2012 ; Yin et al., 2014 ). It is worth noting that from the latter comparison
2012 ; Jaoui et al., 2017 ). Higher homologues of DCA ie from C8-C10 are the oxidation
oxalic acid is excluded as it is by far the dominant DCA ( Kawamura and Bikkina, 2016
product of unsaturated fatty acids such as palmitoleic, oleic and linoleic ( Stephanou and
), but not included in this work or the mentioned ones. Generally, in this sudy, low
Strati- gakis, 1993 ). Another possible formation source of lower molecular weight DCA
molecular weight DCA (C4-C6) accounted from more than 60% of the total DCA in
can be the photooxidation of their higher homologues ( Yang et al., 2008a
each season. An increase in the relative abundance of higher molecular wight DCA (C7-
3
Concentrations of DCA in this work, varied from 18.4 to 313 ng/m ( Table 2 C10) was observed during spring propably due to the increase of its precursors such as
Significant increase from cold to warm months have been observed indicating that the oleic acid. The ratios of diC6/diC9 and PHTHA/diC9 can be used to estimate the
increase of temperature and solar radiation, that enhance the atmospheric photochemical impact of anthropogenic versus biogenic sources to the aerosols. The higher the values,
reactions, may have an impact on their formation ( Fig. 2 ). Same seasonal trends were the more aerosols are affected by anthropogenic activities ( Ho et al., 2006 ; Guo et al.,
also reported for each individual DCA at three industrial sites in Wuhan, China ( Guo 2015 ). Values for diC6/diC9 and PHTHA/diC9 were calculated equal to 1.1 ± 1.1 and
lower levels (0.58) but PHTHA/diC9 was very close to the ratio reported in this work
2.2 ± 1.8 for the entire period ( Table 3 ) which are more than 2 times higher than those
measured in an urban/background site of Bologna, Italy (0.29 ± 0.09 and 0.87 ± (2.16) ( Zhang et al., 2010 ) but in Philadel- phia, USA higher values were calculated,
respectively) ( Pietrogrande et al., 2014 ). In Mainz, Germany, diC6/diC9 was found 1.8atfor diC6/diC9 and 3.2 for PHTHA/diC9 ( Ray and Mcdow, 2005 ). Both ratios pre-
sented their highest average values during winter (1.8 and 3.2,
Fig. 7 – Scatter plot of diC4/diC6 ratio and the diC4 relative abundance (RdiC4 %).
respectively) and their lowest during summer (0.85 and 1.5, respectively) indicating 3
tPHTHA being the most abundant (37.7 ± 27.2 ng/m ), phthalic acid, though, was
that aerosols are mostly affected by anthropogenic sources, especially during winter, 3
dominant during summer (32.7 ± 22.2 ng/m ). As it is clear from Fig. 2 , no seasonal
but during summer an increase of biogenic influence can be observed. Same summer-to-
Fig. 8 – Seasonal trends for the individual aromatic acids.
winter increasing trend was also observed in Wuhan ( Guo et al., 2015 ). It has also been
suggested that the photochemical oxidation of high molecular weight dicarboxylic
acids leads to the formation of their lower homologues, with diC4 and diC5 being the
dominant intermediates ( Yang et al., 2008b ). Moreover, according to Bikkina et al. variations were observed indicating different sources among the individual compounds.
(2015) the significant positive correlation between the relative abundance of diC4 and In Fig. 8 , seasonal concentrations of each individual aromatic acid are presented. BEN,
the ratio of diC4/diC6 reveals the photochemical oxidation of higher homologues as PHTHA and TRIM show significant increase in their concentrations during the seasons
another possible source of succinic acid ( Bikkina et al., 2015 ). Such a relationship with more intense solar radiation and higher temperatures, ie Cwinter < Cautumn <
can be extracted, in this study, from the significant strong correlation ( r = 0.73, p < Cspring < Csummer, revealing secondary sources. On the other hand, TOL, tPHTHA
0.05) between diC4/diC6 and RdiC4 ( Fig. 7 ). Thus, a possible formation source is and iPHTHA presented opposite variations with highest average concentrations during
indicated. autumn and lowest during summer indicating their primary sources as direct sources
were enhanced during autumn. AA have presented different seasonal trends according to
the available literature. For example, in Huangshi, China PHTHA and tPHTHA reached
2.5. Aromatic acids (AA) their highest average concentrations during summer and lowest during winter, whereas
iPHTHA was more abundant during autumn but was drastically decreased during winter
As far as AA, 2 monocarboxylic aromatic acids (BEN and TOL), 3 ( Liu et al., 2019 ). Moreover, in Guangzhou (urban) and Hok Tsui (rural) BEN and
dicarboxylic aromatic acids (PHTHA, iPHTHA and tPH- THA) and one tricarboxylic PHTHA were significantly higher during the warm period whereas tPHTHA and
aromatic acid (TRIM) have been detected. Aromatic acids originate from multiple iPHTHA exhibited increased concentration during the cold period which is parallel with
direct and secondary sources ( He et al., 2018 ). In particular, phthalic acid is con- this work's findings ( Ho et al., 2011 ). A 7-fold and a 2-fold increase for PHTHA and
sidered as an oxidation product of naphthalene, its methyl analogs and anthracene ( iPHTHA, during the summer time, were observed in Nainital, India, when at the same
Kleindienst et al., 2012 ; He et al., 2018 ). Fur- thermore, phthalic acid was proposed as time tPHTHA showed lower concentrations ( Hegde and Kawamura, 2012 ). In
a phthalate ester, such as di-2-ethylhexylphthalte, photooxidation product ( Kumar et al., Chennai, India, wintertime aerosols were more abundant with AA than those of
2015 ), while recently it was proposed as candidate tracer of anthropogenic SOA ( Al- summertime, as each individual AA, showed higher concentration including BEN, TOL
Naiema and Stone, 2017 ). However, primary sources such as biomass and/or plastic and the 3 PHTHA isomers ( Fu et al., 2010 ). Although there is limited data about
burning and motor exhaust have been reported ( Kawamura and Kaplan, 1987 ; Mkoma seasonal concentrations of TRIM, He et al. (2018) reported the highest mean
and Kawamura, 2013 ; Balla et al., 2018 ). Terephthalic acid has been suggested as a concentration during the fall due to stronger atmospheric oxidation activities than in
good tracer for plastic waste burning fresh particles ( Kumar et al., 2015 ) whereas other seasons ( He et al., 2018 ). By seasonality, AA have been separated in two groups.
regarding isophthalic acid correlations with both primary and secondary aerosol tracers BEN, PHTHA and TRIM were strongly and significantly correlated with each other ( r =
have been reported ( Al-Naiema and Stone, 2017 ). Benzoic acid has mostly secondary 0.72–0.80, p < 0.01) ( Table S4 ) suggesting same origin such as secondary formation,
sources including the photodegradation of volatile aromatic compounds such as toluene ( whereas corresponding correlations between iPHTHA, tPHTHA and TOL ranged from
Huang et al., 2012 ; Ho et al., 2015 ) although older studies have proposed primary 0.65 to 0.90 confirming possible common sources.
sources as well ( Kawamura et al., 1985 ). Trimellitic acid (1,2,4-Benzenetricarboxylic In Greece, data is limited about PM bound aromatic acids. In Thessaloniki,
acid) is considered as PAH oxidation product, but more laboratory experiments and field phthalic acid concentrations were higher than those of this study, ranging from 34–380
studies are needed to support this hypothesis ( He et al., 2018 ). 3
ng/m with significant increase during the cold period. Also, association with biomass
3
In this research, AA varied from 23.7 to 163 ng/m ( Table 3 ) with burning was observed ( Balla et al., 2018 ).
2.6. Biogenic secondary organic aerosol (BSOA) tracers

Seven compounds which are oxidation products of BVOCs, such as αnormalization
/β of these results it was clearly observed that the reduction of this ratio was
pinene and isoprene have been studied. Pinene ozonolysis products include ring-
such times higher for NO x values higher than 50 μg/m 3 than the ratio
containing compounds, such as pinonic and pinic acids, and ring-opened products, four
as 3-hydroxyglutaric and 3-methyl-1,2,3-butanetricarboxylic acids ( Jaoui et al., 2005
Fig. 9 – Scatter plot between NO x concentrations ( μg/m 3 ) and the MTLs/2MGA ratio.
Claeys et al., 2007 ; Eddingsaas et al., 2012 ). Pinic and pinonic acids are considered
fresh pinene-SOA compounds as they are produced mostly under low NO x conditions (
Eddingsaas et al., 2012 ). 3-Hydroxyglutaric and 3-methyl-1,2,3-butanetricarboxylic
acids are treated as aged pinene-SOA products as they are formed under high-NOx and observed for lower NO x values. Similarly, in a mountainous forest area, MTLs/MGA
intense radiation conditions after long-time aging ( Claeys et al., 2007 ; Szmigielski et ratio showed the highest value in summer and the lowest in fall-winter even if the NO
x
al., 2007 a). Isoprene oxidation products include 2-methylerythritol, 2-methylthreitol
and 2- methylglyceric acid ( Surratt et al., 2006 ). Isoprene reacts with atmospheric O were significantly lower than those of our study ( Hong et al., 2019 ).
producing a group of reactive intermediates called isoprene epoxydiols (IEPOX) ( Paulot Among PSOA, 3HGA exhibited the highest concentrations, with a mean value
et al., 2009 ). IEPOX partition mostly in the gas phase and through heterogenous reaction 3 3
of 2.3 ± 1.1 ng/m , followed by 3MBTCA (2.1 ± 0.83 ng/m ), PNA (0.93 ± 0.68 ng/m
on the surface of neutral and/or acidic particles produce SOA compounds, such as the 3 3
aforementioned 2-mehtyltetrols ( Surratt et al., 2010 ). On the contrary, 2-methylglyceric ) while the least abundant was PA (0.72 ± 0.53 ng/m ). The dominance of 3HGA and
3MBTCA has been already discussed in urban, rural and mountain sites ( Hu and Yu,
acid produced at rich NO x atmospheres by photooxidation of methacrolein, a gas phase
2013 ; Yuan et al., 2018 ; Hong et al., 2019 ) however in other studies pinonic and
first- generation product of isoprene's oxidation ( Surratt et al. 2006 ). ISOA were more
norpinic acids were the most abundant ( Li et al., 2013 ; Li et al., 2018b ). As already
3
abundant than PSOA, in this study, with concentrations ranging from 2.8–66.7 ng/m mentioned, PA and PNA are first generation PSOA, thus the ratio of (PA +
with a mean value of 13.4 ± 12.3 ng/m 3 , whereas PSOA varied from 0.62 to 18.1 ng/m PNA)/3MBTCA is indicative of fresh versus photochemically processed atmospheric
with an average of 6.1 ± 2.9 ng/m ( Table 1 ). Both compounds classes showed PSOA ( Deshmukh et al., 2019 ). Values presented in this work are on the same levels
3
during each sampling period and each of them is < 1.51 suggesting aged PSOA aerosols
seasonal variations ( Fig. 2 ), with significant ( p < 0.05) increase during spring and
during the entire season ( Yuan et al., 2018 ). The slight increase during summer is
summer. Particularly, summertime concentrations were approximately 5.5 and 2-fold
higher than those of wintertime for ISOA and PSOA respectively. Such increase can be caused probably due to the enhanced pinene emission, lower NO x levels and thus fresher
explained by the excessive BVOCs emissions from plants, the ambient higher particles ( Shen et al., 2015 ).
temperatures and the more intense solar radiation which favor photochemical reactions
( Hu and Yu, 2013 ). Similar increase has been also observed in mountainous forest,
rural and urban areas ( Hu and Yu, 2013 ; Li et al., 2018a ; Hong et al., 2019 ). MTL1 2.7. Hydroxycarboxylic acids (HCA)
was the dominant ISOA tracer in each sampling season with a mean annual
3
concentration of 5.1 ± 4.3 ng/m , which is in accordance with the majority of studies ( Hydroxycarboxylic acids, also referred as polyacids in the literature, are
Lyu et al., 2017 ; Li et al., 2018a ; Deshmukh et al., 2019 ; Hong et al., 2019 ), followed characterized as secondarily produced compounds by the oxidation of their precursor
by MTL2 during spring and summer, and by 2MGA during autumn and winter. The ratio compounds, including malic, tartaric, citric and 2-hydroxyglutaric acid ( Fu et al., 2012
of MTL1/MTL2 was calculated with a mean value equal to 2.3 ± 0.42 ( Table 3 ) which ; Gowda and Kawamura, 2018 ). Malic acid for example, has multiple possible
is in accordance with the value measured other studies, eg 1.5–2.5 times, in various secondary source as it can be the oxidation product of gas phase compounds, such as
locations ( Fu et al., 2016 ; Lai et al., 2018; Li et al., 2018a ; Deshmukh et al., 2019 cyclopentene, cyclohexene and 1- methylcyclopentene ( Gao et al., 2004 ), isoprene (
However, in marine aerosols over the Arctic Ocean the ratio was found from 0.76–2.1 Claeys et al., 2004 ) and 1,3-butadiene ( Jaoui et al., 2014 ). It can be also formed
indicating potential different formation pathways or preference of one of the isomers to through further oxidation from 3-hydroxyglutaric acid ( Hu and Yu, 2013 ). Recently,
atmospheric oxidative aging ( Fu et al., 2013 ). In addition, the ratio of MTLs/2MGA hydroxy-diacids were suggested as intermediates in photochemical reactions of low
molecular weight diacids ( Gowda and Kawamura, 2018 ). On the other hand, in Alaskan
illustrated the impact of NO x levels on ISOA formation ( Surratt et al., 2010 ; Yuan et
aerosols significant and strong correlations have been observed between citric and
al., 2018 ). MTLs/2MGA ratio showed a decreasing trend ( Table 3 ) during the
tartaric acids with isoprene SOA tracers indicating oxidation of isoprene as another
sampling periods when the NO x levels were increased ( Table 1 ). For example, during possible source ( Deshmukh et al., 2019 ). HCA concentrations ranged from 1.4 to 31.9
3
winter and autumn mean values were comparable (2.7 and 2.8, respectively), increased ng/m showing significant ( p < 0.05) concentration increase from winter to summer
during spring (4.8) and reached the maximum during summertime (8.1), confirming the and decrease during autumn ( Fig. 2 ) revealing dependence from atmospheric
propitious formation of 2MGA under high NO x /isoprene ratios although other factors, parameters such as, temperature and solar radiation. MAL was the most abundant HCA
3
such as isoprene rate emission, aerosol acidity etc., may play an important role in the in this study, with concentrations ranging from BDL-17.4 ng/m , with average sum-
2MGA formation ( Edney et al., 2005 ; Jaoui et al., 2010 ). This can be further re- mer concentrations being approximately 8-fold higher than those measured in winter.
inforced from the negative and significant correlation ( r = -0.57, p < 0.05) observed Moreover, during the warmer months (spring and summer) significant ( p < 0.05) higher
between NO x concentrations and the aforementioned ratio ( Fig. 9 ). After further concentrations of each HCA, than those of colder months, have been observed. Such in-
Fig. 10 – Scatter plot of ISOA tracers (ng/m 3 ) and tartaric acid (ng/m 3 ). Fig. 11 – Scatter plot of terephthalic acid and bisphenol A (ng/m 3 ).
crease, during the warm period, has also been observed in In- dia for malic, tartaric and
citric acids ( Fu et al., 2010 ). How- ever, in Guangzhou malic acid presented
( Krumal et al., 2010 ). Higher concentrations were observed in Susa (750 ± 680 ng/m 3 )
significantly lower concentrations than those of this study during summertime with a
3
3 3 and Torino (680 ± 290 ng/m ), Italy ( Piazzalunga et al., 2013 ) and much higher (935 ±
mean value of 0.13 ± 0.14 ng/m which increased during winter (0.40 ± 0.37 ng/m ) (
3
Ho et al., 2011 ). Higher MAL concentrations were measured in Thessaloniki, with 443 ng/m ) in Xi'an, China ( Zhang et al., 2014 ). Lower concentrations were observed
3 3 3
mean concentration of 62 ± 26 ng/m , nevertheless, different seasonal variations were in Oporto, Portugal and Copenhagen, Denmark ( < 150 ng/m and < 50 ng/m ,
observed between PM 10 and PM 2.5 -bound MAL ( Balla et al., 2018 ). respectively) ( Oliveira et al., 2007 ). The ratio of LEV to MAN is often used to estimate
different burning sub- strates. LEV/MAN values between 3-10 are attributable to soft-
In urban atmospheres, it has been reported that MAL can be
wood, 15–25 to hardwood and > 40 to crop residues ( Zhu et al., 2015 ; Kang et al., 2018
photochemically produced by the hydroxylation of diC4 ( Kawamura and Ikushima,
). Values illustrated in this work ( Table 3 ), show that a mixture of softwood/hardwood
1993 ; Hegde and Kawamura, 2012 ). The MAL/diC4 ratio was showed highest average
is used as a burning substrate (mean value of 11.8 ± 7.3) with a slight increase observed
values during summer (0.25 ± 0.09) which is 2.3, 4.2 and 3.1-fold times higher than the
during winter (15.1 ± 11). In Belgrade aerosols, increase of LEV/MAN ratio was
values measured in autumn, winter and spring, respectively, sup- porting this hypothesis
observed during the period where open fires were occurred ( Zangrando et al., 2016 ),
which is parallel with those reported by ( Pavuluri et al. 2010 ; Hegde and Kawamura,
whereas the ratio decrease in summer could show a faster degradation of LEV over
2012 ). MAL, 2HGA and CIT exhibited strong and significant correlations with each
MAN ( Zhu et al., 2015 ).
other ( r = 0.68–0.74, p < 0.05) ( Table S5 ) suggesting that they originate from the
same source, whereas the corresponding concentration of TAR with the other HCA Bisphenol A is an endocrine disrupting compound with widespread use in
ranged from 0.32 to 0.36, indicating different origin for MAL. This source could be the manufacture of plastics and resins. BPA's multivariate effects on living organisms
isoprene's oxidation as it is well correlated with the ISOA tracers ( Fig. 10 ). Similar have been extensively studied as a result, many countries banned the production of BPA-
strong correlation (0.75) has been reported by ( Deshmukh et al., 2019 ), which polymers containing products or decided to use BPA-analogues or substitutes (
reinforces the suggestion of ( Claeys et al., 2004 ) that TAR can be generated from the Michałowicz, 2014 ). There are many studies in- volving BPA levels in soil and aquatic
photochemical oxidation of isoprene. environments, nevertheless, atmospheric-BPA studies are limited ( Fu and Kawamura,
2010 ). In urban atmospheres, open burning of plastic containing materials in domestic
waste is proposed as a source of BPA due to its positive correlation with 1,3,5-
2.8. Biomass burning tracers and bisphenol A triphenylbenzene, a plastic- burning tracer ( Fu and Kawamura, 2010 ). BAP
3
concentrations varied from BDL to 9.5 ng/m ( Table 1 ) with the highest mean con-
Levoglucosan and its isomer, mannosan, are anhydrosugars which are
centrations observed during autumn (3.1 ± 2.5 ng/m 3 ) and winter (2.3 ± 1.7 ng/m 3 )
primarily emitted into the atmosphere by the pyrolysis of cellulose and hemicellulose
3
containing materials ( Simoneit, 2002 ; Zhu et al., 2015 ). Thus, they have been used whereas significant ( p < 0.05) decrease was noticed during spring (0.97 ± 0.96 ng/m )
3
biomass burning tracers to estimate the contribution of open and residential biomass and summer (0.37 ± 0.29 ng/m ), indicating that open burning of plastics was very
burning activities to atmospheric particles ( Pietrogrande et al., 2014 ; Zangrando et al., active during the cold months, however decreased but not negligible during the warmer
3
2016 ). BBTs ranged from 3.0 to 989 ng/m ( Table 1 ) throughout the sampling peri- months. PM 10 -bound BPA was found at higher levels in 2 sites of Thessaloniki, Greece
ods, with their significantly increased concentrations ( p < 0.05) during autumn (401 ± with mean concentrations for the urban/traffic site and the urban/industrial site being
3 3 3 3 3
272 ng/m ) and winter (362 ± 219 ng/m ) over spring (43.2 ± 31.5 ng/m ) and 6.78 ± 6.45 ng/m and 13.2 ± 18.0 ng/m , respectively ( Salapasidou et al., 2011 ).
3
summer (56.5 ± 44.3 ng/m ). High concentrations of BBTs during winter/autumn are High average concentrations of BPA were also observed in Chennai (4.5 ng/m 3 ) and
connected mostly with local biomass burning emissions for residential heating. During Mumbai (2.5 ng/m 3 ), In- dia including both cold and warm periods, whereas
spring/summer, the lack of residential heating emissions leads to much lower
summertime concentrations measured in Christchurch were on the same levels with
concentrations of BBTs, with the ac- cidental fires and the uncontrolled combustion 3
practices, which are common in the studied area, being possible minor sources. In those of this study (0.52 ng/m ) ( Fu and Kawamura, 2010 ). BPA correlated nicely
addition during the warmer seasons the atmospheric degradation of levoglucosan from with terephthalic acid ( r = 0.73, p < 0.05) ( Fig. 11 ) confirming their common emission
OH radicals is favored ( Hoffmann et al., 2010 ; Balla et al., 2018 ). Levoglucosan levels sources. As previously mentioned, terephthalic acid is suggested as tracer from plastic
during fall/winter were comparable with those measured in other European cities, such burning activities ( Zhao et al., 2018 ). Another interesting relationship was observed
3 3 between BPA and the PAH as they were strongly and significantly correlated ( r = 0.80,
as Belgrade, Serbia (424.9 ng/m ), Florence, Italy (371 ng/m ) ( Giannoni et al., 2012 )
p < 0.05) ( Fig. 12 ) indicating that plastic burning emissions, and therefore uncon-
and Brno, Czech Republic (326 ng/m 3 )
Fig. 12 – Scatter plot of PAH and BPA (ng/m 3 ). trolled combustion activities, may be a significant contributor of PAH in the studied
area.
2.9. Influence of ozone Variance (%) 30.8 23.0 9.2 7.7 5.8 Compound 1 2 3 4 5 DIC4 -0.188 0.887 0.135 0.033
0.031 DIC5 0.025 0.866 0.083 0.117 -0.016 DIC6 -0.125 0.921 0.007 0.078 0.036
DIC7 -0.200 0.699 0.175 0.135 0.250 DIC8 -0.160 0.878 -0.002 0.114 0.130 DIC9 -
Atmospheric oxidants such as ozone and OH radicals play an important 0.214 0.827 0.080 0.019 0.192 DIC10 -0.198 0.798 -0.147 -0.013 0.180 BEN -0.275
role on SOA formation which has been demonstrated in field and chamber studies ( Guo 0.454 -0.047 -0.194 0.680 TOL 0.525 -0.189 0.013 0.324 -0.140 PHTHA -0.227 0.318
-0.020 -0.052 0.823 tPHTHA 0.809 -0.040 0.026 0.184 -0.211 iPHTHA 0.778 -0.211
et al., 2012 ; Iinuma et al., 2013 ; Yuan et al., 2018 ). Ozone, in addition, produces OH 0.087 0.309 -0.136 TRIM -0.216 0.487 -0.215 -0.238 0.596 MAL -0.198 0.813 -0.212 -
radicals via photolysis ( Atkinson and Arey, 2003 ), promoting indirectly SOA for- 0.271 -0.057 2HGA -0.226 0.739 0.078 -0.333 0.238 CIT -0.288 0.685 -0.175 -0.331
mation ( Hallquist et al., 2009 ). Increase of ozone levels have led to significant increase 0.148 MAN 0.538 -0.057 0.239 0.510 0.302 LEV 0.567 -0.165 0.265 0.533 0.280 FLU
of secondary organic carbon (SOC) at urban and rural sites of Beijing, China ( Guo et al., 0.092 0.072 -0.180 0.655 -0.286 PHE 0.335 -0.189 0.028 0.794 -0.076 ANT 0.619 -
0.289 0.440 0.032 -0.007 FLT 0.913 -0.217 0.153 0.163 -0.023 PYR 0.912 -0.213
2012 ). In this study, summertime ozone levels were significantly higher ( Fig. S1 ), in 0.124 0.153 -0.025 CHR 0.942 -0.137 0.152 0.032 0.002 BaA 0.915 -0.192 0.145 0.113
this light, the potential impact of ozone on BSOA and the other related polar organic -0.115 BbkF 0.915 -0.215 0.165 0.149 -0.121 BaP 0.913 -0.110 0.195 0.035 -0.013 IPY
groups was examined. Fig. 13 demonstrates the scatter plots of different compound 0.899 -0.148 0.190 -0.118 -0.058 DBA 0.830 -0.279 0.225 -0.031 -0.157 BPE 0.912 -
groups with ozone. The strongest and significant ( p < 0.05) correlation with ozone was 0.225 0.162 0.130 -0.142 BPA 0.826 -0.105 0.127 0.091 -0.123 C12 -0.273 -0.156
0.562 -0.271 0.042 C14 0.353 -0.027 0.786 0.040 0.135 C16 0.110 0.331 0.754 0.340
observed for ISOA tracers ( r = 0.77) ( Fig. 13 a ). Ozone-isoprene reaction is an 0.001 C17 0.330 -0.081 0.587 -0.179 -0.081 C18 0.075 0.261 0.653 0.477 -0.107 C18:1
important SOA formation process, beyond the OH-radical initiated oxidation ( 0.072 -0.083 0.514 -0.247 0.032 C20 0.293 -0.043 0.622 0.046 -0.147
Kleindienst et al., 2007 ). A similar strong correlation between ozone and ISOA
products has been observed in a Chinese forested area ( Wang et al., 2008 ). Positive and
significant correlations of ozone with MTLs and 2MGA have been noticed in rural
sites as well ( Li et al., 2018 a). Additional correlations with ozone ( r = 0.63, p < 0.05) species examined in this study. For this purpose, we included in our analysis all the
have been observed with PSOA tracers ( Fig 13 c ) indicating the important role of detected compounds expect the biogenic SOA tracers whose sources are known. Five
ozone in pinene oxidation although hydroxyl and nitrates radicals are, as well, important factors explained 76.5% of the total variance ( Table 4 ), with 0.5 being the selected
contributors ( Qi et al., 2012 ). Significant ( p < 0.05) increase in HCA and DCA levels ( factor score as the lowest significance level ( Agarwal et al., 2009 ). Fac- tor 1 (30.8% of
r = 0.69 and 0.58, respectively) ( Fig. 13 b, d ) was found with the increased of ozone the variance) is heavily loaded with the majority of the studied PAH, tPHTHA , iPHTHA
concentrations during the sampling period. As DCA and HCA can be generated from , BPA while small loads of the biomass burning tracers and TOL can be observed. As a
the ozonolysis or photochemical oxidation of their corresponding olefin precursors ( Gao result, this factor attributes to mixed combustion sources revealing the impact of the
et al., 2004 ; Bikkina et al., 2015 ; Gowda et al., 2018 ), their higher concentrations can plastic enriched waste combustion activities and the open burning practices which are
be explained by the increased ozone levels, especially during summer when also solar very common in the studied area. Recently, the global PAH emissions from open waste
2
radiation is more intense. Total DCA concentration was also found to be nicely ( R burning were estimated at 334 Gg/yr highlighting that the PAH-budget from open
0.64) correlated with ozone in a French urban/background site ( Mirivel et al., 2011 ). On waste burning is largely underestimated to the global PAH inventory ( Wiedinmyer et
the contrary, the sum of each of the detected aromatic acids didn't present any al., 2014 ). Moreover, aerosols from garbage burning are often clubbed with biomass
relationship with ozone levels ( Fig. 13 e ). However, the three aromatic acids which burning aerosols as biomass burning tracers can be also emitted from waste combustion
exhibited significantly higher concentrations during the warmer months, appear to be ( Christian et al., 2010 ; Akagi et al., 2011 ). Factor 2 is tightly clustered (loadings >
also related with ozone ( Fig. 13 f ) as they are moderately but significantly correlated ( 0.65) with all the detected DCA, from diC4- diC10, MAL, CIT and 2HGA referring to
= 0.44, p < 0.05), reinforcing the hypothesis of their secondary formation. secondary formation source including photochemical oxidation of unsaturated fatty
acids. This is in agreement with ( Pavuluri et al., 2010 ) who also found unsaturated
2.10. Principal component analysis (PCA) fatty acids oxidation as a significant source of C4-C10 dicarboxylic acids and other
related polar organic compounds. Fac- tor 3 (variance of 9.2%) is associated with mixed
primary sources such as vehicle emissions and cooking as it is mainly loaded with
Principal component analysis (PCA) was employed in the whole dataset
monocarboxylic acids which is consistent with the findings
for the evaluation of any potential common sources of the
Component
Fig. 13 – Scatter plot of O 3 ( μg/m 3 ) with (a) ISOA, (b) HCA, (c) PSOA, (d) DCA (e) AA, and (f) S AA (ng/m 3 ). S AA refers to the considered secondarily produced aromatic acids, including the sum of PHTHA, BEN
and TRIM.
of Zhao et al. (2014) . Factor 4 (7.7% of variance) is clustered with two PAH, including
PAH agreed
PHE and FLU, and the biomass burning tracers of LEV and MAN indicating biomass with each other on the dominance of combustion sources, while DRs of the selected
burning as the main source. In other studies, PHE and BbK were associated with carboxylic acids, showed the influence of anthropogenic emissions on aerosols, fresher
biomass burning, however BbkF was mostly loaded in Factor 1 ( Mohanraj et al., 2012 aerosols during spring and winter and fresher SOA aerosols during summer. In addition,
). Factor 5 (variance of 5.8%) is attributed to VOC oxidation products such as increase of ozone levels has led to significant increase of certain compound groups, such
naphthalene and toluene as it is loaded with PH- THA, BEN, and TRIM ( He et al., 2018 as ISOA tracers and HCA, although other parameters affect their formation including
). Zhao et al. (2014) , after PCA analysis, have also found a relative factor which aerosol acidity, their precursor levels etc., while higher NO x levels affect the isoprene
however contained additional TOL, iPHTHA and a sum of other polycarboxylic oxidation chemistry. Emissions from plastic waste burning was the most significant
aromatic acids indicating secondary sources, which nevertheless were associated with factor (30.8%) according to the results from the PCA analysis, followed by oxidation of
emissions from plastic burning emissions in our study. unsaturated compounds (23.0%). Vehicle exhausts/cooking, biomass burning and
oxidation of VOCs explained a respective 9.2%, 7.7% and 5.8% of the variance. The
exported results of this study underline the significance of the plastic enriched waste
3. Conclusions
uncontrolled burning practices in a region where additional urban and industrial sources
are present. For this purpose, future study will emphasize on plasticizers and other
A total of 47 compounds from 7 different classes were iden- tified in combustion tracers in order to have a clearer profile of the used burning materials and
PM 10 aerosol samples collected from Aspropirgos, an urban/industrial site of Greece, the impact on air quality and public health.
during a 1-year period. BBTs were the most abundant compound class during autumn
and winter, DCA was the dominant class during summer and MCA during spring.
Compounds exhibited seasonal variations with significant increase in autumn/winter
concentrations for PAH, MCA, BBTs and BPA and in summer/spring concentrations for
DCA, BSOA tracers, HCA. Indi- vidual AA showed different seasonal trends having Declaration of Competing Interest
both primary and secondary sources. The aerosol carcinogenic and mutagenic potencies
were significantly increased during the colder months while BaPE values exceeded, at a The authors declare that they have no known competing finan- cial interests
3
percentage of 46.4%, the proposed limit of 1 ng/m . The calculated DRs of selected or personal relationships that could have appeared to influence the work reported in this
paper.
Acknowledgments Twenty years of measurement of polycyclic aromatic hydrocarbons (PAHs) in UK ambient air by nationwide
air quality networks. Mengepung. Sci. Proses. Im- pacts 15 (6), 1199–1215 . Cao, F. , Zhang, SC , Kawamura,
K. , Liu, X. , Yang, C. , Xu, Z. , et al. , 2017. Chemical characteristics of dicarboxylic acids and related
This research is co-financed by Greece and the European Union (European
organic compounds in PM2.5 during biomass-burning and non-biomass-burning seasons at a rural site of
Social Fund- ESF) through the Operational Programme «Human Resources Northeast China. Mengepung. Polutan. 231 (Part 1), 654–662 . Christian, TJ , Yokelson, RJ , Cardenas, B. ,
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Development, Education and Lifelong Learn- ing» in the context of the project biofuel use and garbage burning in central Mexico. Atmos. Chem Phys 10 (2), 565–584 . Claeys, M. , Graham,
“Strengthening Human Resources Research Potential via Doctorate Research” (MIS-50
B. , Vas, G. , Wang, W. , Vermeylen, R. , Pashynska, V. , et al. , 2004. Formation of secondary organic
0 0432), imple- mented by the State Scholarships Foundation (IK Υ). aerosols through photooxidation of isoprene. Science 303 (5661), 1173–1176 . Claeys, M. , Szmigielski, R. ,
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Journal of Environmental Sciences

Aerosol organik primer dan sekunder di situs perkotaan / industri: Sumber,

Panagiotis Georgios Kanellopoulos 1 , Eleni Verouti 1 , Eirini Chrysochou,

47,4 ± 30,6 μg / m 3 ( Tabel 1 ). Seperti yang jelas dari Gambar 2 , konsentrasi

dingin dan periode akhir (masing-masing 69 dan 58 μg / m 3 ) ( Terzi et al., 2010 ).

2.2.1. PAH health implications

Ratio Summer Autumn Winter Spring All samples

Fig. 4 – Temporal variations of BaPE (ng/m 3 ).

( BaP − TEQ ) = ( [ BaA ] × 0 . 1 ) + ( [ Chr ] × 0 . 01 ) + ( [ BbkF ] × 0 . 1 )

It should be noted that as separation of BbK and BfK couldn't2.3.

Ratio Summer Autumn Winter Spring All samples

MTLs = MTL1 + MTL2

2.4. Dicarboxylic acids (DCA)

2.6. Biogenic secondary organic aerosol (BSOA) tracers

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