attenuation of polychlorinated biphenyls under anaerobic conditions a thesis submitted to the ...

330 Pages·2012·4.4 MB·English

by  Devrim Kaya

ATTENUATION OF POLYCHLORINATED BIPHENYLS UNDER ANAEROBIC
CONDITIONS

A THESIS SUBMITTED TO
THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES
OF
MIDDLE EAST TECHNICAL UNIVERSITY

BY

DEVRİM KAYA

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR
THE DEGREE OF DOCTOR OF PHILOSOPHY
IN
ENVIRONMENTAL ENGINEERING

SEPTEMBER 2012
Approval of the thesis:

ATTENUATION OF POLYCHLORINATED BIPHENYLS UNDER
ANAEROBIC CONDITIONS

submitted by DEVRİM KAYA in partial fulfillment of the requirements for the
degree of Doctor of Philosophy in Environmental Engineering Department,
Middle East Technical University by,

Prof. Dr. Canan Özgen
Dean, Graduate School of Natural and Applied Sciences

Prof. Dr. Göksel N. Demirer
Head of Department, Environmental Engineering

Prof. Dr. F. Dilek Sanin
Supervisor, Environmental Engineering Dept., METU

Assoc. Prof. Dr. İpek İmamoğlu
Co-Supervisor, Environmental Engineering Dept., METU

Examining Committee Members:

Prof. Dr. Celal F. Gökçay
Environmental Engineering Dept., METU

Prof. Dr. F. Dilek Sanin
Environmental Engineering Dept., METU

Prof. Dr. Kevin R. Sowers
Institute of Marine and Environmental Technology,
University of Maryland, USA

Assist. Prof. Dr. Tuba Hande Ergüder
Environmental Engineering Dept., METU

Assist. Prof. Dr. Barış Kaymak
Environmental Engineering Dept., METU

Date:
I hereby declare that all information in this document has been obtained and
presented in accordance with academic rules and ethical conduct. I also declare
that, as required by these rules and conduct, I have fully cited and referenced
all material and results that are not original to this work.

Name, Last name: Devrim KAYA

Signature :
iii
ABSTRACT

ATTENUATION OF POLYCHLORINATED BIPHENYLS (PCBs) UNDER
ANAEROBIC CONDITIONS

Kaya, Devrim
Ph.D., Department of Environmental Engineering
Supervisor: Prof. Dr. F. Dilek Sanin
Co-Supervisor: Assoc. Prof. Dr. İpek İmamoğlu

September 2012, 302 pages

Polychlorinated biphenyls (PCBs) are toxic and persistent anthropogenic
contaminants. Concern on their adverse health effects has led to their regulation in
air, water and/or soil in addition to sludge. Hence, removal of PCBs in various
matrices, including transformer oils (TO) is a priority. This study aims to investigate
PCB-118 and Aroclor 1254 toxicity and dechlorination by varying certain critical
experimental components including electron donor (sludge or fatty acids), inocula
(unacclimated or acclimated culture) and the doses of PCB and TO under anaerobic
conditions. Anaerobic toxicity assays (ATA) reactors, lab-scale anaerobic batch
digesters and sediment microcosms were used for this purpose. Increase in PCB-118
and TO doses affected anaerobic digester performance by negatively influencing
methanogenesis, while favoring dechlorination only with the increase in PCB-118
dose. Up to 22% PCB-118 removal was attained with unacclimated culture. Studies
with acclimated cultures showed Grasse River (GR) sediment to be the most active
when compared to Fox River and Baltimore Harbor sediments. In GR sediment
microcosms, PCB-118 and Aroclor 1254 removal efficiencies decreased when TO
was present (1%), while 10% TO inhibited PCB dechlorination. Waste activated
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sludge was shown to be an effective electron donor, similar to fatty acids. Aroclor
1254 dechlorination was dechlorinated through removal of flanked meta and para
chlorines, however, dechlorination pathways appeared to differ according to the
presence/absence of TO. No ortho or unflanked chlorines were removed. Molecular
tools (qPCR and DHPLC) were used to confirm the presence of active PCB
dechlorinators. Dechlorination of PCBs was shown to be growth-linked.

Keywords: Anaerobic Digestion, Aroclor 1254, Molecular Tools, PCB 118,
Transformer Oil

v
ÖZ

ANAEROBİK ŞARTLAR ALTINDA POLİKLORLU BİFENİLLERİN
(PCBler) GİDERİMİ

Kaya, Devrim
Doktora, Çevre Mühendisliği Bölümü
Tez Yöneticisi: Prof. Dr. F. Dilek Sanin
Ortak Tez Yöneticisi: Doç. Dr. İpek İmamoğlu

Eylül 2012, 302 sayfa

Poliklorlu bifeniller (PCBler) toksik ve insan kaynaklı kalıcı kirleticilerdendir.
PCBlerin sağlık üzerindeki olumsuz etkilerinden kaynaklanan endişeler, onların
çamurun yanı sıra havada, suda ve/veya topraktaki miktarlarının sınırlandırılmasına
dair düzenlemelere yol açmıştır. Böylece, PCBlerin çeşitli matrislerden, özellikle de
trafo yağlarından giderimi öncelik kazanmıştır. Bu çalışmanın amacı, PCB-118 ve
Aroklor 1254‟un klorsuzlaştırılması, bunlardan kaynaklı toksisitenin belirlenmesi ve
değişen PCB ve trafo yağı (TO) dozlarının, elektron donör (çamur veya yağ asitleri),
bakteri kültürü (aklime veya aklime olmayan kültür) gibi çeşitli kritik deneysel
öğelerin etkilerinin anaerobik koşullar altında araştırılmasıdır. Bu sebeple, anaerobik
toksisite testi (ATA) reaktörleri, laboratuvar ölçekli anaerobik kesikli reaktörler ve
sediman mikrokozmları kurulmuştur.

PCB-118 ve TO dozundaki artışın metanojenlerin aktivitesi üzerindeki etkisi negatif
iken, sadece PCB-118‟in dozundaki artış klorsuzlaştırılmasında pozitif yönde katkı
sağlamıştır. Aklime olmayan kültür eklenen çamur reaktörlerinde, PCB-118 giderimi
en çok %22 bulunmuştur. Aklimasyon çalışmaları, Grasse River (GR) sedimanının,
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Baltimore Harbor ve Fox River‟a nazaran daha aktif olduğunu göstermiştir. GR
reaktörlerinde, PCB-118 ve Aroklor 1254 giderim verimi %1 TO varlığında önemli
olçüde düşüş gösterirken, %10 TO varlığında giderim tamamen durmuştur. Atık
çamurun da yağ asitlerine benzer şekilde etkin bir eletron donör olduğu gözlenmiştir.
Aroklor 1254‟ün klorsuzlaştırılmasında, bakterilerin özellikle iki yanı ve/veya tek
yanı klorlarla çevrili meta ve para konumlarındaki klorları hedeflediği gözlenmiş,
TO varlığı ve yokluğunun klorsuzlaştırma yollarında farklılığa sebep olduğu
bulunmuştur. Ortho veya etrafı diğer klorlarla çevrili olmayan klorlarda giderim
gözlenmemiştir. Moleküler araçlar (qPCR ve DHPLC gibi) kullanılarak, PCBlerin
parçalanmasında rol alan bakterilerin varlığı ispatlanmış ve klorsuzlaştırmanın
bakterilerin büyüme hızıyla ilişkili olduğu tespit edilmiştir.

Anahtar Kelimeler: Anaerobik Stabilizasyon, Aroklor 1254, PCB 118, Moleküler
Araçlar, Trafo Yağı
vii
To my grandma, Derdi,
and to my brother, Zafer

viii
ACKNOWLEDGEMENTS

First, I would like to acknowledge, to express my deepest gratitude and to thank my
advisors Prof. Dr. F. Dilek Sanin and Assoc. Dr. Ipek Imamoglu for their guidance,
support, criticism, and advice throughout the research. This has been a little bit, “just
a little bit”, long and incredible journey of learning and challenging experiences, but
also, of great personal and intellectual growth.

My special thanks go to Prof. Dr. Kevin Sowers, who has luckily become my
informal adviser-my third adviser-my advisory committee member, for giving me the
chance to go to Baltimore, opening his laboratory doors to me and providing all the
necessary lab supplies to perform this work. Without him, this thesis would not exist!
I had a great and productive year at the Institute of Marine & Environmental
Technology under his supervision. I feel very lucky!!!

I would like to acknowledge my other Supervising Committee Member, Prof. Dr.
Celal F. Gökçay and my former Supervising Committee Member, Assoc. Prof. Dr.
Sibel Uludağ-Demirer, for their view of the study and valuable recommendations. I
also thank to the Examining Committee Members, Assist. Prof. Dr. Tuba Hande
Ergüder and Assist. Prof. Dr. Barış Kaymak, for their valuable suggestions.

One of special thanks goes to Dr. Rayford Payne for all the help, teaching, editing
some of my chapters, answering my all maybe sometimes stupid questions while
putting up with a lot of questions from someone without any prior molecular biology
experience and the friendship. “Thank you Ray for „tolerating me” (with your words
:). And Dr. Nathalie Lombard, my first and best friend in USA, now in France. I am
very lucky: you were there and opened your home to me. Thank you Nathalie, for all
the help and teaching me how to use COY!! My friends, Dr. Jose Antonio Robledo,
Dr. Yi-Ying Lee and Erin Jenkins, chatting, climbing, restaurants, happy hours with
you guys were the wonderful times. I know our friendship will last forever, we will
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meet again as we did this year in Turkey. Where is the next destination? I would also
like to thank to Ms. Ethel Apolinario for the technical assistance and friendship and
Brigit Queen for the technical help. Also, I would like to thank a former member of
Sowers lab, Dr. Birthe Kjellerup for lighting my way with her deep experiences on
PCB dechlorination and dechlorinating cultures, allocating some of her limited time
to answer my questions, and for her friendship.

I would like to thank to my friends: Dr. Fatma Ozturk, D. Deniz Genc Tokgoz,
Sema Yurdakul, Dr. Gamze Gungor-Demirci, Dr. Pembegul Uyar, Dr. Umay Gokce
Ozkan-Yucel, Merve Bogurcu, Eylem Dogan, and Sevgi Ulugöl, for being a part of
my life, the help, all the friendship and support, and turning my tears into laughs.

One of the biggest thanks goes to Taliye Canpolat, who is my friend, my soul-sister,
my angel, and a gift from God to me!, and to Fatma Vatanlar for being a part of life
and trusting me and all the support. I am very lucky to have you in my life.

The technical assistance of Kemal Demirtas, Mehmet Dumanogullari, and Mehmet
Hamgul, and the help of Hande Bozkurt, Muneer Ahmed, Ece Kendir, Emin Calbay,
and Yigit Ozsen during the some analysis and the preparation of the large numbers of
reactor sets are gratefully acknowledged.

My parents, even though the distance, thank you for the unconditional love and
support that they consistently provide to me touches me beyond words. Thank you
for shaping and molding me into who I am today you have and are always right here
with me. My dearest sisters, Meral and Cigdem, who are my first friends and my
little bro, Adem, thank you all for always supporting me and encouring me, all the
love and patience you have shown me. And my big brother, Zafer, I miss you so
much, you have saved my life and I never had a chance to thank you…Thank you!!!
Thank you very much!!! Love you!!!

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