Petrogenic Polycyclic Aromatic Hydrocarbons in the Aquatic Environment: Analysis, Synthesis, Toxicity and Environmental Impact -  - E-Book

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Although a lot is known about the influence of Polycyclic Aromatic Hydrocarbons (PAHs) on the marine environment, there are still many unanswered questions. Petrogenic Polycyclic Aromatic Hydrocarbons in the Aquatic Environment is a monograph that sums up basic knowledge about this topic while highlighting current research practices useful in studying the aquatic environment. It starts with an introduction to effect of PAH in the marine environment. It then proceeds to provide information on techniques to monitor PAH levels and investigate the affected environment in order to control the subsequent negative effects. Chapters also detail the carcinogenic and endocrine effects of PAHs on fish as well as the degradation of PAHs by microorganisms. This monograph is a useful reference for environmental science students and professionals learning about the role of PAH in the marine environment.

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Table of Contents
BENTHAM SCIENCE PUBLISHERS LTD.
End User License Agreement (for non-institutional, personal use)
Usage Rules:
Disclaimer:
Limitation of Liability:
General:
FOREWORD
PREFACE
List of Contributors
Introduction to Petrogenic Polycyclic Aromatic Hydrocarbons (PAHs) in the Aquatic Environment
PETROGENIC PAHs
BIOACCUMULATION OF PAHs IN AQUATIC ORGANISMS
QUANTIFICATION OF PAHs IN BIOTA
BIOLOGICAL EFFECTS OF PAHs
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
References
The Presence of Petrogenic PAHs in the Aquatic Environment, a Focus on Monitoring Studies
INTRODUCTION
Causes of the Presence of PAHs in the Aquatic Environment
Natural Occurrence
Oil Exploration and Production
Accidental Releases
Other Anthropogenic Sources
Monitoring of PAHs in the Aquatic Environment
Chemical Monitoring
Biological Monitoring
Biomonitoring of Sediment Contamination
Biomonitoring of the Water Column
Confounding Factors
The Water Column Monitoring Program in Norway: A Case Study
The Way Forward in Biological Effect Measurement for PAH Contaminations
In situ, Online and Real-Time Monitoring Tools for PAH Monitoring Purposes
Highly Sensitive Methods for Tracking Sources of PAH Contamination
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
References
Oil Spill Fingerprinting – Identification of Crude Oil Source of Contamination
INTRODUCTION
Crude Oil
Advancement in Analytical Chemistry
Environmental use of Petroleomics
Future Directions
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
References
Carcinogenicity of Petrogenic PAHs
INTRODUCTION
CARCINOGENICITY OF PETROGENIC PAHS IN THE MARINE ENVIRONMENT: FOCUS ON FISH AS SENTINEL ORGANISMS
1. Neoplasia in Fish Associated to Polluted Areas
2. The Relationship between PAHs and Observed Tumor Development in Fish
CARCINOGENICITY OF PAHs IN AQUATIC ORGANISMS OTHER THAN FISH
MODE OF TOXIC ACTION ASSOCIATED TO PAHS: TOWARDS THE “BIOLOGICAL PLAUSIBILITY” OF THE ASSOCIATION BETWEEN EXPOSURE AND NEOPLASIA
1. In vitro Genotoxic/Mutagenic Potential of PAHs in Relation to the Aquatic Environment
2. Carcinogenic Effects of PAHs in the Marine Environment: Use of Biomarkers of Genotoxicity/Mutagenicity in Sentinel Organisms
2.1. CYP Enzyme as Biomarker of Exposure to PAHs
2.2. DNA Adducts as Biomarkers of “Biological Effective Dose” to Genotoxic PAHs in the Marine Environment
2.3. Other Biomarkers of Genotoxicity Associated to PAHs in the Marine Environment
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
PAH Metabolites in Fish and Invertebrates: Analysis and Endocrine Disruptive Potential
PAH METABOLITE FORMATION IN AQUATIC SPECIES
PAH Metabolites in Fish
PAH Metabolites in Invertebrates
Sexual Hormone Disruption
Endocrine Effects in Fish
Endocrine Effects in Invertebrates
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Synthesis of Environmental Relevant Metabolites
INTRODUCTION
Naphthols
Formation of Naphthols by Hydroxylation of Halonaphthalenes
Formation of Naphthols by Hydroxylation of Naphthylboronic Acids
Synthesis of Naphthalene Diols
Metabolites of Acenaphthene and Acenaphthylene
Acenaphthenols
Acenaphthenones
Metabolites of Fluorene
Fluorenols
9-Fluorenone
Metabolites of Phenanthrene
Phenanthrols
Phenanthrene-Diols
Chrysene Metabolites
Chrysenols
Syntheses of Dihydro Diols and Diol Epoxides of Chrysene
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Microbial Degradation in the Aquatic Environment
INTRODUCTION
Hydrocarbon Degrading Microorganisms
Microbial Diversity Involved in PAH Degradation
Bacterial PAH Degraders
Aerob Heterotroph Bacterial Metabolism
Uptake into the Cell
Intracellular Transformation
Genetic Background Encoding PAH Degradation Enzymes
Kinetics of Biodegradation
Importance of Interaction
CONCLUDING REMARKS
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES

Petrogenic Polycyclic Aromatic Hydrocarbons 

in the Aquatic Environment: 

Analysis, Synthesis, Toxicity and Environmental Impact

Edited by 

Daniela M. Pampanin

International Research Institute of Stavanger
University of Stavanger,Norway
&

Magne O. Sydnes

University of Stavanger,Norway

BENTHAM SCIENCE PUBLISHERS LTD.

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FOREWORD

Research about polyaromatic hydrocarbons (PAHs) as environmental stressors is a long term topic with multiple aspects. Its importance implies that we will not see any final papers within the area for a long time. As the research unfolds, both extensive global reviews and more limited reviews addressing recent or expected advances are needed. As new investigative methods emerge it is useful to sum up recent findings and the possible directions being opened to us. This is the purpose of this book.

The analysts now refer to the oil fingerprinting field as “petroleomics”, indicating how the field is advancing based on more powerful tools. The analytical advances are not only regarding the parent PAH compounds, but also the metabolized PAHs, known for their high hazardousness. High resolution mass spectrometry will probably soon lead to the detection of a wider range of metabolized and oxidised PAHs too, which will need follow up in different directions.

The analysts ability to synthesize reference PAH metabolites is one of them, and new research challenges will be posed regarding their potential environmental effects. Other logical following steps are revisits of the PAH compounds bioavailability, biodegradability and carcinogenicity. This is the reason these themes are taken up in this book, accompanied by other advances within each of their respective topics. Finally, suggestions are given to how the advances will open for new monitoring methods and strategies leading to one of our important goals: an improved control of a challenged marine environment for which there is an increasingly growing concern.

May this book be an important drop in the ocean that diminishes the PAH part of that concern and help fellow researchers and ourselves to be on top of this complex issue!

Steinar Sanni International Research Institute of Stavanger University of Stavanger Norway

PREFACE

Crude oil and consequently polycyclic aromatic hydrocarbons (PAHs) have been released to the marine environment long time before humans discovered oil through natural oil seeps. Nature has quite efficient systems for cleaning up these releases of contaminants. Since the first human oil excavation started at sea, many oil spills of small and large sizes, have been taking place (chapter 1, 2 and 3). These types of incidents represent an overdose to the natural processes.

The natural defense system for oil degradation is micro organisms, mainly bacteria, which can use the components in oil as an energy source (chapter 7). However, these bacteria preferably use the readily available straight chain hydrocarbons as their first choice of nutrition. This results in a very slow natural removal of larger components such as PAHs, which requires more processing in order to utilize the energy found in the molecules. With great abundance of easily accessible energy sources available, e.g. alkanes, which is the case in an oil spill, PAHs will accumulate in the environment. The micro organisms will only start breaking down these compounds in order to get energy once other energy sources are used up. In the meantime PAHs, which have been pointed out as the most toxic organic compounds found in oil, will impact marine life.

Research has shown that PAHs cause severe effects on fish at all life stages, with the most severe effects found on fish embryos. The book will convey an up to date overview of the current state of knowledge regarding the negative health effects of PAHs on marine life (chapter 1 and 4). Most of the health problems related to exposure to PAHs are caused by the oxidized metabolites that organisms generate in vivo in order to excrete the unwanted compounds (chapter 5). The metabolites are much more reactive and therefore also more toxic than their mother compounds (chapter 4 and 5). These secondary compounds are prone to react with DNA and proteins to form adducts.

Central in research directed towards understanding the mode of action for PAH metabolites in vivo has been the preparation of synthetic material (chapter 6). This material has been utilized as standards for analysis and starting point for studying further metabolism in vivo. Moreover, due to their presence in the marine environment and their genotoxicity, there is a standing requirement for oil and gas operators to monitor their concentration and influence on marine life through environmental monitoring studies (e.g. the Water Column monitoring) (chapter 2).

Although a lot is known about the influence of PAHs on the environment, and the marine environment in particular, there are still many unresolved questions that are awaiting answers. It is our intention that this book will give a solid basis facilitating the pursue of these unanswered questions.

Daniela M. Pampanin International Research Institute of Stavanger University of Stavanger Norway &Magne O. Sydnes University of Stavanger Norway

List of Contributors

Andrea BagiFaculty of Science and Technology, Department of Mathematics and Natural Science, University of Stavanger, Stavanger, NorwayAnna MarqueñoEnvironmental Chemistry Department, IDAEA-CSIC, 08034 Barcelona, SpainCinta PorteEnvironmental Chemistry Department, IDAEA-CSIC, 08034 Barcelona, SpainDaniela M. PampaninInternational Research Institute of Stavanger, Stavanger, Norway Faculty of Science and Technology, Department of Mathematics and Natural Science, University of Stavanger, Stavanger, NorwayDenise FernandesEnvironmental Chemistry Department, IDAEA-CSIC, 08034 Barcelona, SpainEmil LindbäckFaculty of Science and Technology, Department of Mathematics and Natural Science, University of Stavanger, Stavanger, NorwayJérémie Le GoffADn’tox SAS, Centre de Lutte contre le Cancer François Baclesse, Caen, FranceMagne O. SydnesFaculty of Science and Technology, Department of Mathematics and Natural Science, University of Stavanger, Stavanger, NorwayMontserrat SoléMarine Science Institute (ICM-CSIC), 08003 Barcelona, Spain

Introduction to Petrogenic Polycyclic Aromatic Hydrocarbons (PAHs) in the Aquatic Environment

CONFLICT OF INTEREST

The author confirms that the author has no conflict of interest to declare for this publication.

ACKNOWLEDGEMENTS

Declared none.

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The Presence of Petrogenic PAHs in the Aquatic Environment, a Focus on Monitoring Studies

INTRODUCTION

Monitoring of the aquatic environment is extremely important for providing concrete information for the preservation of ecosystems against the adverse effect of anthropogenic sources of contamination. Great attention is focused nowadays on the cocktail of chemicals present in the aquatic environment and their potential

detrimental influence [1]. Within the cocktail of contaminants, the presence of polycyclic aromatic hydrocarbon (PAH) compounds are of particular concern due to their proven carcinogenic properties [2, 3]. Some refer to PAHs as PBT substances: Persistent, Bioaccumulative and Toxic substances. Sensitive and solid source of contamination trackers are still under development. This is particularly relevant for legal issues and chronic contaminations.

Due to the large number of publications related to techniques and approaches for monitoring the presence of PAHs in the aquatic environment [4], this book chapter will focus on giving an overview of the most recent successfully applied strategies in sediment, water and biota. In particular, the chapter will highlight new promising methodologies for tracking PAH contamination sources in biota that concurrently provide information about the real effect of PAH contamination on the aquatic ecosystem and about the source of contamination.

Causes of the Presence of PAHs in the Aquatic Environment

Petrogenic PAHs are present in the marine environment in significant concentrations [5]. They are naturally present in crude oil and coal. In coastal areas, they enter the water primarily from sewage, runoff from roads, smelter industries and oil spills while the presence of PAHs offshore is mostly related to oil seeps, oil spills and produced water discharge from oil and gas installations [3] (Fig. 1).

Evaluation of PAH sources and their effects has been reported since the ‘80s, as shown for example in the National Research Council (US) Committee on pyrene and selected analogues [6]. Examples of sources of PAHs in the aquatic environment are reported herein and a selection of relevant references is proposed.

Natural Occurrence