Organic Chemicals An Environmental Perspective

873 Pages·1999·7.01 MB·English

by  Alasdair H. Neilson

Neilson, Alasdair H. "Frontmatter"
Organic Chemicals : An Environmental Perspective
Boca Raton: CRC Press LLC,2000
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Preface
This book stems from the author’s experience with a variety of problems on
the fate, distribution, and toxicity of organic compounds in the aquatic envi-
ronment. It became increasingly clear that the procedures for investigating
these problems crossed the traditional boundaries of organic and analytical
chemistry, microbiology, and biology, and after many years this resulted in
the idea of selecting the relevant aspects of these and writing the present
book. Environmental problems have become increasingly complex and envi-
ronmental impact studies should be based as far as possible on incontrovert-
ible scientific facts. In this book the basic issues of chemical analysis,
distribution, persistence, and ecotoxicology have therefore been discussed
although the emphasis has been placed on microbial reactions with which the
author is most familiar. Throughout the book an attempt has been made to
include a wide range of structurally diverse compounds as illustration, and
a mechanistic approach to degradation and transformation has been
adopted. At the same time, the limitations in this book should be clearly
appreciated: it is not designed for the specialist in any of the traditional dis-
ciplines, although it is hoped that the level of detail is acceptable to those who
seek discussions of a range of environmental issues. The book is by no means
comprehensive but a list of references for those seeking further detail is pro-
vided at the end of each chapter.
This volume may be considered a new edition of a previous one Organic
Chemicals in the Aquatic Environment. It differs from that volume not only in
attempting to bring up to date the contents of the original chapters and cor-
recting some errors, but in incorporating extensive new material. This
includes more extensive discussion in Chapter 2 of recent analytical proce-
dures, a more thorough discussion in Chapter 4 of chemical and photochem-
ical reactions including those in the troposphere, a presentation in Chapter 7
of more recent aspects of ecotoxicological assays, and a new chapter on biore-
mediation that makes extensive use of principles introduced in previous
chapters. More extensive discussions have been given to the terrestrial and
tropospheric environments, and this justifies the widening of the title from
the original one.
©2000 CRC Press LLC
Acknowledgments
When all is said and done, it remains to thank all those who have contributed
in many different ways to the making of this book. It is a pleasure to express
my deep gratitude to the following.
My teachers in the Universities of Glasgow, Cambridge, Oxford and the
University of California, Berkeley — including many who are no longer with
us — for illustrating by example the rigors of scientific inquiry.
The late Percy W. Brian FRS for patiently directing my faltering footsteps
into microbiology many years ago.
Östen Ekengren, Director, Environmental Technology and Toxicology for
allowing me a number of privileges including free access to library and copy-
ing facilities.
My collaborators, Ann-Sofie Allard, Per-Åke Hynning, Marianne Malmberg,
and Mikael Remberger not only for their scientific contributions but also for
their friendship and tolerance over many years.
Ann-Sofie Allard for her expertise in producing the numerous figures from
sometimes erratic drafts, and for allowing me to expand and update our ear-
lier review that has become Chapter 8.
Mirja S. Salkinoja-Salonen and her colleagues in the Department of
Applied Microbiology and Applied Chemistry, University of Helsinki for
friendship and stimulation during many years.
The Knut and Alice Wallenberg Foundation and its executive director Pro-
fessor Gunnar Hoppe for providing instrumentation that opened new hori-
zons to our research.
My good and long-standing friends the Søndmør families in Øversjødalen,
Norway for providing the tranquility during which most of the revision of
the original text was undertaken.
Eva Berg, without whose continued support and encouragement this book
would never have materialized.
©2000 CRC Press LLC
To A.N. and G.N.M. who no longer tread the Highland hills
©2000 CRC Press LLC
Contents
1. Introduction
1.1 Orientation
1.2 Literature Cited
1.3 Limitations
1.3.1 Organochlorines
1.3.2 Dictates for Inclusion
1.3.3 Modeling
1.3.4 Enzymes and Relatedness
1.4 Biotechnology
1.5 Terrestrial Systems
1.6 The Atmosphere
1.7 Natural Products and Microbial Metabolites
1.7.1 Organohalogen Compounds
1.7.2 Polymeric Compounds
1.7.3 Polypyrroles
1.7.4 Polycyclic Aromatic Hydrocarbons
1.8 The Effect of Xenobiotics on Microbial-Mediated Processes
References
2. Analysis
2.1 Sampling
2.2 Extraction and Cleanup
2.2.1 Solvents and Reagents
2.2.2 Cleanup Procedures
2.2.3 Toxicity-Directed Fractionation
2.2.4 Specific Matrices: Water Samples
2.2.5 Specific Matrices: Sediments and Soils
2.2.6 Specific Matrices: Biota
2.2.7 Volatile Analytes
2.2.8 Atmospheric Sampling and Analysis
2.3 Procedures Involving Chemical Reactions: Derivatization
2.3.1 Introduction
2.3.2 Specific Procedures for Derivatization
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2.4 Identification and Quantification: Basic Definitions
2.4.1 Experimental Techniques: Identification
2.4.1.1 X-Ray Diffraction
2.4.1.2 Mass Spectrometry
2.4.1.3 Nondestructive Procedures: NMR
2.4.1.4 Fluorescence Line-Narrowing Spectroscopy
(FLN Spectroscopy)
2.4.2 Experimental Techniques: Separation
and Quantification
2.4.2.1 GC Systems
2.4.2.2 HPLC Systems
2.4.2.3 CE Systems
2.4.3 Application of Immunological Assays
2.4.4 Stable Isotope Fractionation
2.5 General Comments
2.5.1 Introduction
2.5.2 Laboratory Practice
2.5.3 Flexibility in Operation: An Open Approach
2.5.4 The Spectrum of Analytes
2.5.5 Multicomponent Commercial Products and Effluents
2.6 Conclusions
References
3. Partition: Distribution, Transport, and Mobility
3.1 Partitioning into Biota: Uptake of Xenobiotics
from the Aqueous Phase
3.1.1 Direct Measurements of Bioconcentration Potential
3.1.1.1 Outline of Experimental Procedures
3.1.1.2 The Molecular Size of Xenobiotics and the Role
of Lipid Content of Biota
3.1.2 The Role of Particulate Matter and Uptake via Food
3.1.3 Concentration of Xenobiotics into Algae and Higher
Plants
3.1.4 Surrogate Procedures for Evaluating Bioconcentration
Potential
3.1.5 Interdependence of Bioconcentration and Metabolism
3.1.6 Cautionary Comments
3.2 Partition between the Aquatic and Sediment Phases
3.2.1 Outline of Experimental Procedures
3.2.2 Reversibility: Sorption and Desorption
3.2.3 Aging and Bioavailabilty
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3.2.4 Mechanisms of Interaction between Xenobiotics and
Components of Solid Matrices
3.3 Phase Heterogeneity: Dissolved Organic Carbon,
Interstitial Water, and Particulate Matter
3.3.1 The Inhomogeneity of the Water Column
3.3.2 The Role of Interstitial Water
3.3.3 The Role of Sediment and Particulate Matter
in the Aquatic Phase
3.4 Partitions Involving the Atmospheric Phase
3.4.1 Partitioning between the Aquatic Phase
and the Atmosphere
3.4.2 Partition between Solid Phases and the Atmosphere
3.5 Dissemination of Xenobiotics
3.5.1 Transport within Aquatic Systems: The Role of Water
and Sediment
3.5.2 Transport within Aquatic Systems: the Role of Biota
3.5.3 The Role of Atmospheric Transport
3.5.4 Biomagnification
3.5.5 The Role of Models in Evaluating the Distribution
of Xenobiotics
3.5.6 Leaching and Recovery from Other Solid Phases
3.6 Monitoring
3.6.1 Choice of Samples
3.6.2 Temporal Record of Input
3.6.3 Choice of Analytes
3.6.4 Monitoring and Ecoepidemiology
3.7 Conclusions
References
4. Persistence: General Orientation
4.1 Abiotic Reactions
4.1.1 Photochemical Reactions in Aqueous and Terrestrial Environments
4.1.2 Reactions in the Troposphere
4.1.3 Chemically Mediated Transformation Reactions
4.1.3.1 Hydrolytic Reactions
4.1.3.2 Dehalogenation Reactions
4.1.3.3 Oxidation Reactions
4.1.3.4 Reduction Reactions
4.1.3.5 Thermal Reactions during Incineration
4.2 Biotic Reactions
4.2.1 Definitions — Degradation and Transformation
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4.2.2 Biodegradation of Enantiomers
4.2.3 Sequential Microbial and Chemical Reactions
4.3 The Spectrum of Organisms
4.3.1 Introduction
4.3.2 Aerobic and Facultatively Anaerobic Bacteria
4.3.3 Organisms Using Electron Acceptors Other Than
Oxygen
4.3.4 Anaerobic Bacteria
4.3.5 Phototrophic Organisms
4.3.6 Eukaryotic Microrganisms: Fungi and Yeasts
4.3.7 Other Organisms
4.4 Mechanisms for the Introduction of Oxygen
4.4.1 Microbial Monooxygenase and Hydroxylase Systems
4.4.1.1 Monooxygenases
4.4.1.2 Cytochrome P-450 Systems
4.4.2 Bacterial Dioxygenase Systems
4.4.3 Eukaryotic Dioxygenases
4.4.4 Oxidases, Peroxidases, and Haloperoxidases
4.5 Interactions
4.5.1 Single Substrates: Several Organisms
4.5.2 Cometabolism and Related Phenomena
4.6 Determinative Parameters
4.6.1 Physical Parameters
4.6.1.1 Temperature
4.6.1.2 Oxygen Concentration
4.6.1.3 Redox Potential
4.6.1.4 The Role of Association of Bacteria
with Particulate Material
4.6.2 Substrates: Concentration, Transport into Cells,
and Toxicity
4.6.3 Bioavailability: “Free” and “Bound” Substrates
4.6.4 Preexposure: Pristine and Contaminated
Environments
4.7 Rates of Metabolic Reactions
4.7.1 Kinetic Aspects
4.7.2 Metabolic Aspects: Nutrients
4.8 Regulation and Toxic Metabolites
4.8.1 Regulation
4.8.2 Toxic or Inhibitory Metabolites
4.9 Catabolic Plasmids
4.10 Conclusions
References
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5. Persistence: Experimental Aspects
5.1 Abiotic Reactions
5.2 Microbial Reactions
5.2.1 Determination of Ready Biodegradability
5.2.2 Isolation and Elective Enrichment
5.2.3 General Procedures
5.2.4 Basal Media
5.2.5 Organic Substrates
5.2.6 Procedures for Anaerobic Bacteria
5.3 Design of Experiments on Biodegradation
and Biotransformation
5.3.1 Pure Cultures and Stable Consortia
5.3.2 Microcosm Experiments
5.3.3 Experiments in Models of Natural Aquatic Systems
5.4 Experimental Problems: Water Solubility, Volatility, Sampling,
and Association of the Substrate with Microbial Cells
5.5 Procedures for Elucidating Metabolic Pathways
5.5.1 The Principle of Sequential Induction
5.5.2 Application of Mutants
5.5.3 Application of Metabolic Inhibitors
5.5.4 Use of Synthetic Isotopes
5.5.5 Application of NMR and Electron
Paramagnetic Resonance
5.6 Application of Surrogate Substrates to Establish Enzymatic
Activity
5.7 Classification and Identification of Organisms
5.8 Procedures for Analysis of Degradative Populations
5.8.1 Specific Metabolic Activity
5.8.2 Nondirected Examination of Natural Populations
5.8.3 Examination for Established Metabolites or Specific
Enzymes
References
6. Pathways of Degradation
and Biotransformation
6.1 Aerobic Degradation of Nonaromatic Hydrocarbons
6.1.1 Alkanes
6.1.2 Cycloalkanes
6.1.3 Alkenes
6.1.4 Alkynes
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