Pollutant-Solid Phase Interactions Mechanisms, Chemistry and Modeling

426 Pages·2001·3.82 MB·English

by  Tarek A. T. Aboul-Kassim (auth.), T. A. T. Aboul-Kassim, B. R. T. Simoneit (eds.)

Foreword
Organic compounds, both natural and synthetic, are a vital part of everyday life.
They come in various forms such as foods, fuels, antibiotics, plastic containers,
rubber tires, agricultural fertilizers, photocopying compounds, etc. Society can-
not survive in its present form without these materials from the chemical in-
dustry. Growth in the numbers of organic chemicals during recent decades has
been extraordinary. Presently, more than 70,000 organic compounds are in com-
mercial production with approximately 1000 added each year. Most are complex
compounds that can be released directly and/or indirectly to the surrounding
environment. Of these, more than 1000 compounds are of environmental con-
cern because of their production quantities, toxicity, persistence, and tendency
to bioaccumulate. A view is emerging in relation to environmental protection
and hazardous substance management that: (1) some organic chemicals and/
or organic leachates from solid waste materials (SWMs) and contaminated sites
are of such extreme environmental concern that all use should be highly con-
trolled including isolation for disposal, and (2) most hazardous substances are
of sufficient social value that their continual use, production and disposal are
justified. For these chemicals their sources, fate, behavior and effects must be
fully assessed and understood. Assessment and understanding are essential for
society to accept risks of adverse ecological or human health effects.
Concern regarding the adverse effects of organic compounds has resulted in
the worldwide initiation of plans for the registration of new chemicals before
commercial use has commenced. Examples of these are the US Toxic Substances
Control Act, the Environmental Contaminants Act in Canada, and the Scheme
for the Hazard Assessment of Chemicals (OECD) Guidelines in the European
Community.
In order to have a better and healthy environment, it is important that the
environmental chemodynamics of such complex organic mixtures (COMs) and/
or leachates from SWMs and contaminated sites be predicted accurately. It is
imperative that the molecular organic composition of such pollutant mixtures,
their transport processes and migration in and between the various multimedia
environments be fully understood. In addition, their chemical and biochemical
transformation processes (e.g., sorption, desorption, photolysis, volatilization
and biodegradation) as well as their effects on the interacting organisms, that
occupy these multimedia, should be completely delineated.
Answers to some of these questions can be found in the present book which
addresses those properties of an organic compound present in solution and/or
leachate that determine its tendency to: (1) adsorb on solid phase systems (i.e.
XIV Foreword
soil, sediment, suspended matter, colloids and biocolloids/biosolids), (2) leach
through the subsurface environment, (3) volatilize/evaporate into the atmos-
phere, or (4) be absorbed across a biological membrane and bioconcentrated/
biomagnified in the aquatic environment. In addition, after being released into
the environment, an organic pollutant leached from complex mixtures may be
photochemically degraded, oxidized/reduced, hydrolyzed or metabolized by
microorganisms. The important consideration in environmental chemody-
namics of organic pollutants and leachates of COMs is which pollutants react in
a given transformation process, what product will be formed and at what rate
these changes occur. An understanding of these ideas is important in many
aspects such as defining exposure and predicting hazard from such complex
mixtures, and providing a basis for developing strategies for preventing or
minimizing exposure.
Accordingly, the present book, entitled “Pollutant-Solid Phase Interactions:
Mechanisms, Chemistry and Modeling”, is considered an essential step toward a
comprehensive understanding of an important chemodynamic mechanism
such as the interactions between organic pollutants (i.e., present in aqueous
systems or as SWM leachates) and various solid phases. The present volume is
divided into five interrelated chapters. Each chapter has its own objectives.
The first chapter, entitled “Organic Pollutants in Aqueous-Solid Phase En-
vironments: Types, Analyses and Characterizations”, has three main goals. The
first is to present a complete review of the most toxic organic pollutant types
which are present in both aqueous and solid phase environments. These pol-
lutants include petroleum hydrocarbons, pesticides, phthalates, phenols, PCBs,
organotin compounds and surfactants. The second goal is to provide a complete
and comprehensive critical review of the different analytical techniques used for
the determination of these organic compounds. The third objective is to discuss
and review the up-to-date instrumental developments and advancements for the
identification and characterization of such organic compounds.
The second chapter, entitled “Interaction Mechanisms between Organic Pol-
lutants and Solid Phase Systems”, discusses the different solid phase composi-
tions, the interaction mechanisms between these phases and the organic pol-
lutants, and factors affecting sorption mechanisms with the role-played by
humic substances in such interactions.
Chapter three, entitled “Sorption/Desorption of Organic Pollutants from Com-
plex Mixtures: Modeling, Kinetics, Experimental Techniques and Transport Para-
meters”, reviews the most widely used modeling techniques in the field in order
to analyze sorption/desorption data generated from environmental systems.
Some important aspects of the kinetics, chemistry and modeling approaches of
sorption/desorption processes of solid phase systems are discussed. In addition,
a background theory and experimental techniques for the different sorption/
desorption processes are considered, while the estimation of transport param-
eters of organic pollutants from such laboratory studies are presented and
evaluated.
Chapter four, entitled “QSAR/QSPA and Multicomponent Joint Toxic Effect
Modeling of Organic Pollutants at Aqueous-Solid Phase Interfaces”, reviews
several interdisciplinary approaches, such as: (1) some physical and chemical
Foreword XV
properties of organic pollutants in complex mixtures which can affect their
sorption/ desorption chemodynamics, (2) the fundamentals of both quantitati-
ve-structure activity and structure-property relationships, with special empha-
sis on using molecular connectivity indices as useful properties for pollutant
mobility and bioavailability prediction, and (3) the multicomponent joint
toxic/gentoxic effect models to predict the bioavailable fraction and action of
organic pollutants at aqueous-solid phase interfaces. Then, it discusses and eva-
luates how these interdisciplinary approaches can be applied and integrated
using a group of toxic and carcinogenic pollutants such as PCBs and PAHs.
The last chapter, entitled “Microbial Transformations at Aqueous-Solid Phase
Interfaces: A Bioremediation Approach”, presents the basic principles of micro-
bial associations at aqueous-solid phase interfaces, and the types and mecha-
nisms of biodegradation and biotransformation, showing how those principles
relate to bioremediation engineering technologies. It considers some of the
microbiological,chemical,environmental,engineering and technological aspects
of biodegradation/biotransformation.
It is important to mention that information about chemodynamics of organic
pollutants at aqueous-solid phase interfaces is too large, diverse and multidis-
ciplinary, and its knowledge base is expanding too rapidly to be fully covered in
a single book. Nevertheless, we have attempted to present, as much as we can, the
most important and valid key principles that underlie the science and engineer-
ing for possible chemistry, interactions, and modeling at these interfaces. Thus,
knowledge from one or two disciplines was not sufficient, information from
many disciplines was needed. For instance, the characterization of organic pol-
lutants requires knowledge of organic chemistry/geochemistry; their fate and
behavior follow chemical and physical principles; changes in toxicity, hazard
and exposure represent topics of concern in environmental toxicology; the areas
(media) containing the organic pollutants represent interfacial environments
with unique properties; and the modeling techniques are based on approaches
common in environmental engineering. Thus, this book is addressed to
chemists, ecologists, oceanographers, environmental scientists and environ-
mental engineers and should prove to be of use.
We hope that the present information helps to continue the search for creative
and economical ways of limiting the release of contaminants into the environ-
ment, developing highly sensitive techniques for tracking organic pollutants
once released, and to find effective methods to remediate our spoiled resources
and environment.
Corvallis, Oregon, USA, March 2001 Tarek A.T. Aboul-Kassim
Bernd R.T. Simoneit
CHAPTER 1
Organic Pollutants in Aqueous-Solid Phase
Environments: Types, Analyses and Characterizations
1 2
Tarek A.T. Aboul-Kassim , Bernd R.T. Simoneit
1 Department of Civil, Construction and Environmental Engineering,
College of Engineering, Oregon State University, 202 Apperson Hall, Corvallis,
OR 97331, USA
e-mail:
2 T.A.T. Aboul-Kassim and B.R.T. Simoneit
2.7 Surfac tants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.7.1 Anionic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.7.2 Cationic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.7.3 Nonionic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.7.4 Amphoteric (Zwitterionic) . . . . . . . . . . . . . . . . . . . . . . . 51
3 Analysis of Environmental Organic Pollutants . . . . . . . . . . . 52
3.1 Rec overyM easurements . . . . . . . . . . . . . . . . . . . . . . . . 52
3.2 Pre-Extraction and Preservation Treatments . . . . . . . . . . . . . 54
3.3 Extraction Techniques . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.1 Supercritical Fluid Extraction . . . . . . . . . . . . . . . . . . . . . 55
3.3.2 Soxhlet Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3.3 Blending and Ultrasonic Extraction . . . . . . . . . . . . . . . . . 56
3.3.4 Liquid-Liquid Extraction . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.4.1 Concentration Procedures . . . . . . . . . . . . . . . . . . . . . . . 58
3.3.4.2 Advantages and Drawbacks . . . . . . . . . . . . . . . . . . . . . . 58
3.3.5 Solid-Phase Extraction . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.3.5.1 Off-Line Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.3.5.2 On-Line Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.3.6 Column Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3.7 Comparative Extraction Studies . . . . . . . . . . . . . . . . . . . . 61
3.3.8 Micro-Extraction Methods . . . . . . . . . . . . . . . . . . . . . . 63
3.4 Clean-Up Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4.1 Measurement of Extractable Lipids/Bitumen . . . . . . . . . . . . 64
3.4.2 Removal of Lipids/Bitumen . . . . . . . . . . . . . . . . . . . . . . 64
3.4.2.1 Saponification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.2.2 Sulfuric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.2.3 Solid Phase Clean-Up . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.2.4 Gel Permeation Chromatography . . . . . . . . . . . . . . . . . . . 66
3.4.2.5 Supercritical Fluid Clean-Up . . . . . . . . . . . . . . . . . . . . . 67
3.4.2.6 Sulfur Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.5 Automation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.5.1 Robotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.5.2 On-Line Automation . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.6 Multi-Residue Schemes . . . . . . . . . . . . . . . . . . . . . . . . 70
4 Identification and Characterization of Organic Pollutants . . . . . 71
4.1 Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.2 Gas Chromatography-Mass Spectrometry . . . . . . . . . . . . . . 72
4.2.1 Mass Spectrometry Ionization Methods . . . . . . . . . . . . . . . 73
4.2.1.1 Electron Impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.1.2 Chemical Ionization . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.1.3 Electrospray Ionization . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.1.4 Fast-Atom Bombardment . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.1.5 Plasma and Glow Discharge . . . . . . . . . . . . . . . . . . . . . . 74
4.2.1.6 Field Ionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
1 Organic Pollutants in Aqueous-Solid Phase Environments: Types, Analyses and Characterization 3
4.2.1.7 Laser Ionization Mass Spectrometry . . . . . . . . . . . . . . . . . 74
4.2.1.8 Matrix-Assisted Laser Desorption Ionization . . . . . . . . . . . . 74
4.2.2 Types of Mass Spectrometers . . . . . . . . . . . . . . . . . . . . . 75
4.2.2.1 Quadrupole Mass Spectrometry . . . . . . . . . . . . . . . . . . . . 75
4.2.2.2 Magnetic-Sector Mass Spectrometry . . . . . . . . . . . . . . . . . 75
4.2.2.3 Ion-Trap Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . 75
4.2.2.4 Time-of-Flight Mass Spectrometry . . . . . . . . . . . . . . . . . . 76
4.2.2.5 Fourier-Transform Mass Spectrometry . . . . . . . . . . . . . . . . 76
4.2.3 Fragmentation Pattern and Environmental Applications . . . . . . 76
4.3 Liquid Chromatography-MS . . . . . . . . . . . . . . . . . . . . . . 78
4.4 Isotope Ratio Mass Spectrometry . . . . . . . . . . . . . . . . . . . 79
4.4.1 Environmental Reviews . . . . . . . . . . . . . . . . . . . . . . . . 79
4.4.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.4.3 Sample Preparation and Handling . . . . . . . . . . . . . . . . . . 80
4.4.4 On-Line Coupling of IRMS . . . . . . . . . . . . . . . . . . . . . . 81
4.4.5 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.4.5.1 Carbon Isotope Analysis . . . . . . . . . . . . . . . . . . . . . . . . 82
4.4.5.2 Nitrogen Isotope Analysis . . . . . . . . . . . . . . . . . . . . . . . 82
4.4.5.3 Hydrogen Isotope Analysis . . . . . . . . . . . . . . . . . . . . . . 83
4.4.5.4 Oxygen Isotope Analysis . . . . . . . . . . . . . . . . . . . . . . . . 83
4.4.5.5 Chlorine Isotope Analysis . . . . . . . . . . . . . . . . . . . . . . . 84
4.4.6 Modern Application Examples . . . . . . . . . . . . . . . . . . . . 85
4.5 Future Developments in Organic Pollutant Identification
andC harac terization . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
List of Abbreviations
BSTFA Bis(trimethylsilyl)trifluoroacetamide
CI Chemical ionization
COMs Complex organic mixtures
CSIA Compound specific isotope analysis
DEHP Diethyl phthalate
DOP Dioctyl phthalate
ECD Electron capture detector
EI Electron impact
EPA Environmental Protection Agency
ESI Electrospray ionization
FAB Fast-atom bombardment
FI Field ionization
GC Gas chromatography
GC-AED Gas chromatography with atomic emission detection
4 T.A.T. Aboul-Kassim and B.R.T. Simoneit
GC-FPD Gas chromatograph with flame photometric detection
GC-MS Gas chromatography-mass spectrometry
GPC Gel permeation chromatography
HCs Hydrocarbons
HPLC High performance liquid chromatography
HTGC-MS High temperature gas chromatography-mass spectrometry
IDMS Isotope dilution mass spectrometry
IRMS Isotope ratio mass spectrometry
ITD Ion trap detector
LC Liquid chromatography
LIMS Laser ionization mass spectrometry
LLE Liquid-liquid extraction
MALDI Matrix-assisted laser desorption ionization
MS Mass spectrometry
OCPs Organochlorine pesticides
PAEs Phthalic acid esters
PAHs Polycyclic aromatic hydrocarbons
PCBs Polychlorinated biphenyls
PD Plasma desorption
PGD Plasma and glow discharge
RIMS Resonance ionization mass spectrometry
SFC Supercritical fluid chromatography
SFE Supercritical fluid extraction
SIMS Secondary ionization mass spectrometry
SPE Solid phase extraction
SPME Solid phase microextraction
SSJ/LIF Supersonic jet laser-induced fluorescence
SWMs Solid waste materials
TOC Total organic carbon
TOF-MS Time of flight-mass spectrometry
TPs Transformation products
1
Introduction
The twenty-first century can properly be called the age of organic chemistry due
to the huge worldwide increase in organic chemical production (more than
70,000 compounds) and utilization. Many of these organic compounds have pro-
ven to be toxic, carcinogenic, and mutagenic to various aquatic organisms and,
directly and/or indirectly, to humans [1]. The dramatic increase in the
production of organic chemicals has completely altered our immediate human
environment and provided a wealth of new compounds which, in many cases,
were more toxic and carcinogenic than the parent compounds.
With environmental protection high on the agenda of many industrial
countries, new rules and regulations are currently being set up for monitoring
1 Organic Pollutants in Aqueous-Solid Phase Environments: Types, Analyses and Characterization 5
greater numbers of hazardous organic pollutants. Organic pollutants present in
the various environmental multimedia may occur naturally [2] and/or derive
from anthropogenic sources [3–13]. Anthropogenic input may derive from
industrial sources [14–20], urban wastes [21–35], agricultural activity [36–44],
and from degradation products [45–52]. Organic pollutants have different
polarities and chemical properties; hence, low detection limits are necessary for
studying the fate and transport of these organic compounds in and/or within the
different environmental multimedia, as well as their interactive behavior with
other solid phase surfaces.
Accordingly, environmental organic analysis has expanded dramatically in
the last 25 years. With the development of commercially available gas chroma-
tography-mass spectrometer (GC-MS) systems, there has been a significant
increase in the number of organic pollutant fingerprints that have been dis-
covered and identified [53–73]. Identities of individual compounds or com-
positional fingerprints can be determined by highly sophisticated and advanced
instruments [5, 64, 74–88] and are used to provide information about the type
[62, 64, 82, 89–92], amount [89, 93–96], and source confirmation [1, 53–55, 97]
of these pollutants.
Different terms have been used in the literature to describe various environ-
mental organic pollutants/contaminants that are characterized in terms of their
molecular structures [1, 53–55]. The term chemical fossil was first used by
Eglinton and Calvin [98] to describe organic compounds in the geosphere whose
carbon skeleton suggested an unambiguous link with a known natural product.
In addition, other terms such as biological markers, organic tracers, biomarkers,
or molecular fossils, have also been used to describe such organic compounds
[1, 53–56, 60, 61, 63, 66, 68–73]. In line with the current trends in environmental
organic chemistry and for the sake of consistency, the term molecular marker
(MM) suggested by Aboul-Kassim [1] will be used in this book to describe both
naturally occurring (i.e., biological and hence biomarker) and/or anthropo-
genically-derived organic (i.e., non-biomarker) compounds that are present in
both aqueous and solid phase environments.
The main objectives of this chapter are: (1) to review the different toxic
organic pollutants present in both liquid and solid (i.e., sediment, soil, sus-
pended matter and biosolids as bacteria, plankton, etc.) phase environments as
well as complex organic mixture (COM) leachates from solid waste materials of
landfills and disposal sites; (2) to summarize the most recent analyses of these
MM pollutants; and (3) to discuss the optimum instrumental analytical
methods for organic pollutant characterization.
It is intended that the review of the different aspects and goals in this chap-
ter provides an up-to-date background for the succeeding chapters in this
volume. This will clarify the discussions about the different interaction
mechanisms between organic pollutants and various solid phases, their chem-
istry, and applicable modeling techniques that are presented in the subsequent
chapters.
6 T.A.T. Aboul-Kassim and B.R.T. Simoneit
2
Types of Organic Pollutants
Approximately one-half of the industrially produced organic chemicals reach
the global environment via direct and/or indirect routes, for example agricul-
tural practices, municipal and industrial wastes, and landfill effluents. These
products include a variety of pesticides and their metabolites, aliphatic and
aromatic organic derivatives of petroleum hydrocarbons and plastics, organic
solvents and detergents, phenols, PCBs, and organotin compounds. When these
substances reach the natural environment, various degradation and transfer
processes are initiated. The chemical properties of each organic compound
(such as molecular structure, volatility, ionic charge and ionizability, polarizabil-
ity, and water-solubility) determine which processes predominate. Currently
the prevalent opinion is that interaction processes, leading to activation in-
activation, physical sorption, and/or chemical binding or partitioning are
among the most widespread and important phenomena affecting toxic organic
pollutants in the global environment. Some general considerations and pro-
perties of major organic pollutant groups, of relevance to the environment and
of importance to human health, will be summarized briefly in the following
subsections.
2.1
Petroleum Hydrocarbons
Hydrocarbons (HCs) of petroleum origin are widespread organic pollutants that
are found in both aquatic and solid phase environments [1, 53–56, 99, 100]. The
most common groups of compounds are aliphatic and polycyclic aromatic
hydrocarbons (PAHs). Of these the PAHs are toxic, carcinogenic, and sometimes
mutagenic to both aquatic organisms and ultimately humans [1]. The following
is a brief description of each group.
2.1.1
Aliphatic Compounds
Aliphatic hydrocarbons, a diverse suite of compounds, are an important lipid
fraction which is either natural (i.e., from photosynthesis by marine biota in-
habiting the surface waters or by terrestrial vascular plants) or anthropogenic
(i.e., of petroleum origin from land runoff, and/or industrial inputs). Aliphatic
hydrocarbons have been studied and characterized from various environmental
multimedia [1, 53–56, 99–109].
Aliphatic hydrocarbons of petroleum origin (Fig. 1) (also coal) in the en-
vironment are usually composed of:
1. Homologous long chain n-alkane series ranging from <C15 to >C38 with no
carbon number predominance [1, 53–55, 73, 109–114]
2. Unresolved complex mixture (UCM) of branched and cyclic hydrocarbons [1,
53–56, 68, 70, 113, 115–119]
1 Organic Pollutants in Aqueous-Solid Phase Environments: Types, Analyses and Characterization 7
Fig. 1. Chemical structures of some aliphatic hydrocarbon molecular markers as cited in the
text
3. Isoprenoid hydrocarbons such as norpristane (2,6,10-trimethylpentade-
cane), pristane (2,6,10,14-tetramethylpentadecane), and phytane (2,6,10,14-
tetramethylhexadecane) (Structures I–III, Fig. 1) [1, 53–56, 68, 70, 120–123]
4. Tricyclic terpanes (Structure IV, Fig. 1), usually ranging from C19H34 to
C30H56 , and in some cases to C45H86 [68, 124–126]
5. Tetracyclic terpanes such as 17,21- and 8,14-seco-hopanes (Structures V–VI,
Fig. 1) [125–127]
6. Pentacyclic triterpanes, such as the 17a(H),21b(H)-hopane series (Struc-
tures VII–VIII, Fig. 1), consisting of 17a(H)-22,29,30-trisnorhopane (Tm),