This publication includes peer-reviewed manuscripts from the 2009 International Network of Environmental Forensics (INEF) held in Calgary, Canada on August 31 through September 1, 2009. INEF is an organization founded by environmental forensic scientists for the express purpose of sharing and disseminating environmental forensic information to the international scientific community. Environmental forensic information presented at the Calgary conference included topics on contaminant age dating, chemical biomarkers, environmental statistics, the interpretation of forensic data, emerging analytical techniques used in forensic investigations, legal sampling and strategies, petroleum hydrocarbon fingerprinting and diagnostic markers used to age date chlorinated solvents. All of these topics were presented in the context of using these techniques to ultimately identify the origin and age of contaminants released into the environment. This professionally edited book is the first of a series of conference publications chronicling the current state of the art in environmental forensics. The intent of this publication and subsequent INEF conference volumes is to compile a library of state of the art scientific articles dealing with environmental forensic topics.
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Robert Morrison has a B.S. in Geology, a M.S. in Environmental Studies, a M.S. in Environmental Engineering and a Ph.D. in Soil Physics from the University of Wisconsin at Madison. He has worked for 38 years as an environmental consultant on projects related to soil and groundwater contamination, including site investigations and remediation. His current specialization is in the forensic review and interpretation of scientific data for the purpose of identifying the source and age of a contaminant release. Gwen O'Sullivan is currently an environmental chemist with Trium Environmental Solutions Inc. (TRIUM). In this role she is responsible for project management, business development, litigation support, and independent scientific investigation. She has B.Sc. in Environmental Sciences from University of Limerick in 1999, and a Ph.D from the Environmental Engineering Research Center within the department of Engineering at Queen's University of Belfast in 2004. She has worked on numerous projects and designed and managed environmental forensics investigations involving compounds of major concern.
This publication includes peer-reviewed manuscripts from the 2009 International Network of Environmental Forensics (INEF) held in Calgary, Canada on August 31 through September 1, 2009. INEF is an organization founded by environmental forensic scientists for the express purpose of sharing and disseminating environmental forensic information to the international scientific community. Environmental forensic information presented at the Calgary conference included topics on contaminant age dating, chemical biomarkers, environmental statistics, the interpretation of forensic data, emerging analytical techniques used in forensic investigations, legal sampling and strategies, petroleum hydrocarbon fingerprinting and diagnostic markers used to age date chlorinated solvents. All of these topics were presented in the context of using these techniques to ultimately identify the origin and age of contaminants released into the environment. This professionally edited book is the first of a series of conference publications chronicling the current state of the art in environmental forensics. The intent of this publication and subsequent INEF conference volumes is to compile a library of state of the art scientific articles dealing with environmental forensic topics.
Differentiating Aged Petroleum Hydrocarbons from Modern Phytogenic Hydrocarbons in High Organic Content Soils Using Biomarkers Gwen O'Sullivan, Jay Bilyk, Jevins Waddell, and Court Sandau, 1,
Oil Profiling of a Diesel Spill at Sea: Semi-Volatile Organics and Trace Metals Analysis Sonia Campbell, 12,
Estimating Contaminant Emissions via Wind-Blown Particles Walt Shields and Rengie Chan, 22,
Stable Isotope Diagnostics of Chlorinated Solvents in Contaminated Aquifers Gregory Smith and Yi Wang, 30,
Forensic Application of Environmental Isotopes in Chlorinated Solvent Investigations Yi Wang, Alan Jeffrey and Gregory Smith, 38,
Forensic Visualization of the Transport and Accumulation of Anthracene in Kandelia Caudel (L.) Druce Leaves Ping Wang, Yaxian Zhu and Yong Zhang, 51,
Position Specific Isotope Analysis: the Ultimate Tool in Environmental Forensics? Caroline Gauchotte, Gillian Connal, Gwen O'Sullivan and Robert Kalin, 60,
Application of CDOM Fluorescence to Indicate Physical Dynamics on the Ocean Surface Jian Ning Chen, Fang Wu, Mao-Cai He, Bei-Bei Liu, Yaxian Zhu and Yong Zhang, 71,
Chemical Oxidative Degradation of MTBE in Groundwater by Waste Steel Scrap Jai-Young Lee, So-Young Moon, Sang-!! Choi and Byung-Taek Oh, 83,
Dendroecological Methods for Dating Petroleum Releases to Soil and Groundwater: The Use of Elemental Markers Gil Oudijk and Jean-Christopher Balouet, 91,
Environmental Forensics and Environmental Law in French and European Perspectives: A Two Ways Approach Yvan Razafindratandra, 108,
Scientist as Historian or Historian as Scientist: Developing Useful History for Litigation of Groundwater Contamination by TCE Stanley Feenstra and James Feenstra, 114,
Environmental Forensics: An Evolutionary Perspective Paul Philp, 129,
Gasoline Leakage Forensics using Compound-Specific Hydrogen Isotope Analyses: A Case Study Yi Wang, 153,
Forensic Tracking of Sewage Waste Stephen Mudge and Wolfram Meier-Augenstein, 164,
Sulphur and Boron Isotope Variations to Track Air Pollutant Deposition in the Castle River of Southern Alberta, Canada John Xie, Ann-Lise Norman, Steve Henley and Michael Wieser, 176,
The Use and Misuse of the National Health and Nutrition Examination Survey (Nhanes) Data for Assessing Human Exposure to Environmental Chemicals Donald Patterson, Gwen 0 'Sullivan and Court Sandau, 188,
Principle Components Analysis of Environmental Chemical Data: Experience and Application Glenn Johnson, 202,
Forensic Methods for Chlorinated Solvents Brian Murphy, 210,
Use of Statistical Tools to Improve Confidence in Analytical Conclusions Rachel Mohler and Jun Lu, 228,
Molecular Microbial Forensics Raul Cano, 240,
Measurement of Laboratory Uncertainty Chris Swyngedouw and Robert Lessard, 259,
Sampling Strategies in Environmental Criminal Cases Marion Stelling and Anita Biezeman, 275,
Age Dating the Release of PCE, TCE and TCA using Stabilizers and Feedstock Impurities as Indicators Robert Morrison and Justin Hone, 289,
Author Index, 305,
Subject Index, 306,
DIFFERENTIATING AGED PETROLEUM HYDROCARBONS FROM MODERN PHYTOGENIC HYDROCARBONS IN HIGH ORGANIC CONTENT SOILS USING BIOMARKERS
G. O'Sullivan, J. Bilyk, J. Waddell, and C.D. Sandau
TRIUM Inc., 2207, 120–5 Avenue W, Cochrane, AB T4C OA4, Canada
I INTRODUCTION
Canada is rich in petroleum hydrocarbon (PHCs) resources and processes involved in the extraction and transportation of these resources has led to the detection of elevated levels of petrogenic hydrocarbons at a wide variety of sites including well sites and along pipelines. Often, particularly in remote locations, PHCs impacts are not detected until the well head or pipeline is decommissioned and it is at this point that remediation activities occur to achieve site closure as required by environmental regulations.
Current PHC analytical protocols from the Canadian Council of Ministers of the Environment (CCME) categorizes a wide range of PHC compounds into four fractions Fl to F4; F1 composed of carbon number (C) C6 to C10, F2 from C10 to C16, F3 from C16 to C32, and F4 from C32 to C50. The CCME protocols therefore assume that all hydrocarbons detected in the C6 to C50 range originate from petroleum sources. However organically rich soils, such as muskeg or peat, contain naturally occurring phytogenic hydrocarbons, which may be detected within the F3 fraction. Phytogenic material in soils and sediments may be derived from the presence of plant debris and are prevalent in moist, highly vegetated environments where organic material may accumulate (e.g. peat and marshlands). Phytogenic compounds may include tannins, waxes, terpenes, fats, oils, and polar compounds, such as organic acids, alcohols, and phenols.
If additional sample clean-up, prior to analysis, is not performed for soil and sediment samples containing phytogenic materials, the presence of these compounds may inflate the measured concentrations of PHCs in the samples. The presence of phytogenic hydrocarbons may also increase the perceived extent of an impact since natural background hydrocarbons may be identified as PHCs. Remedial action plans require the delineation of impacts, which at sites with organically rich soils is made difficult, using regulatory methods, by the inability to separate naturally occurring phytogenic organic material from petrogenic sources. The use of more advance analytical techniques such as gas chromatogram mass spectrometry (GS-MS) for the analysis of PHC biomarker compounds may be used as a complementary tool to indicate the conclusive presence of PHCs.
2 PETROLUEM BIOMARKERS
Petroleum biomarkers are chemical fossils that can act as unique tracers for petroleum contaminants. They originate from previously living organisms which constitute the organic materials from which PHCs are derived (Figure 1). During PHC formation mechanisms, such as sedimentation and diagenesis (biological, chemical, and physical alteration of organic matter in sediments), the basic structures of biomarkers remain relatively intact and therefore give scientists an indication of the source material (e.g. terrestrial or marine etc.).
During catagenesis (thermal alteration of organic matter in rocks through burial and heating), biomarkers undergo structural changes. The degree of change may be used to infer the age of PHCs. Therefore, biomarkers may provide information pertaining to the nature, source, type, and geological conditions of formation of PHCs. A number of biomarker classes, covering a wide range of boiling points and carbon numbers have been used to differentiate sources of hydrocarbons including n-alkanes, isoprenoids, sesquiterpanes, tri, tetra-, and pentacyclic terpanes etc. In particular n-alkanes may be used to differentiate naturally occurring modem phytogenic sources of hydrocarbons from PHC derived sources. More resistant biomarkers have been used to characterize degraded petroleum hydrocarbons, particularly aged crude oil, where weathering has removed potential indicator compounds such as the n-alkanes, branched alkanes, polycyclic aromatic hydrocarbons and their alkyl homologues. A number of biomarkers are extremely weather resistant and may be present in...
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