Forensic Chemistry Handbook

Lawrence Kobilinsky, Lawrence Kobilinsky

• Publisher: Wiley
• Year: 2011
• ISBN:
  9781118062234
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Analytic Chemistry

A concise, robust introduction to the various topics covered by the discipline of forensic chemistry

The Forensic Chemistry Handbook focuses on topics in each of the major chemistry-related areas of forensic science. With chapter authors that span the forensic chemistry field, this book exposes readers to the state of the art on subjects such as serology (including blood, semen, and saliva), DNA/molecular biology, explosives and ballistics, toxicology, pharmacology, instrumental analysis, arson investigation, and various other types of chemical residue analysis. In addition, the Forensic Chemistry Handbook:

• Covers forensic chemistry in a clear, concise, and authoritative way
  
  

• Brings together in one volume the key topics in forensics where chemistry plays an important role, such as blood analysis, drug analysis, urine analysis, and DNA analysis
  
  

• Explains how to use analytical instruments to analyze crime scene evidence
  
  

• Contains numerous charts, illustrations, graphs, and tables to give quick access to pertinent information
  
  

Media focus on high-profile trials like those of Scott Peterson or Kobe Bryant have peaked a growing interest in the fascinating subject of forensic chemistry. For those readers who want to understand the mechanisms of reactions used in laboratories to piece together crime scenes—and to fully grasp the chemistry behind it—this book is a must-have.

Chapter 1

Forensic Environmental Chemistry

Anthony Carpi and Andrew J. Schweighardt

John Jay College of Criminal Justice, The City University of New York, New York

Summary

Forensic environmental chemistry involves the use of trace chemical techniques for investigating environmental spills in an effort to determine civil or criminal liability. The field can be broken down into two broad areas based on the techniques used to determine liability: chemical fingerprinting and spatial association. In chemical fingerprinting, complex mixtures of chemicals or chemical isotopes are used to associate a spill or environmental release with a source. In spatial association, geographical information systems and geochemical techniques are used to attribute the location of a contaminant with a possible source in physical space.

1.1 Introduction

As technology for trace chemical analysis has expanded in recent decades, so has its application to criminal and civil casework. This has transformed traditional forensic investigations and has expanded their applicability to less traditional areas, such as those involving environmental crimes. Prior to 1950, environmental law in the United States was based on tort and property law and was applied to a very limited number of incidents. Driven by growing environmental awareness in the 1950s and 1960s, the U.S. Congress passed the first Clean Air Act in 1963. This was followed by a slow but steady string of further developments, including the founding of the Environmental Protection Agency (EPA) in 1970 and the passage of the Clean Water Act in 1972, the Endangered Species Act in 1973, and the Comprehensive Environmental Response, Compensation, and Liability Act (Superfund) in 1980. International law began to address environmental issues with the signing of the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) in 1975 and other international treaties. These early milestones have been bolstered by recent amendments, new agencies, and renewed funding, all of which make up a series of laws and regulations that define criminal practices and govern civil liability cases involving the environment. Increased legislation and improved enforcement have led to a significant decrease in easily identifiable environmental disasters, such as when the Cuyahoga River in Cleveland, Ohio burst into flames in 1969 as a result of industrial discharge. As these visible issues have diminished, environmental scientists have found themselves faced with questions that are more difficult to identify and are more intractable in nature. This has led, in turn, to advances in the investigative techniques used to investigate environmental crimes.

It is impossible to pinpoint the exact birth date of forensic environmental science. However, one source attributes the origin of the term environmental forensics to the scientific contractor Battelle in the late 1990s (Haddad, 2004). One of the company's specialties is forensic environmental chemistry, and the company provides services in hydrocarbon fingerprinting, contamination identification, and product identification. Regardless of when the field was named, most sources would agree that the field began gathering momentum about 30 years ago. Since that time, various subdivisions have emerged. Some of these divisions have their roots in diverse areas such as geology, toxicology, biology, physics, and chemistry. As such, the term environmental forensics might be considered a misnomer for two reasons. The first is the tendency of the word forensics to be semantically confusing, because it has no real meaning when used in this context. The second is the loss of the word science, for this serves as a necessary reminder of the field's vast and diverse capabilities, spanning across not just one but many sciences.

The term environmental forensics is often misapplied to what should rightfully be called forensic environmental chemistry. For example, environmental forensics has been defined as “the systematic investigation of a contaminated site or an event that has impacted the environment,” a definition that is clearly biased toward the chemistry perspective (Stout et al., 1998). The broad capabilities of the field are unnecessarily simplified to the question: Who caused the contamination, and when did it occur? (Ram et al., 1999). Surely this is not the only question that environmental forensics is capable of answering. Nevertheless, this mindset has persisted because it is acknowledged and reaffirmed repeatedly. Many of the shortfalls of the earlier definitions of environmental forensics have been identified and amended in subsequent definitions. Many of these revisions offer a more generic, all-inclusive definition. One source defines forensic environmental science simply as “litigation science” (Murphy, 2000); another as “environmental ‘detective work’ … operating at the interface junction points of several main sciences including chemistry and biochemistry, biology, geology and hydrogeology, physics, statistics, and modeling” (Petrisor, 2005). Vives-Rego (2004) defines it not just as the environmental application of chemistry, biology, and geology, but as “science and the art of deduction.” Finally, Carpi and Mital (2000) define it as “the scientific investigation of a criminal or civil offense against the environment.” These updated definitions more accurately reflect the capabilities of forensic environmental science beyond the chemistry realm. In particular, the definition provided by Carpi and Mital (2000) specifically includes the use of DNA to solve crimes perpetrated against wildlife and plant life. In this chapter we focus on the specific subarea of forensic environmental chemistry and leave to another source the broader description of the methods and techniques that apply to environmental forensics.

However one chooses to define this growing field, one thing is certain: Forensic environmental science is filling the significant niche left void by forensic science and environmental science. Due in large part to its close association with the core sciences, forensic environmental science has experienced significant growth since its inception, especially in recent years. Aside from technological achievements in the past 30 years, several important advances have helped propel forensic environmental science from a burgeoning offshoot of forensic science to a scientific discipline in its own right. One such advancement was the founding of the journal Environmental Forensics in 2000 (Taylor & Francis, London). Although research pertaining to forensic environmental science occurred before the journal existed, the journal can be credited with offering a place for environmental research that falls under the forensic science umbrella. Thus, Environmental Forensics provides a forum to facilitate the exchange of information, ideas, and investigations unique to forensic environmental science (Wenning and Simmons, 2000).

Forensic environmental science has become such a diverse field that it is difficult to find a single work that adequately covers all its subdisciplines. The literature on the subject that enjoys the most success does so because it focuses on a specific area of forensic environmental science. As such, in this chapter we focus on forensic environmental chemistry. Our aim is to elaborate on several key areas of forensic environmental chemistry, perhaps where other resources have been unable to or have failed to do so. In particular, we focus on chemical fingerprinting and its subsidiaries, such as hydrocarbon fingerprinting, isotope fingerprinting, and complex mixture fingerprinting. Chemical fingerprinting attempts to individualize a chemical and trace it back to its origin. This technique has become increasingly important not only to identify that a chemical spill has indeed occurred, but also to identify the party responsible. We also focus on spatial analysis for the purpose of source attribution. Several cases are discussed that are illustrative of the capabilities of spatial analysis and chemical fingerprinting as they pertain to forensic environmental chemistry.

1.2 Chemical Fingerprinting

Chemical fingerprinting is a subsidiary of forensic environmental chemistry that examines the constituents of a mixture for the purpose of creating a unique chemical signature that can be used to attribute the chemicals to their source. At one time it was sufficient to arrive at a generic classification and quantitation of the chemical mixture so that appropriate remediation measures could be designed and implemented. However, modern analytical techniques that are focused on individualizing and associating a mixture with a source have become increasingly popular, both for liability reasons and because of the recognition and attempt to apportion liability when multiple and/or temporally distant parties may be responsible for chemical contamination. The main objectives of chemical fingerprinting are to characterize, quantitate, and individualize a chemical mixture (Alimi et al., 2003). In this section we provide the reader with a review of some of the constituents of a mixture that are useful for assembling a chemical fingerprint as well as the techniques used to screen for these constituents. The efficacy of these analytes and of detection techniques are evaluated by illustrating their application in several cases.

1.2.1 Hydrocarbon Mixtures

The majority of chemical spills involve hydrocarbon mixtures; as a result, many techniques are tailored for these mixtures (Sauer and Uhler, 1994). Early techniques were used simply to quantify the total petroleum hydrocarbon concentration, but modern techniques must be capable of quantification as well as identification and individualization (Zemo et al., 1995). The latter two are especially important for litigation purposes. However, identification and individualization may also provide for the design of a more effective remediation plan that accounts for dispersal, weathering, and degradation of the chemical mixture (Zemo et al., 1995).

Petroleum hydrocarbon mixtures may be broadly classified into three general groups. Petrogenic hydrocarbons are present in crude oil or its refined products. Pyrogenic hydrocarbons are the combusted remnants of petrogenic hydrocarbons and other by-products. Biogenic hydrocarbons are those that arise from more recent natural processes: for example, swamp gas or the volatile hydrocarbon mixtures released by decaying plant or animal tissue exposed to anaerobic conditions. Within each of these three broad groups, hydrocarbons are generally separated into three types: saturated aliphatics (alkanes), unsaturated aliphatics (alkenes, etc.), and aromatic hydro...

Table of contents

• Cover
• Title Page
• Copyright
• Preface
• Contributors
• Chapter 1: Forensic Environmental Chemistry
• Chapter 2: Principles and Issues in Forensic Analysis of Explosives
• Chapter 3: Analysis of Fire Debris
• Chapter 4: Forensic Examination of Soils
• Chapter 5: Analysis of Paint Evidence
• Chapter 6: Analysis Techniques Used for the Forensic Examination of Writing and Printing Inks
• Chapter 7: The Role of Vibrational Spectroscopy in Forensic Chemistry
• Chapter 8: Forensic Serology
• Chapter 9: Forensic DNA Analysis
• Chapter 10: Current and Future Uses of DNA Microarrays in Forensic Science
• Chapter 11: Date-Rape Drugs with Emphasis on GHB
• Chapter 12: Forensic and Clinical Issues in Alcohol Analysis
• Chapter 13: Fundamental Issues of Postmortem Toxicology
• Chapter 14: Entomotoxicology: Drugs, Toxins, and Insects
• Color Plates
• Index