Evolution of Organic Analytical Methods in Environmental Forensic Chemistry

Over the past few decades the development of environmental regulations, advances in analytical chemistry and other scientific disciplines, and increased rigor in quality control procedures have created a new discipline, environmental forensics. The need for analytical methods that determine qualitatively and quantitatively organic compounds in the environment, especially in drinking waters, was recognized in the early 1950s. These methods were developed gradually by the early 1960s. The important tools of gas chromatography and mass spectroscopy that evolved in the 1970s provided the early environmental forensic chemist for the first time with the ability to produce scientifically sound data that was admissible in court. By the 1990s, multivariate statistical techniques became available and accepted, including principal component analysis (PCA) and polytopic vector analysis (PVA). These techniques, coupled with the advancing analytical methods, have enabled forensic investigator tools to evaluate and demonstrate unique attributes of a set of data. Analyses of marker compounds, PCBs, PCDD/Fs and petroleum hydrocarbons are all shown to be potentially valuable in deciphering the source and fate of contamination. This paper shows how advancements in environmental analytical chemistry provide the forensic chemist with tools to assess the source(s) of site contamination.     

Application of Forensic Techniques for Age Dating and Source Identification in Environmental Litigation

A multitude of forensic techniques are available for age dating and source identification, including corrosion models for underground storage tanks, the commercial availability of a compound, chemical associations with discrete types of manufacturing processes, chemical profiling, proprietary additives, stable isotope analysis, degradation models, biomarkers and contaminant transport models. The selection and use of these techniques in environmental litigation must be thoroughly understood and applied to be effective as forensic evidence. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to present an overview of commonly used environmental forensic techniques and their possible applications so that a user can decide which technique or combination of methods is most appropriate for their case.     

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.     

The application of positive matrix factorization in the analysis, characterisation and detection of contaminated soils

Multivariate factor analytical techniques are widely used for the approximation, in terms of a linear combination of factors, of multivariate experimental data. The chemical composition of soil samples are multivariate in nature and provide datasets suitable for the application of these statistical techniques. Recent developments of multivariate factor analytical techniques have led to the approach of Positive Matrix Factorization (PMF), a weighted least squares fit of a data matrix in which the weights are determined depending on the error estimates of each individual data value. This approach relies on more physically significant assumptions than methods like Principal Components Analysis which is frequently used in the analysis of soil datasets. In this paper we apply PMF to characterise the pollutant source in a set of geographically referenced soil samples taken within a 200 m radius of a site characterised by a high concentration of heavy metals. Each sample has been analysed for major and minor elements (using wavelength-dispersive X-ray fluorescence spectrometry), carbon, hydrogen and nitrogen (using a CHN elemental analyzer) and mercury (using cold-vapour atomic absorption spectrometry). Analysis of the soils using PMF resulted in a successful partitioning of variances into sources related to background soil geochemistry, organic influences and those associated with the contamination. Combining these results with a geostatistical approach successfully demarcated the main source of the combined organic and heavy metal contamination.     

Dimension reduction and source identification for multispecies groundwater contamination

Assessment of chemical contamination at large industrial complexes with long and sometimes unknown histories of operation represents a challenging environmental problem. The spatial and temporal complexity of the contaminant may be due to changes in production processes, differences in the chemical transport, and the physical heterogeneity of the soil and aquifer materials. Traditional mapping techniques are of limited value for sites where dozens of chemicals with diverse transport characteristics may be scattered over large spatial areas without documentation of disposal histories. In this context, a site with a long and largely undocumented disposal history of shallow groundwater contamination is examined using principal component analysis (PCA). The dominant chemical groups and chemical "modes" at the site were identified. PCA results indicate that five primary and three transition chemical groups can be identified in the space of the first three eigenvectors of the correlation matrix, which account for 61% of the total variance of the data. These groups represent a significant reduction in the dimension of the original data (116 chemicals). It is shown that each group represents a class of chemicals with similar chemo-dynamic properties and/or environmental response. Finally, the groups are mapped back onto the site map to infer delineation of contaminant source areas for each class of compounds. The approach serves as a preliminary step in subsurface characterization, and a data reduction strategy for source identification, subsurface modeling and remediation planning.     

Preliminary evaluation of bitumen contamination in environmental samples using comprehensive gas chromatography GcxGc – Time of flight mass spectrometry (GCxGC-TOFMS)

Abstract

Bitumen and bitumen impacted soil and water samples were investigated for their relative chemical composition using comprehensive gas chromatography GcxGc – time of flight mass spectrometry (GCxGC-TOFMS). The results reveal the presence of key compounds which could serve as environmental biomarkers for bitumen impacted soils and aquifers. Prominent alkanes such as 3-methylpentane; 2,2,4-trimethylpentane; 1,3,5-trimethyladamantane; 2,6,10-trimethyldodecane; 3-ethyl-2,2-dimethyl pentane were tentatively identified and are likely potent biomarkers in environmental forensic assessment of bitumen contamination while the presence of some aromatic compounds: 1,2-benzenedicarboxylic acid, 1,2-dimethyl-3-propylbenzene; 3,4-bis(methoxycarbonyl)benzoic acid; 1,3-bezenedicarboxylic acid, 1,2-benzenediol; 1,3-dimethylbenzene; 1,2-2-(2-ethylhexoxycarbonyl)benzoic acid; (4-methylpentan-2-yl)benzene; 2,4-dimethyl benzo(H)quinolone will further confirm the bitumen contamination in an area under investigation. A host of additional compounds were tentatively identified, mainly in the bitumen samples. The results obtained in this study provides baseline data for effective monitoring, and source apportionment of oil/oil products spills.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Air sampling and analysis of volatile organic compounds with solid phase microextraction

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Comments on the NAS Report: Odors From Stationary and Mobile Sources

ABSTRACT

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Approaches for quantifying reactive and low-volatility biogenic organic compound emissions by vegetation enclosure techniques - part A

The high reactivity and low vapor pressure of many biogenic volatile organic compounds (BVOC) make it difficult to measure whole-canopy fluxes of BVOC species using common analytical techniques. The most appropriate approach for estimating these BVOC fluxes is to determine emission rates from dynamic vegetation enclosure measurements. After scaling leaf- and branch-level emission rates to the canopy level, these fluxes can then be used in models to determine BVOC influences on atmospheric chemistry and aerosol processes. Previously published reports from enclosure measurements show considerable variation among procedures with limited guidelines or standard protocols to follow. This article reviews this literature and describes the variety of enclosure types, materials, and analysis techniques that have been used to determine BVOC emission rates. The current review article is followed by a companion paper which details a comprehensive enclosure technique that incorporates both recommendations from the literature as well as insight gained from theoretical calculations and practical experiences. These methods have yielded new BVOC emission data for highly reactive monoterpenes (MT) and sesquiterpenes (SQT) from a variety of vegetation species.     

Investigation,Remediation and Cost Allocation of Contaminants from the Britannia Mine in British Columbia: A Case Study

This case study, from the province of British Columbia, is described to illustrate the use of environmental forensic techniques. The study involves acid rock drainage (ARD) from the Britannia Mine, a mine located in southwestern British Columbia, that has been closed for approximately 25 years and discharges between 4 and 40 million litres of ARD, depending on the time of year into nearby Howe Sound every day. The ARD occurs as an oxidation of sulphide mineralization exposed to air and water. The sources of ARD contamination from this site are copper, aluminium, iron, zinc and manganese. Current copper concentrations discharging from the 4100 Portal Level range from 40 to 100 mg/L. Environmental forensic techniques are applied to describe the origin of the contaminant release, the timing of the release, the distribution of the contamination, finding the responsible parties and allocating remediation costs for cleanup. Other forensic techniques described include the use of geochemistry to determine contaminant degradation.     

State of the Art Report on Multivariate Chemometric Methods in Environmental Forensics☆

Environmental forensic analysis has evolved significantly from the early days of qualitative chemical fingerprint evaluations. The need for quantitative rigor has made the use of numerical methods critical in identifying and mapping contaminant sources in complex environmental systems. Given multiple contaminant sources, the environmental scientist is faced with the challenge of unraveling the contributions of multiple plumes with overlapping spatial and temporal distributions. The problem may be addressed through a multivariate statistical approach, but there is a mind-boggling array of the available "chemometric" methods. This paper provides an overview of these methods, along with a review of their advantages, disadvantages, and pitfalls. Methods discussed include principal component analysis and several receptor-modeling techniques.     

State of the Art Report on Multivariate Chemometric Methods in Environmental Forensics

Environmental forensic analysis has evolved significantly from the early days of qualitative chemical fingerprint evaluations. The need for quantitative rigor has made the use of numerical methods critical in identifying and mapping contaminant sources in complex environmental systems. Given multiple contaminant sources, the environmental scientist is faced with the challenge of unraveling the contributions of multiple plumes with overlapping spatial and temporal distributions. The problem may be addressed through a multivariate statistical approach, but there is a mind-boggling array of the available “chemometric” methods. This paper provides an overview of these methods, along with a review of their advantages, disadvantages, and pitfalls. Methods discussed include principal component analysis and several receptor-modeling techniques.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative "fingerprinting" analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the "prime suspects" for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative “fingerprinting” analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the “prime suspects” for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Critical Review of Environmental Forensic Techniques: Part II

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a chemical, chemical associations with discrete types of equipment, chemical profiling, degradation models and contaminant transport models. The success of these techniques in environmental litigation and their applicability to a particular fact situation is rarely discussed in the literature. When these techniques are introduced as scientific evidence, their governing assumptions and the adequacy of the underlying data are rigorously scrutinized and often, successfully challenged. The purpose of this paper is to review selected forensic techniques and discuss their merits so that the user can select the technique or combination of techniques most appropriate for the factual elements of the case.