It is the responsibility of humans, as environmental stewards, to monitor our impact on the environment so that efforts can be made to remediate the effects of our actions and change behaviors. To better understand our environmental footprint, sensitive and simple analytical methods are needed to quantify the contaminants that we discharge into our natural surroundings. Emerging environmental contaminants are of particular concern because there is limited or no information available on their occurrence, fate, and toxicity. As a result, the implications of using these chemicals are not well understood. Therefore, accurate environmental data are needed to help scientists and government policy-makers make informed decisions on research directions and chemical regulation. However, challenges exist for the analysis of emerging contaminants, including a lack of suitable analytical standards and internal standards, their broad range of chemical properties, and that they are frequently present at trace levels and in complex environmental matrices. The work presented within this dissertation focuses on the development, validation, and comparison of analytical methodologies based on large-volume injection high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS) for the analysis of emerging environmental contaminants in aqueous environmental matrices. Large-volume injection (e.g. 900 [micro]L to 4,500 [micro]L) is an analytical technique that eliminates sample preparation associated with pre-concentration by injecting larger-than-traditional volumes of sample directly onto a HPLC column. In Chapter 2, a direct aqueous large-volume injection method was developed and validated for the quantification of natural and synthetic androgenic steroids in wastewater influent, wastewater effluent, and river water. This method was then applied to hourly composite samples of wastewater influent that were taken over the course of a single day. This work expands on the research of the endocrine-disrupting chemicals that occur in wastewater and provides an estimate of the community use/abuse of synthetic androgenic steroids. Environmental analytical methods should be as environmentally friendly as possible and efforts should be made to reduce the waste generated during analysis while maintaining analytical performance. In Chapter 3, a method based on large-volume injection was compared to two methods based on solid-phase extraction. The purpose of this comparison was to demonstrate that the same method performance could be achieved by large-volume injection as that by solid-phase extraction while reducing waste, labor, and costs. Estrogens and perfluorinated chemicals were used as model analytes and wastewater influent was used as a model matrix. The results of this study provide convincing reasons for analysts to adopt large-volume injection as an alternative to solid-phase extraction. In Chapter 4, a novel analytical method was developed and validated to quantify newly-identified and legacy fluorinated chemicals in groundwater. The final method combined micro liquid-liquid extraction, non-aqueous large-volume injection, and orthogonal chromatographic separations. Ground water samples collected from six different U.S. military bases was used to demonstrate the method. This is the first report on the occurrence of these newly-identified fluorinated chemicals in any environmental media and serves as a rational for conducting future research on their environmental fate and toxicity. The breadth of the research presented in this dissertation advances the field of environmental analytical chemistry in several areas. First, classes of environmental contaminants for which there is limited (synthetic androgenic steroids) or no (newly-identified fluorochemicals) environmental data were studied. Second, novel methods based on direct-aqueous and non-aqueous large-volume injection were developed and validated to identify and quantify those contaminants. Third, it was demonstrated that solid-phase extraction is not a "necessary evil" needed to develop methods for emerging environmental contaminants in aqueous matrices. Finally, this work is a platform on which other environmental chemists can use to develop large-volume injection methods in the future.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 - 3,000 ng/L. The method provided excellent recovery (86 - 119%) and precision (10 - 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C60 surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices.

This book is an updated, completely revised version of a previous volume in this series entitled: ENVIRONMENTAL ANALYSIS -- Techniques, applications and quality assurance. The book treats different aspects of environmental analysis such as sample handling and analytical techniques, the applications to trace analysis of pollutants (mainly organic compounds), and quality assurance aspects, including the use of certified reference materials for the quality control of the whole analytical process. New analytical techniques are presented that have been developed significantly over the last 6 years, like solid phase microextraction, microwave-assisted extraction, liquid chromatography-mass spectrometric methods, immunoassays, and biosensors. The book is divided into four sections. The first describes field sampling techniques and sample preparation in environmental matrices: water, soil, sediment and biota. The second section covers the application areas which are either based on techniques, like the use of gas chromatography-atomic emission detection, immunoassays, or coupled-column liquid chromatography, or on specific application areas, like chlorinated compounds, pesticides, phenols, mycotoxins, phytotoxins, radionuclides, industrial effluents and wastes, including mine waste. Validation and quality assurance are described in the third section, together with the interpretation of environmental data using advanced chemometric techniques. The final section reports the use of somewhat advanced analytical methods, usually more expensive, less routinely used or less developed, for the determination of pollutants.

This book addresses the highly relevant subject of emerging pollutants, which are especially alarming since most of the available treatment technologies are unable to degrade them. It discusses the sources of these pollutants and their fate in the environment, and the main tools available for their analysis. It also describes the representative environmental matrices (air, soil and water) and appropriate analytical methods for each matrix. Furthermore, it examines aspects of toxicology, chemometrics, sample preparation and green analytical chemistry. As such, it provides a broad overview of the potential analytical approaches for monitoring and controlling emerging pollutants. This book fills a gap in the literature, and is a valuable resource for all professionals concerned with emerging pollutant control in real-world situations.

With an increasing population, use of new and diverse chemicals that can enter the water supply, and emergence of new microbial pathogens, the U.S. federal government is faced with a regulatory dilemma: Where should it focus its attention and limited resources to ensure safe drinking water supplies for the future? Identifying Future Drinking Water Contaminants is based on a 1998 workshop on emerging drinking water contaminants. It includes a dozen papers that were presented on new and emerging microbiological and chemical drinking water contaminants, associated analytical and water treatment methods for their detection and removal, and existing and proposed environmental databases to assist in their proactive identification and regulation. The papers are preceded by a conceptual approach and related recommendations to EPA for the periodic creation of future Drinking Water Contaminant Candidate Lists (CCLsâ€"produced every five yearsâ€"include currently unregulated chemical and microbiological substances that are known or anticipated to occur in public water systems and that may pose health risks).

Illicit drugs are an emerging class of environmental contaminants and mass spectrometry is the technique of choice for their analysis. This landmark reference discusses the analytical techniques used to detect illicit drugs in wastewater and surface water, details how to estimate the levels of contaminants in the environment, and explores the behavior, fate, and toxic effects of this new class of contaminants, now a ubiquitous presence in wastewater and surface water. The book details how an estimate of illicit drug consumption in a given population can be developed from an analysis of the residues of illicit drugs in wastewater. An important resource for analytical chemists, environmental researchers, forensic scientists, biologists, and toxicologists.

The presence of contaminants of emerging concern (CECs) in the environment is a growing field of research for analytical environmental scientists. CECs are a class of anthropogenic pollutants not regulated by governmental agencies, and their potential deleterious environmental and human impacts are largely unknown. One of the main sources of CEC entry into the aquatic environment is wastewater treatment plant (WWTP) effluent as the treated water is often released into bodies of water, such as river and streams. Because most WWTPs were not designed to remove organic micropollutants, many CECs are poorly removed in traditional WWTPs and persist in the treated effluent waters. As a model system for study, the University Park WWTP treats the wastewater from the Penn State main campus. Following primary and secondary treatment, effluent water is then disinfected using sodium hypochlorite ("chlorine contact") and pumped for spray irrigation of over 500 acres of agricultural and forested lands called the Living Filter. The full characterization of CECs in environmental matrices requires the use of both targeted and non-targeted analysis employing a variety of advanced analytical techniques and multi-residue extraction methods. Comprehensive two-dimensional gas chromatography (GCxGC) coupled to time of flight mass spectrometry (TOFMS) is utilized for the separation and analysis of complex samples, such as wastewater. In these studies, GCxGC-TOFMS has been utilized for the non-targeted analysis of wastewater influent, effluent, and Living Filter irrigation water. Over the course of three years, these samples were investigated for CECs, revealing a new class of benzotriazole corrosion inhibitors and their transformation products. The tentatively identified chloromethyl-benzotriazole isomers were detected at higher concentrations in the effluent and irrigation water than the influent. Upon further investigation with a lab-scale synthesis, it was determined that the methyl-benzotriazoles in the influent react with sodium hypochlorite during chlorine disinfection to form previously unidentified chloromethyl-benzotriazoles. These compounds were not detected in the groundwater below the Living Filter. Traditionally, the extraction of wastewater and aqueous environmental samples is performed using liquid-liquid extraction (LLE). This method is time consuming and solvent intensive therefore a microextraction method, stir bar sorptive extraction (SBSE) was investigated. SBSE and LLE were compared for their application to multiclass organic contaminants in the University Park wastewater with GCxGC-TOFMS. LLE was found to be a better method for the quantitative analysis of a broader range of contaminants. SBSE was determined to be a more sensitive method for the non-targeted analysis of trace contaminants in effluent samples. These extraction methods were further tested and verified using wastewater from the Bellefonte, PA municipal WWTP as well as surface waters downstream of the WWTP outfall. 32 CECs, including a variety of pharmaceuticals and personal care products, were detected and tentatively identified in the samples. To further explore the fate and transport of CECs in the University Park wastewater, the soil and crops at the Living Filter were investigated. Specifically, corn roots, leaves, and grain were examined separately to determine the uptake and translocation of contaminants throughout the plant. The Living Filter samples were also compared to a corn crop control site at the agricultural research center at Rock Springs because it is not irrigated with the WWTP effluent. Target compounds detected in the soil and corn samples include herbicides, phthalates, and polycyclic aromatic hydrocarbons. Non-targeted principal component analysis of each sample type showed chemical differences between the control and Living Filter samples attributed to the treated wastewater irrigation. In addition, new chloro-dimethyl-benzotriazole compounds were tentatively identified in the wastewater as well as the Living Filter soil and corn root samples. Lastly, another class of CEC, microplastic particles (MPs), was investigated using a different set of analytical techniques. The surface characteristics and chemical composition of neat MP standards were compared to those extracted from personal care products and effluent water from the University Park WWTP. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, and Optical Profilometry were all utilized for a more comprehensive view of the MP samples. This proof-of-concept study is the first to combine the three methods for MP analysis and demonstrate that MPs extracted from personal care products and WWTP effluent differ greatly from neat microsphere standards of similar sizes. The following research presented in chapters 2-6 has been published or submitted for publication in peer reviewed journals. Chapter 2 has been published in Science of the Total Environment and chapter 6 was published in Analytical Methods. Chapter 3 has been accepted for publication in Talanta. Chapter 4 has been submitted for publication in Analytical Methods and chapter 5 has been submitted to Chemosphere. I am first author on all five of these publications.