This volume provides a primer on the environmental challenges created by perfluorinated compounds (PFCs). PFCs have been documented to occur globally in wildlife and humans. The most commonly studied PFC classes are the perfluorinated sulfonates (PFSAs) and the perfluorinated carboxylates (PFCAs). The most commonly detected classes of these compounds in the environment are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). These compounds are bioaccumulative and very persistent to abiotic and biotic degradation. Compounds like PFOS are known as persistent organic pollutants (POPs) under the Stockholm Convention. Both PFCAs and PFSAs have been produced for more than 50 years, but have only become of interest to regulators and environmentalists since the late 1990s. Renewed and increasing interests in these compounds are due to the recent advances in analytical methodology that has enabled their widespread detection in the environment and humans at trace levels. PFCs have been found in outdoor and indoor air, surface and drinking water, household dust, animal tissue, human blood serum, and human breast milk. Because of the high persistence of PFOS and PFOA, the two compounds accumulate in the environment; concentrations in humans and environmental media are now believed to be at levels of great concern. Of acute concern to communities is the presence of these compounds in a number of drinking water supplies in the US, Canada, and throughout Europe and other continents.

For more than five decades these chemical compounds have been widely used as processing aids and surfactants in the manufacturing of fluoropolymers, which have gone into the making of a multitude of consumer-oriented commercial products. Fluoropolymers such as polytetrafluoroethylene (PTFE) are films (e.g., on nonstick cookware) or membranes (e.g., in outerwear) and are characterized by a fluorocarbon chain within the polymer backbone. Residual PFCA is present in fluoropolymer films and membranes used in manufacturing many different consumer articles. These chemicals are present as reaction impurities in various consumer products containing fluorinated polymers, which are added to products to make them stain, soil, water, and grease resistant.

Fluorinated polymers comprise a hydrocarbon backbone (e.g., polyesters, polyurethanes, polyethers) with perfluorinated side-chains. Consumer products treated with fluorinated polymers include clothing and textiles, carpets, leather, paper, and cardboard. PFSAs and related compounds have often been incorporated into fluorinated polymers used in making protective coatings for carpets and apparel, paper coatings approved for food contact, insecticide formulations, and surfactants, as, for example, in firefighting foams. Many articles in general use by consumers have found their way to municipal landfills at the end of their life cycle where years of leaching into the subsurface has resulted in contaminated groundwater. Facilities like airports, military bases, refineries, shipping ports, oil terminals, and many industrial complexes have for decades relied on and stockpiled aqueous firefighting foams, which contain PFAS compounds. These facilities have performed countless firefighting training drills, plus in some instances, responded to fire incidents in which the spent foams were then washed on to land, into surface waters, and into sewers which impacted public water treatment plants.

In 2001, the principal manufacturer of PFOS and related compounds with a chain length of eight carbon atoms ceased its manufacturing, leaving only small producers in Europe and Asia. In 2006, the USEPA began working with eight major leading companies in the per- and polyfluoroalkyl substances (PFASs) industry to join in a global stewardship program to commit to achieve, no later than 2010, a 95 percent reduction (as measured from a year 2000 baseline) in facility emissions to all media of perfluorooctanoic acid (PFOA), precursor chemicals that can break down to PFOA, and related higher homologue chemicals and product content levels of these chemicals; and further, to commit to working toward the elimination of these chemicals from emissions and products by 2015. Participating companies include Arkema, Asahi, BASF Corporation (successor to Ciba), Clariant, Daikin, 3M/Dyneon, DuPont, and Solvay Solexis. While these phase-out programs have largely been on track, the persistence of these chemical compounds in the environment from more than five decades of use continues to provide an open pathway to human exposure, particularly through the ingestion of contaminated water supplies. Furthermore, the chemical compounds, which have been touted as environmentally friendly replacements for PFAS (known as telomers), are now proving to be just as controversial as they also bioaccumulate, in some instances actually breakdown to PFOS/PFOA related chemicals when in the environment, and have few and incomplete health risk studies which support claims that the products are of “green” chemistry. PFAS are so stable in the environment that, in fact, the only way these man-made chemical compounds can be effectively destroyed is by high temperature incineration at thousands of degrees Celsius. The general population (consumers) continues to be exposed to PFOS and PFOA from the use of various PFC-containing products and the intake of contaminated food, environmental media, and house dust. In fact, comprehensive assessment of consumer exposure to PFOS and PFOA, including all relevant pathways, is missing from the scientific arsenal, thus placing the public at indeterminate levels of risk.

The USEPA and other international regulatory and health agencies are concerned about these long-chain PFCs because they are now found worldwide in the environment, wildlife, and in humans. Many or all of these chemical compounds bioaccumulate in wildlife and humans, are extremely persistent in the environment, and many are toxic to laboratory animals and wildlife, producing reproductive, developmental, and systemic effects in laboratory test animals. The USEPA anticipates that continued exposure could increase body burdens to levels that would result in adverse outcomes. The agency has already concluded that PFOA is a “likely human carcinogen.” It further points to numerous studies which document the prevalence of PFOA in the human environment and in bodily tissues, including studies that report the presence of PFOA in infants’ umbilical cord blood.

According to the Agency for Toxic Substances and Disease Registry, PFAS accumulates and remains in the human body, and the amount reduces very slowly over time. Scientists and medical professionals are concerned about the effects of these chemicals on human health and the lack of comprehensive health risk studies. The studies that have been conducted for humans have shown that certain PFAS may be associated with developmental delays in the fetus and child, including possible changes in growth, learning, and behavior; decreased fertility and changes to the body’s natural hormones; increased cholesterol; changes to the immune system; increased uric acid levels; changes in liver enzymes; and prostate, kidney, and testicular cancer.

In preparing this volume, the author examined more than 36,000 well sampling results from public water supplies across the United States. The analysis identifies many states and counties that are potentially at risk from exposure to these chemicals through endangered public water supplies. The study presented in this volume further accentuates a recently published study by the Harvard T.H. Chan School of Public Health, which reports levels of PFAS that exceed federally recommended safety levels in public drinking-water supplies for 6 million people in the United States, and that up to 100 million people could potentially be at risk. In Europe, the problem may be even more acute as guidelines for drinking water quality are less restrictive than in the United States, and certainly there remain many other parts of the world where PFAS chemicals continue to be produced and used while no enforceable drinking water standards exist. Groundwater contamination by these chemicals is a worldwide problem. This volume covers the EU as well as US drinking water quality advisories and recommended limits.

The volume further explores options for groundwater treatment. Unfortunately, the only technology currently applicable is carbon adsorption. While this water treatment technology has been around for decades, its adaptation to remediating water supplies that are impacted by PFAS compounds is still evolving. Each application poses significant technical and engineering challenges due to the presence of other contaminants and the levels of cleanup that are now being imposed to achieve quality that is considered low risk from exposure. The technology thus far has proven costly and has shown mixed results in certain operations. The volume explores the design criteria and steps that are taken to evaluate this technology for applications to public water supplies.

PFAS in the environment and especially in drinking water supplies represents a worldwide problem. It is fair to state that these chemicals may very well represent the chemical industry’s tobacco. It is a well-known historical fact that the tobacco industry understood and concealed the addictive nature and harmful effects of smoking from the public in order to reap untold fortunes. The chemical industry most certainly faces the very same scrutiny and public scorn because considerable evidence is now emerging that some chemical providers understood how dangerous these chemicals are but failed to warn of the consequences of their use. Placing this in perspective, a mere handful of chemical manufacturers created, developed, and distributed a broad spectrum of end-user market applications and products which incorporated these chemical ingredients whose consequence is only now being understood to have foreboding impacts to natural resource damages and worldwide public safety.

There are vast numbers of publications and articles which are in the public domain and available through the WWW on this subject. Yet the literature is fragmented, and even confusing and misleading. There does not appear to be a single source or even a handful of publications which provide a comprehensive overview of the issues surrounding these contaminants in straightforward language. The chemistry of these surfactants is sophisticated, complex, and in a number of instances, being hidden from the public. The fate and transport of these chemicals is incomplete and not fully defined. There is a noticeable lack of comprehensive health risk studies which should be of great concern to national and local governments. Further, there should be focused attention given to historical exposure issues to communities that are the result of legacy pollution — an area of concern that seems to receive little attention in the media and in state of the art reviews. To this end, the author prepared this volume for a broad spectrum of readers. It is intended as a primer — for the public at large, for public water providers that are now faced with monitoring these chemical contaminants and may be facing costly remedies, for environmental engineers who are now consulting and working to remedy legacy contamination problems stemming from the use and disposal of products and wastes containing PFAS, and for environmental policy makers who need to be much more versed in the public health risk issues and do require more than a cursory background to understand the pathways of exposure and their consequences to public risks.

There are ten chapters to this volume: Chapter 1 provides an overview of fluoropolymers and PFCs; Chapter 2 covers historical uses and evolution of PFCs; Chapter 3 discusses the use of these chemicals in firefighting foams; Chapter 4 covers health risk studies; Chapter 5 provides an overview of environmental concerns; Chapter 6 discusses supply chain and pathways of exposure to these chemicals in manufacturing and consumer products; Chapter 7 summarizes drinking water and other standards; Chapter 8 provides an overview of water treatment technology options; Chapter 9 covers adsorption technologies which are currently viewed as the preferred water treatment technology; and finally, Chapter 10 provides some cases studies.

The author wishes to thank Mohit Dayal of No-Pollution Enterprises for reviewing and editing the volume and Scrivener Publishing for its fine production of this book.

Nicholas P. Cheremisinoff, Ph.D.