Emerging POPs : Perfluorochemicals and Their Ecodynamics

 

Kurunthachalam Kannan

Wadsworth Center, New York State Department of Health

                                                                                                                                                                                    

Persistent organic pollutants (POPs) are a group of organic chemicals exhibiting the combined properties of persistence, bioaccumulation, toxicity, and long-range environmental transport.  Currently, twelve substances or substance groups are included under the Stockholm Convention on POPs.   The United Nations Environmental Program (UNEP) also suggests the need for identifying additional POPs as candidates for future international action.  While monitoring studies are being implemented in developing countries to evaluate sources and effects of the twelve POPs, the samples or sample extracts collected for current monitoring can be used for the determination of emerging POPs in environmental and biological matrices.  Such planning will provide effective and efficient use of resources.  Several contaminants such as, polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), and perfluorooctanesulfonate (PFOS) are reported as emerging global environmental contaminants.  In this presentation, environmental distribution, sources, dynamics and impacts of a new class of global contaminants, namely perfluorinated compounds (PFCs), will be discussed.

 

Perfluorinated compounds are used in a wide variety of consumer products for more than 50 years.  These compounds are persistent and bioaccumulative in the food chain.  But, until recently, the environmental distribution of PFCs was unknown. Recent developments in analytical techniques using high performance liquid chromatography-negative ion electrospray tandem mass spectrometry (HPLC-MS/MS) permitted the survey of PFCs in biota and water on a global scale.  The HPLC-MS/MS analysis detected PFOS, perfluorooctanesulfonamide (PFOSA), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonate (PFHS) in human blood and wildlife tissues from all over the world.   In biological matrices PFOS is the most abundant compound of all the perfluorinated acids measured so far.  In water, PFOA is a major perfluorinated contaminant detected in several locations.  In air samples, particularly in indoor air, fluorotelomer alcohols and perfluoroalkylsulfonamidoalcohols are the major perfluorochemicals measured.

 

High concentration of PFOS in biological samples including humans and wildlife is due to its great biomagnification potential.  Despite the predominance of PFOA in water samples, the bioconcentration and biomagnification potentials of this compound are relatively low.  While PFOS is a metabolic product of various sulfonated perfluorochemicals, PFOA is a metabolite of fluorotelomer alcohols and is also processing aid in the production of various fluoropolymers. 

The occurrence of PFCs in remote marine environment has led to several hypotheses related to long-range transport of PFCs.  PFOS and PFOA, because of their strong acidity, are expected to be present in ionized form, with little propensity for volatilization, under normal environmental conditions.  Atmospheric transport of relatively more volatile precursor compounds, such as polyfluoroalkylated sulfonamides, sulfonamidoalcohols, and fluorotelomer alcohols, to remote marine locations, where the precursors break down, by biological or non-biological degradation processes, to PFOS and PFOA, has been a plausible explanation for the occurrence of these compounds in biota from remote areas.   However, studies on the measurement of precursor compounds in water or air from remote areas are not available.  Precursor compounds are also expected to be present in biota which has less metabolic capacity.  Monitoring of precursor compounds in biotic and abiotic matrices is a subject of further investigation.

 

The complex chemistry of PFCs also poses problems in their risk assessment.  Toxicological studies have focused primarily on PFOA and PFOS, but not on intermediates of PFC metabolism and precursor compounds.   PFOS has been shown to affect genes involved in hormone regulation and fatty acid metabolism.  Further studies are needed to understand the toxic effects of precursors of PFCs including telomer alcohols.  Studies are also needed to understand the critical endpoint (most sensitive biomarker of exposure) of toxicity, which can be used in the assessment of risks from exposure to PFCs.    

 

Overall, perfluorinated acids are global environmental pollutants.  Several of the PFCs are persistent and bioaccumulative in the food chain.  These compounds can reach remote marine environment.  The mechanisms of transport and toxic effects of these compounds are the subjects of further investigations.