PFCs In the Environment.

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Presentation transcript:

PFCs In the Environment

What are PFCs? Anthropogenic or “man-made” Fully fluorinated carbon chains Perfluorochemicals, Perfluorinated Compounds Polyfluorinated Compounds Used in many commercial and household products (Gao et. al. 2015)

Fluorine Most Electronegative element on the Periodic Table Typically exists in nature as an insoluble compound Very Pretty but dangerous (Okazoe 2009)

Carbon Not as pretty as Fluorine unless it’s a diamond Not as dangerous as Fluorine Basis for organic chemistry, as it occurs in all living organisms. (Dr. Nalley, C.U. 2015)

The Carbon-Fluorine Bond The C-F bond is the strongest in organochemistry This high-energy bond give PFCs extreme thermal and chemical stability Resists degradation Bioaccumulates

The Family is Large… Groups of PFCs: PASs – perfluoroalkyl surfactants PFCAs – perfluorocarboxylic acid PFSAs – polyfluorinated alkyl substances FTOH – fluorotelomer alcohols PFAAs – perfluoroalkyl acids Minnesota Pollution Control Agency (2008) http://www.pca.state.mn.us/index.php/view-document.html?gid=2855

Individual PFCs PFBA – perfluorobutanoic acid PFBS – perfluorobutane sulfonate PFPeA – perfluoropentanoic acid PFHxA – perfluorohexanoic acid PFHxS – perfluorohexane sulfonate PFHpA – perfluoroheptanoic acid PFOA – perfluorooctanoic acid PFOS – perfluorooctane sulfonate PFOSA – perfluorooctane sulfonamide PFNA – perfluorononanoic acid PFDA – perfluorodecanoic acid PFUnA – perfluoroundecanoic acid PFDoA – perfluorododecanoic acid Minnesota Pollution Control Agency (2008) http://www.pca.state.mn.us/index.php/view-document.html?gid=2855

The Two Most Studied PFCs are: PFOA – perfluorooctanoic acid PFOS – perfluorooctane sulfonate

These same qualities, allow them to persist in nature The unique qualities of PFCs make them very attractive in many industrial and manufacturing uses These same qualities, allow them to persist in nature They are resistant to biodegradation and have been shown to bioaccumulate (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

How is a PFC made? Two main processes use to produce PFCs… Electrochemical Fluorination (ECF) -uses electrolysis to produce a linear or branched isomer. Telomerization -chemical reaction to produce longer chains adding a hydrophyllic and hydrophobic end to the chain. Telomerized chains are useful as surfactants. (Jahnke et. al. 2007)

PFCs are most well noted for their use as Polymers and Surfactants… Polymer: a substance that has a molecular structure consisting chiefly or entirely of a large number of similar units bonded together, e.g., many synthetic organic materials used as plastics and resins.

Surfactant: a substance, such as a detergent that can reduce the surface tension of a liquid, thus allowing it to foam or penetrate solids; a wetting agent. Collins English Dictionary - Complete & Unabridged 2012 Digital Edition © William Collins Sons & Co. Ltd. 1979, 1986 © HarperCollins Publishers 1998, 2000, 2003, 2005, 2006, 2007, 2009, 2012

PFCs are found in 98% of Humans Worldwide PFCs are found in 98% of Humans Worldwide. How are PFCs getting into our bodies? Food Water Air Soil Products

Microwave Popcorn Bags Non-stick Cookware (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Household products… (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Personal Care Products & Cosmetics (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Textiles: Fabrics & Carpeting (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Waterproofing… (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Paints & Adhesives (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Fire Foams and Flame Retardants… (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

And many other products... (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Waste Sludge, Effluent Wastewater, Landfill Leaching… (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

Where they end up… (Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

(Domingo et. al. 2012; Ding et. al. 2012; Mao et. al. 2015)

PFCs have been found in ALL biological and environmental matrices… Air (indoor and outdoor) Water (surface and groundwater) Arctic Ice Soils Birds (avian species) Polar Bears (nonhuman mammals) Humans (mammals) Marine Organisms (Wen et. al. 2013)

Brief History of the PFC By accident, Roy J. Plunkett makes the discovery of what would become, the first PFCs (1938) (Lindstrom et. al. 2011)

The First of Many of Uses…WWII (Lindstrom et. al. 2011)

Timeline… 1949 - DuPont introduces Teflon® brand 1967 - FDA approves a Zonyl® for use in food packaging 1968 - Organic fluorine found in human serum 1978 - 3M reports PFOA found in blood of workers 1984 - PFOA found in local drinking water near Washington Works plant, WV Adapted from:(Lindstrom et. al. 2011)

1998 - 3M reports EPS fluoro-chemicals widespread in human blood bank 2000 - 3M announces phase out of C8 based chemistry 2002 - EPA begins review of data linking C8 to health problems 2006 - EPA and 8 major companies launch 2010/2015 PFOA Stewardship Program 2009 - PFOS and related compounds are listed under Annex B of the Stockholm Convention on Persistent Organic Pollutants Adapted from: (Lindstrom et. al. 2011)

PFCs are globally ubiquitous… Research was conducted to see how PFCs travel Observed: Tibetan Mountain Snow Readings taken from 1980-2010 Temporal Trends show a decrease, most likely due to the decrease in manufacturing Study done by Wang et. al. 2013

s 1. Mt. Muztagata, 2. Namco Lake, 3. Mt. Zuoqiupu. Adapted from: (Wang et. al. 2013)

(Wang et. al. 2013)

He compared three sites, with Arctic Ice. The purpose of Wang’s study was to determine, if possible, how PFCs were showing up in remote locations. He compared three sites, with Arctic Ice. His study also shows, that PFCs travel via the atmosphere, not just through oceans. The trend shows that PFC concentrations decreased as the manufacturing of PFCs decreased. (Wang et. al. 2013)

Air In a research study done by Fraser et. al. (2011), air samples were tested in office buildings. The findings were that the highest levels of PFCs were found in the newest building constructed, the second highest levels were recorded from an older building that was newly renovated, and the lowest levels were found to be in an older building with no renovations.

Health Concerns… Long half-lives of PFCs in Humans 2.3-7.3 years (Fraser et. al. 2011) Due to hydrophilicity and lipophobicity, it binds to proteins Proteins are the building blocks of our bodies Toxicity has been demonstrated in rodent, avian, reptilian, mammalian and nonmammalian wildlife. Immunotoxicity in Children (DeWitt et. al. 2012; Dixon et. al. 2012; Grandjean et. al. 2013)

Worth mentioning…. Standardization, although better now was not so evident in earlier studies Since PFCs are in so many products used in the laboratory, experiment results may/could have been compromised by the use of these items The general concensus is, more research is needed!

The Future Alternative compounds Remediation Efforts So prevalent, will be living with them a long, long, long time

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Dixon, Darlene, Casey E. Reed, Alicia B. Moore, Eugene A Dixon, Darlene, Casey E. Reed, Alicia B. Moore, Eugene A. Gibbs-Flournoy, Erin P. Hines, Elizabeth A. Wallace, Jason P. Stanko, Yi Lu, Wendy N. Jefferson, Retha R. Newbold, and Suzanne E. Fenton. Histopathologic Changes in the Uterus, Cervix and Vagina of Immature CD-1 Mice Exposed to Low Doses of Pefluorooctanoic Acid (PFOA) in a Uterotrophic Assay. Reproductive Toxicology. 2012, 33 (4), 506-512. Domingo, José L., Ingrid Ericson-Jogsten, Gemma Perelló, Martί Nadal, Bert Van Bavel, and Anna Kärrman. Journal of Agricultural and Food Chemistry. 2012, 60, 4408-4415.

Collins English Dictionary - Complete & Unabridged 2012 Digital Edition © William Collins Sons & Co. Ltd. 1979, 1986 © HarperCollins Publishers 1998, 2000, 2003, 2005, 2006, 2007, 2009, 2012 Fraser, Alicia J., Thomas F. Webster, Deborah J. Watkins, Jessica W. Nelson, Heather M. Stapleton, Antonia M. Calafat, Kayoko Kato, Mahiba Shoeib, Verónica M. Vieira, and Michael D. McClean. Polyfluorinated Compounds in Serum Linked to Indoor Air in Office Environments. Environmental Science and Technology. 2012, 46,1209-1215.

Gao, Yan, Jianjie Fu, Huiming Cao, Yawei Wang, Aiqian Zhang, Yong Liang, Thanh Wang, Chunyan Zhao, and Guibin Jiang. Differential Accumulation and Elimination Behavior of Perfluoroalkyl Acid Isomers in Occupational Workers in a Manufactory in China. Environmental Science and Technology. 2015, 49, 6953-6962. Grandjean, Philippe, Esben Budtz-Jørgensen. Immunotoxicity of perfluorinated alkylates: calculation of benchmark doses based on serum concentrations in children. Environmental Health. 2013, 12, 35.

Jahnke, Annika, Lutz Ahrens, Ralf Ebinghaus, Urs Berger, Jonathan L Jahnke, Annika, Lutz Ahrens, Ralf Ebinghaus, Urs Berger, Jonathan L. Barber, and Christian Temme. An improved method for the analysis of volatile polyfluorinated alkyl substances in environmental air samples. Analytical and Bioanalytical Chemistry. 2007, 387, 965-975. Lindstrom, Andrew B., Mark J. Strynar, and E. Laurence Libelo. Polyfluorinated Compounds: Past, Present, and Future. Environmental Science and Technology. 2011, 45, 7954-7961.

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Nalley, Elizabeth. Cameron University. 2015. Personal Contact. Okazoe, Takashi. Overview on the history of organofluorine chemistry from the viewpoint of material industry. Proceedings of the Japan Academy, Series B Physical and Biological Sciences. 2009, 85, 8, 276-289.

Wang, Xiaoping, Crispin Halsall, Garry Codling, Zhiyong Xie, Baiqing Xu, Zhen Zhao, Yonggang Xue, Ralf Ebinghaus, and Kevin C. Jones. Accumulation of Perfluoroalkyl Compounds in Tibetan Mountain Snow: Temporal Patterns from 1980 to 2010. Environmental Science and T echnology. 2014, 48, 173-181. Wen, Bei, Longfei Li, Yu Liu, Hongna Zhang, Xiaoyu Hu, Xiao-quan Shan, and Shuzhen Zhang. Mechanistic studies of perfluorooctane sulfonate, perfluorooctanoic acid uptake by maize (Zea mays L. cv. TY2). Plant and Soil: An International Journal on Plant-Soil Relationships. 2013. 370, 345- 354.