School of Chemical, Biological and Environmental Engineering (CBEE) Detection of Leaching Organic Migrants from Polyethylene Terephthalate (PETE #1) and Polycarbonate (PC #7) water bottles. Paul Dornath School of Chemical, Biological and Environmental Engineering (CBEE) Mentor: Dr. Skip Rochefort Partners: Brian Maloney (SBI) and Moey Handloser (ASE)

Chemical Leaching Chemicals from inside plastic i.e., small molecules moving through the solid polymer matrix Degraded surface particles Get skip example

Polyethylene Terephthalate (PETE) Plastic Known to consumers as #1 PETE in recycling codes Most common uses: water and 2 L. soda bottles Ester of ethylene glycol and terephthalic acid Shorten this “polyethylene …. You may know it best as pepsi bottles or #1 plastic. Here is it’s chemical composition… here’s what’s inportant… move on.

What May Cause PETE to Leach? UV radiation Photo-Fries rearrangement 310 nm wavelength Unreacted polymer and plasticizers from inside the plastic can diffuse at 40 C.

Why We Are Concerned Cause Effect Placement of PETE merchandise Unknown storage conditions Solar sterilization Effect Bad taste (acetaldehyde) Organic molecules entering into our body Really long…. Here’s a picture in India, look at all these bottles! Being exposed to sunlight for hours, days or weeks before they are sold. PAUL—include a picture that Moey had for using water bottles for purification of drinking water…corrugated water bottles on the roof. Also, show a picture of your rooftop bottle experiments.

Hypothesis and Objectives Sunlight causes PETE to degrade into organic fragments via Photo-Fries rearrangement and elevated heat. Compounds of interest are acetaldehyde, phthalate plasticizers and aromatic organic fragments. Objectives Determine if organic compounds leach from PETE bottles when exposed to sunlight using SPE and GC/MS Determine types of molecules using GC/MS Quantify extent of leaching as a function of exposure time using GC/MS

Method of Exposure Bottles placed on the roof of Kelley Engineering Center for up to 3 months Record temperatures three times per day (morning, noon, evening) Air temperature Inside middle and end bottles Underneath bottles PAUL..replace this picture with one of the bottles on the roof. These really show nothing---except your partners.

Polycarbonate (PC) Plastic Ester of Bisphenol A (BPA) and phosgene Commonly sold as Nalgene water bottles (#7 PC) and as baby bottles. Reports of BPA leaching have made them less popular and led to their removal from some markets Camelback Bottle Nalgene Bottle Just say “This is BPA and the BPA leaching has to be unreacted monomver Phosgene Bisphenol A A Polycarbonate

Bisphenol A Toxicology First toxicology tests at WSU in 1997 indicated that lab rats eating polycarbonate cages that had been autoclaved were getting sick BPA acts like estrogen and can disrupt the endocrine cycle in high doses High temperatures , scrubbing (surface abrasion), strong detergents increase leaching . A lot of literature says conflicting results. Some say that it leaches enough to harm you, some say it does not leach at all and many say it leaches at 4 ppb

Hypothesis and Objectives BPA will leach out of heated polycarbonate water bottles in very small amounts (less than 10 ppb) Objectives Develop a technique to determine the concentration of BPA in water contained in autoclaved bottles Develop a standard GC/MS curve for BPA in water. Determine the level of BPA leaching (if any) as a function of hot water washing cycles. For this we had to develop a method for extracting bisphenol A from water

Method of exposure Autoclave PC water bottles containing water. Run GC/MS tests on the water (after solid phase extraction SPE) Multiple passes of bottles through autoclave Autoclave T = 121 C. P = 2 bar

Let’s review PETE (#1) PC Disposable plastic water bottles Measure effect of UV and sunlight over an extended time period (rooftop exposure) PC Camelback and Nalgene bottles Determine how much Bisphenol A (BPA) is leaching when PC bottles are autoclaved

Solid Phase Extraction Short and sweet. MISSPELLING: ORGANICS Make sure you say Nitrogen or gas, NOT AIR

Gas Chromatograph and Mass Spectroscopy (GC/MS) Ionizes molecules Separates molecules by mass Feeds MS a stream of molecules one a time from lightest to heaviest Mass spectrometer Measures mass of individual molecules Compounds identified by specific spectrum Can only measure one mass at a time “GC MS is a two part system. The gc ionizes and seperates all of the molecules and the MS identifies and relatively quantifies each molecule.

Flow Chart of Process

GC/MS Results for PETE USE paint so you can draw in the peaks. Draw the best you can! Top left is MS results for DEHP. This is the standard spectrum from the database. Bottom left: This is the MS of our sample showing a 91% match for DEHP. Sample of water exposed for two months on KEC roof RIGHT: this is the GC that shows the relative abundance of DEHP (marked in red) MS: Identified DEHP to 91% confidence (Water sample with 2 month exposure) GC: DEHP of unknown concentration (in red)

GC/MS Results for PC Top (GC): First autoclave shows BPA is about 10 ppb Bottom (MS): Identified BPA to 93 % confidence I don’t understand these data..did the BPA leach at 10ppb in the first run and 3 ppb in the 2nd pass? Is that what this is showing? We have potential to get a lot more data, GC/MS doesn’t work well We are just waiting for GC/MS to be up and running again.

How Much BPA Comes Out? You get 50 times more BPA from eating canned food than you do drinking from water autoclaved in PC EPA says the maximum dose per day is 50 micrograms/kg/day We found BPA leaching at an average concentration of 4 ppb after autoclaving A 70 kg human would have to consume 1,000,000 liters of this autoclaved water per day in order to achieve the minimum toxic dosage of BPA

Conclusions Polycarbonate (PC) Studies PETE Studies Preliminary results show no concentration of BPA going over 10 ppb from autoclaved PC bottles We were successful in designing an extraction and concentration system for BPA We are currently waiting to run a series of test that will make our data statistically accurate PETE Studies Very few harmful chemicals were identified (only low levels of DEHP) Acetaldehyde will be the next molecule of interest to test Emphasize potential for more data

Special Thanks Howard Hughes Medical Institute Dr. Kevin Ahern, HHMI Coordinator CBEE Dr. Skip Rochefort Dr. Mohammad Azizian Brian Maloney (SBI) Moey Handloser (ASE) Chemistry Department Dr. Christine Pastorek Dr. Emile Firpo Kristi Edwards Greg Jones SBI***