1. 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)

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

3. 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.

4. 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.

5. 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.

6. 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

7. 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.

8. 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

9. 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

10. 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

11. 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

12. 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

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

14. 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.

15. Flow Chart of Process

16. 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)

17. 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.

18. 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

19. 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

20. 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***