Detection of Leaching Organic Migrants from Detection of Leaching Organic Migrants from Polyethylene Terephthalate (PETE #1)Polyethylene Terephthalate (PETE #1) and and

Polycarbonate (PC #7) Polycarbonate (PC #7) water bottles.water bottles.

Paul DornathPaul Dornath

School of Chemical, Biological and Environmental School of Chemical, Biological and Environmental Engineering (CBEE)Engineering (CBEE)

Mentor: Dr. Skip RochefortMentor: Dr. Skip Rochefort

Partners: Brian Maloney (SBI) and Moey Handloser Partners: Brian Maloney (SBI) and Moey Handloser (ASE)(ASE)

Chemical LeachingChemical Leaching

Chemicals from inside Chemicals from inside plastic plastic

i.e., small molecules i.e., small molecules moving through the moving through the solid polymer matrixsolid polymer matrix

Degraded surface Degraded surface particlesparticles

Polyethylene Terephthalate (PETE) Polyethylene Terephthalate (PETE) PlasticPlastic

Known to consumers as Known to consumers as #1 PETE in recycling #1 PETE in recycling codescodes

Most common uses: Most common uses: water and 2 L. soda water and 2 L. soda bottles bottles

Ester of ethylene glycol Ester of ethylene glycol and terephthalic acidand terephthalic acid

What May Cause PETE to What May Cause PETE to Leach?Leach?

UV radiationUV radiation– Photo-Fries Photo-Fries

rearrangementrearrangement– 310 nm wavelength310 nm wavelength

Unreacted polymer and Unreacted polymer and plasticizers from inside plasticizers from inside the plastic can diffuse at the plastic can diffuse at 40 C.40 C.

Why We Are ConcernedWhy We Are ConcernedCauseCause

Placement of PETE Placement of PETE merchandisemerchandise

Unknown storage Unknown storage conditionsconditions

Solar sterilizationSolar sterilization

EffectEffectBad taste (acetaldehyde) Bad taste (acetaldehyde)

Organic molecules Organic molecules entering into our body entering into our body

Hypothesis and ObjectivesHypothesis and Objectives

HypothesisHypothesis– Sunlight causes PETE to degrade into organic Sunlight causes PETE to degrade into organic

fragments via Photo-Fries rearrangement and fragments via Photo-Fries rearrangement and elevated heat. Compounds of interest are elevated heat. Compounds of interest are acetaldehyde, phthalate plasticizers and aromatic acetaldehyde, phthalate plasticizers and aromatic organic fragments. organic fragments.

ObjectivesObjectives– Determine if organic compounds leach from PETE Determine if organic compounds leach from PETE

bottles when exposed to sunlight using SPE and bottles when exposed to sunlight using SPE and GC/MSGC/MS

– Determine types of molecules using GC/MSDetermine types of molecules using GC/MS– Quantify extent of leaching as a function of exposure Quantify extent of leaching as a function of exposure

time using GC/MStime using GC/MS

Method of ExposureMethod of Exposure

Bottles placed on the roof of Bottles placed on the roof of Kelley Engineering Center for up Kelley Engineering Center for up to 3 monthsto 3 months

Record temperatures three Record temperatures three times per day (morning, noon, times per day (morning, noon, evening)evening)– Air temperatureAir temperature– Inside middle and end bottlesInside middle and end bottles– Underneath bottlesUnderneath bottles

Polycarbonate (PC) PlasticPolycarbonate (PC) Plastic

Ester of Bisphenol A Ester of Bisphenol A (BPA) and phosgene(BPA) and phosgene

Commonly sold as Commonly sold as Nalgene water bottles Nalgene water bottles (#7 PC) and as baby (#7 PC) and as baby bottles. bottles.

Reports of BPA Reports of BPA leaching have made leaching have made them less popular and them less popular and led to their removal led to their removal from some markets from some markets

Bisphenol A A

Phosgene

Nalgene BottleCamelback Bottle

Polycarbonate

Bisphenol A ToxicologyBisphenol A Toxicology

First toxicology tests at WSU First toxicology tests at WSU in 1997 indicated that lab rats in 1997 indicated that lab rats eating polycarbonate cages eating polycarbonate cages that had been autoclaved were that had been autoclaved were getting sickgetting sick

BPA acts like estrogen and BPA acts like estrogen and can disrupt the endocrine can disrupt the endocrine cycle in high dosescycle in high doses

High temperatures , scrubbing High temperatures , scrubbing (surface abrasion), strong (surface abrasion), strong detergents increase leaching .detergents increase leaching .

Hypothesis and ObjectivesHypothesis and Objectives

HypothesisHypothesis– BPA will leach out of heated polycarbonate water bottles BPA will leach out of heated polycarbonate water bottles

in very small amounts (less than 10 ppb)in very small amounts (less than 10 ppb)

ObjectivesObjectives– Develop a technique to determine the concentration of Develop a technique to determine the concentration of

BPA in water contained in autoclaved bottlesBPA in water contained in autoclaved bottles– Develop a standard GC/MS curve for BPA in water.Develop a standard GC/MS curve for BPA in water.– Determine the level of BPA leaching (if any) as a function Determine the level of BPA leaching (if any) as a function

of hot water washing cycles. of hot water washing cycles.

Method of exposureMethod of exposure

Autoclave PC water Autoclave PC water bottles containing water.bottles containing water.

Run GC/MS tests on the Run GC/MS tests on the water (after solid phase water (after solid phase extraction SPE)extraction SPE)

Multiple passes of bottles Multiple passes of bottles through autoclavethrough autoclave

AutoclaveAutoclave

T = 121 C. P = 2 barT = 121 C. P = 2 bar

Let’s reviewLet’s review

PETE (#1)PETE (#1)– Disposable plastic Disposable plastic

water bottles water bottles

– Measure effect of UV Measure effect of UV and sunlight over an and sunlight over an extended time period extended time period (rooftop exposure)(rooftop exposure)

PC PC – Camelback and Nalgene Camelback and Nalgene

bottlesbottles

– Determine how much Determine how much Bisphenol A (BPA) is Bisphenol A (BPA) is leaching when PC leaching when PC bottles are autoclavedbottles are autoclaved

Solid Phase ExtractionSolid Phase Extraction

Gas Chromatograph and Mass Gas Chromatograph and Mass Spectroscopy (GC/MS)Spectroscopy (GC/MS)

Gas chromatograph Gas chromatograph – Ionizes moleculesIonizes molecules– Separates molecules by massSeparates molecules by mass– Feeds MS a stream of molecules one a time Feeds MS a stream of molecules one a time

from lightest to heaviestfrom lightest to heaviest

Mass spectrometerMass spectrometer– Measures mass of individual moleculesMeasures mass of individual molecules– Compounds identified by specific spectrumCompounds identified by specific spectrum– Can only measure one mass at a timeCan only measure one mass at a time

Flow Chart of ProcessFlow Chart of Process

GC/MS Results for PETEGC/MS Results for PETE

MS: Identified DEHP to 91% confidence (Water sample with 2 month exposure)

GC: DEHP of unknown concentration (in red)

GC/MS Results for PC GC/MS Results for PC

Top (GC):First autoclave shows BPA is about 10 ppb

Bottom (MS):Identified BPA to 93 % confidence

How Much BPA Comes Out?How Much BPA Comes Out?

EPA says the maximum dose EPA says the maximum dose per day is 50 per day is 50 micrograms/kg/day micrograms/kg/day

We found BPA leaching at an We found BPA leaching at an average concentration of 4 ppb average concentration of 4 ppb after autoclavingafter autoclaving

A 70 kg human would have to A 70 kg human would have to consume consume 1,000,0001,000,000 liters of liters of this autoclaved water per day this autoclaved water per day in order to achieve the in order to achieve the minimum toxic dosage of BPAminimum toxic dosage of BPA

You get 50 times more BPA from eating You get 50 times more BPA from eating canned food than you do drinking canned food than you do drinking from water autoclaved in PCfrom water autoclaved in PC

ConclusionsConclusionsPolycarbonate (PC) StudiesPolycarbonate (PC) Studies

Preliminary results show no concentration of BPA going Preliminary results show no concentration of BPA going over 10 ppb from autoclaved PC bottlesover 10 ppb from autoclaved PC bottles

We were successful in designing an extraction and We were successful in designing an extraction and concentration system for BPA concentration system for BPA

We are currently waiting to run a series of test that will We are currently waiting to run a series of test that will make our data statistically accuratemake our data statistically accurate

PETE StudiesPETE StudiesVery few harmful chemicals were identified (only low Very few harmful chemicals were identified (only low levels of DEHP) levels of DEHP)

Acetaldehyde will be the next molecule of interest to testAcetaldehyde will be the next molecule of interest to test

Howard Hughes Medical Institute Howard Hughes Medical Institute

Dr. Kevin Ahern, HHMI CoordinatorDr. Kevin Ahern, HHMI Coordinator

CBEECBEE– Dr. Skip RochefortDr. Skip Rochefort– Dr. Mohammad AzizianDr. Mohammad Azizian– Brian Maloney (SBI)Brian Maloney (SBI)– Moey Handloser (ASE)Moey Handloser (ASE)

Chemistry DepartmentChemistry Department– Dr. Christine PastorekDr. Christine Pastorek– Dr. Emile Firpo Dr. Emile Firpo – Kristi EdwardsKristi Edwards– Greg JonesGreg Jones

Special ThanksSpecial Thanks