Specific Identification of Organic Pollutants in the Catawba Watershed Wastewater Treatment Plant Effluents

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Specific Identification of Organic Pollutants in
the Catawba WatershedWastewater Treatment Plant
Effluents

• John Turner
• Faculty Mentor Dr. Pat Owens
• Faculty Committee Members Dr. Pat Owens,
• Dr. Cliff Calloway, Dr. Peter Phillips

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Threats posed by organics

• Many are toxic (harmful), carcinogenic
  (cancer-causing), or mutagenic (capable of
  altering genetic material) at very low levels
• Many organics have been shown to be endocrine
  disruptors capable of altering the sex of fishes

• May have the capability for bioaccumulation in
  the fat cells and membranes

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From The Charlotte ObserverOctober 4th, 2004
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The Status Quo

• Presently there is no testing of organic levels
  in WWTP effluents within the Catawba watershed
• Furthermore, testing of drinking water and river
  water for organics is not being done.

• Some organics such as 1,4-dioxane have been known
  to travel as far as 200 kilometers from its point
  of entry in a watershed. (Draper et al, 2000)

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Research Design and Methods

• Collection of WWTP samples
• Bottle washing procedure
• Glass bottles (approximately 600 mL) were used
  with glass stoppers
• 2 mL HPLC grade Methanol added to each bottle
• Stoppers returned to bottle and rolled and
  flipped so that Methanol completely covered the
  inside of the bottle
• This was then repeated using reagent grade Ethyl
  Acetate
• Unstopped bottles were placed in a dry oven at
  108oC for 24 hours

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Research Design and Methods

• Collection of WWTP samples
• Samples were collected from 2 WWTPs
• Samples were collected from Rock Hill (Manchester
  Creek) and Fort Mill WWTPs.
• The samples that were collected were composite
  samples

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WWTP Locations

• Rock Hill WWTP (Manchester)
• Fort Mill WWTP

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Research Design and Methods

• Organic Extraction
• The Basic Apparatus

Glass Funnel Membrane Filter Vacuum
Hose Erlenmeyer Vacuum Flask
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Research Design and Methods

• Organic Extraction
• Empore C18 Membrane Filter Preparation
• An Empore C18 Membrane Filter was placed at the
  bottom of the Glass Funnel on the screen.
• 25 grams of Empore Filter Aid glass beads were
  added to the funnel
• The disk was washed with 20 mL of elution solvent
  (methanol or ethyl acetate) and then allowed to
  dry
• 20 mL of methanol was used to condition the disk

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Research Design and Methods

• Organic Extraction
• Concentration of Organics onto the filter
• The sample was decanted into the glass funnel.
• The vacuum was then applied and the sample was
  allowed to run through the disk.
• The vacuum was allowed to continue to run for
  5-20 minutes so that residual water was removed.

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Research Design and Methods

• Organic Extraction
• Organic Elution
• The organics were eluted from the disk into an
  organic phase, and they were collected by placing
  a Kuderna-Danish flask under the membrane filter.
  
• 10 mL of elution solvent was then added (either
  methanol or ethyl acetate) so that it covered the
  disk completely
• The vacuum was used to pull the solvent that now
  contains the organics into the Kuderna-Danish
  flask.

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Research Design and Methods

• Organic Extraction
• Concentration of Elution
• Once the organics were concentrated into 10 mL of
  solvent they were further concentrated for
  analysis.
• Two mL of elution solvent was removed.
• Then the remaining 8 mL of elution solvent was
  evaporated down to approximately 1 mL.
• This was done by blowing a gentle stream of
  nitrogen that passed through an organic carbon
  filter over the solvent.

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Research Design and Methods

• Organic Extraction
• Analytical Plan

500 mL of Water
10 mL of extract
1 µL analyzed
1/50th
1 mL of extract
1/500th
1 µL analyzed
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Research Design and Methods

• Run Gas Chromatography-Mass Spectrometry

• 1 µl of extract was injected into the GC column
• The extract contains a mixture of the organics
  that were originally found in the wastewater but
  have now been concentrated into an organic phase.
• The GC column separated the analytes based upon
  their polarity.
• The MS measured the molecular weight of the
  various ions and a chromatogram was produced.

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Results

• Siloxanes
• Phenol
• Phthalates

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Siloxanes D5

• Rock Hill WWTP
• 8.044 min with Ethyl Acetate
• 8.043 min with Methanol

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D5 (cyclopentasiloxane)
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Library Match for D5
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Siloxanes D6 (cyclohexasiloxane)

• Rock Hill WWTP
• 11.915 min with Ethyl Acetate

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Library Match for D6
Loss of 88
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Siloxanes D7(cycloheptasiloxante)

• Rock Hill WWTP
• 16.512 min with Ethyl Acetate

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Library Match for D7
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Siloxanes D8 (cyclooctasiloxane)

• Rock Hill WWTP
• 21.165 min with Ethyl Acetate

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Siloxanes D9 (cyclononasiloxane)

• Rock Hill WWTP
• 25.317 35.826 min with Ethyl Acetate

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Siloxanes D10 (cyclododecasiloxane)

• Rock Hill
• 29.171, 32.651, 38.769, 41.553, 44.177, 46.642,
  48.208, and 49.746 min with Ethyl Acetate
• 15.744 min with Methanol
• Fort Mill
• 37.174 and 42.471min with Ethyl Acetate
• 45.103 min with Methanol

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Library Match for D10
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Risks Associated with Siloxanes

• Bioaccumulation in tissues and organs
• Capable of inhibiting estrogen, leading to
  reproductive problems

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Phenol

• Rock Hill WWTP
• 17.699 min with Ethyl Acetate
• 17.672 min with Methanol

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Library Match for Phenol
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Risks Associated with Phenol

• Most affects are related to the exposure to large
  quantities over time
• Probably not a major problem unless found in
  substantial quantities

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Bis (2-ethylhexyl) phthalate

• Rock Hill WWTP
• 42.699 min with Methanol
• Fort Mill
• 42.726 min with Methanol

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Library Match for a Phthalate
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Risks Associated withBis (2-ethylhexyl) phthalate

• Has been shown to bioaccumulate in tissue
• Affects the abilities of males to father babies

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Conclusions

• GC-MS was shown to be an effective means of
  identifying organics in wastewater
• Within the organics identified, the siloxanes and
  phthalates have serious health effects at very
  low levels
• This research established a basic understanding
  of the use of GC-MS in identifying organics in
  wastewater and has accumulated information to
  fuel further research in this area in the future
  at Winthrop