A Survey of Endocrine Disrupting Chemicals and Pharmaceuticals

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A Survey of Endocrine Disrupting Chemicals and Pharmaceuticals Powered By Docstoc
					  Occurrence and Fate of
Endocrine Disruptors in the
    San Marcos Area
             Adam Foster
            Glenn Longley
  Texas State University - San Marcos
        Acknowledgements
• City of San Marcos
• Texas Parks and Wildlife (SM Lab)
• Edwards Aquifer Research and Data
  Center (Texas State University)
         Purpose of This Study
1) Determine efficiency of the San Marcos
   Wastewater Treatment Plant (WWTP) in
   removing certain common OWCs
  •   determine which treatment step is the most effective
2) Determine if the WWTP effluent is affecting the
   concentration of these compounds in the San
   Marcos river
3) Determine if the hospital is contributing any of
   these compounds to the WW collection system
4) Determine the occurrence of these compounds
   in the San Marcos water supply
             Study Design
• Collect multiple water samples from each
  sample site
  – seven locations at the WWTP
  – upstream and downstream of the WWTP
    effluent discharge
  – two discharge ports at the hospital
  – influent and effluent of the WTP
• Use GC/MS and LC/MS to determine
  concentrations
                San Marcos WWTP
                Influent        Bar Screens      Grit Removal


                      Primary Sludge          Primary Clarification

     Sludge
 Dewatering and                                  Aeration (O2)
                                Return
    Disposal
                               Activated
             Waste              Sludge
                                                  Secondary
            Activated
                                                  Clarification
             Sludge

Reaeration Basin (O2)               UV             Sand/GAC
  D.O.: >6.0 mg/L              Disinfection         Filtration


     Effluent                                             Sampling Site
      Compounds Investigated
• Hormones: Ethynylestradiol, coprostanol, estradiol
• Detergent metabolites: Nonylphenol, octylphenol
• Pharmaceuticals: Carbamazepine (Carbatrol®), codeine,
  diltiazem (Cardizem®), fluoxetine (Prozac®)
• Antibiotics: Sulfamethoxazole, trimethoprim
• Fire retardants: Tributyl phosphate, Tris(2-
  chloroethyl)phosphate
• Pesticides: Diazinon
• Nonprescription Drugs: Acetaminophen, cotinine,
  caffeine
• PAHs: Fluoranthene
• Flavors and fragrances: Benzophenone, triethyl citrate
• Household wastewater compounds: DEET, triclosan
• Industrial wastewater compounds: Bisphenol A
           Quality Assurance
•   Field Blanks and Lab Blanks
•   Surrogates
•   Matrix Spikes
•   Duplicate Samples
                                           Example of                                                         MS2                                 Experiment
C:\Xcalibur\data\24Jan\24Jan01                                                            7/24/2007 1:00:30 PM                          #680 EDC 2500 ng/mL
#680 EDC 2500 ng/mL
                                     :
                                                                                                      RT: 16.43                                                                                                       NL: 7.67E3
                                                                                                      AA: 38267                                                                                                       m/z= 147.5-148.5 F: +
                                                                                                      SN: 122                                                                                                         c ESI Z ms [
                      100
                                                                                                                                                                                                                      99.75-300.25] MS
                                                                                                                                                                                                                      ICIS 24Jan01
                      50

                       0
                                                                                                      RT: 16.43                                                                                                       NL: 1.80E4
                                                                                                      AA: 86831                                                                                                       m/z= 217.5-218.5 F: +
                                                                                                      SN: 172                                                                                                         c ESI Z ms [
 Relative Abundance




                      100
                                                                                                                                                                                                                      99.75-300.25] MS
                                                                                                                                                                          RT: 16.97                                   ICIS 24Jan01
                      50
                                                                                                                                                                          AA: 276
                                                                                                                                                                          SN: 1
                       0
                                                                                                      RT: 16.43                                                                                                       NL: 9.72E3
                                                                                                      AA: 48349                                                                                                       m/z= 254.5-255.5 F: +
                                                                                                      SN: 94                                                                                                          c ESI Z ms [
                      100
                                                                                                                                                                                                                      99.75-300.25] MS
                                                                                                                                                                                                                      ICIS 24Jan01
                      50

                       0
                                    15.8     15.9     16.0      16.1      16.2         16.3       16.4             16.5         16.6       16.7           16.8     16.9        17.0           17.1   17.2      17.3
                                                                                                                  Time (min)


 24Jan01 # 1143-1152 RT: 16.38-16.47                           AV: 10 NL: 2.55E4
 F: + c ESI Z ms [ 99.75-300.25]
                                                                                                                                                                                                                      289.9
              100


                       80
                                                                                                                                       [M-2Cl]
 Relative Abundance




                       60
                                                             [M-C6H22Cl]                                                                          218.1                               [M-Cl]
                       40

                                                                                                                                                     220.1                            255.0
                                                                  148.1
                       20
                                                               146.1                                                                                                            253.0
                                                                                                                                                                                                               289.0
                                  110.2 114.1 121.0   133.1 142.1      149.0     162.1        173.1               189.1        202.2      217.1            227.1     243.2 252.1         255.9       273.1                 291.0
                        0
                            100              120              140                160                   180                     200                  220               240                 260                280                   300
                                                                                                                               m/z
                     Results
Of the 23 compounds investigated…
• 18 of those were detected in at least one sample
  – Cotinine, diazinon, ethynylestradiol, trimethoprim, and
    Prozac® were not detected in any samples
• 14 were detected each sampling event
• 12 were detected in WWTP effluent samples
  (Concentrations ranged from 9 - 215 ng/L)
• 11 were detected in downstream samples
  (Concentrations ranged from 6 - 1230 ng/L)
• One was detected in the San Marcos water
  drinking supply (Bisphenol A @ 8 ng/L)
        WWTP Effluent Samples
                                                   Frequency of Detection (% )
                                         0   10   20       30    40      50      60   70

           flavors and fragrances (2)

household wastewater compounds (2)

     prescription pharmaceuticals (4)

                   fire retardants (2)

 nonprescription pharmaceuticals (3)

           plant or animal sterols (3)

                       antibiotics (2)

      detergents and degradates (2)

                       pesticides (1)

                            PAHs (1)
                                                       - Concentrations ranged from
 industrial wastewater compounds (1)                   9-215 ng/L
      USGS WWTP Study Comparison
                                            Frequency of Detection (%)
                                        0   10   20   30    40   50   60   70     80

                     fire retardants
             plant or animal sterols
 nonprescription pharmaceuticals                                       USGS Study
     prescription pharmaceuticals                                      SM Study
             flavors and fragrances
household wastewater compounds
       detergents and degradates
                                                           - US Study: 78 out of 110 OWCs
industrial wastewater compounds                            were detected at least once.
                          pesticides                       (Concentrations ranged
                          antibiotics                      from 10 – 38,000 ng/L).
                                                           - SM Study: 12 out of 23 OWCs
                               PAHs
                                                           were detected at least once.
                                                           (Concentrations ranged
                                                           from 6 – 1,230 ng/L).
Glassmeyer et al., 2005
                                                                                      Frequency of Detection (%)
                                                  pe
                                                       st
         pr                                              ic
                                                            i




                                                                                  0
                                                                                      10
                                                                                           20
                                                                                                30
                                                                                                     40
                                                                                                          50
                                                                                                               60
                                                                                                                    70
                                                                                                                               80
                                                                                                                                         90
                                                                                                                                               100
                                                                                                                                                     110
           es                                                   de
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        np                                               st
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                    ip                                                 s
                                                                                                                                    Influent

                                                                                                                    Effluent




                                                                           (3
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                      te                      m                    s
                         rg                                                (1
                            e    nt
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                                                         ra
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                          as                   m                           (2
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                                   w                      u
                                    at                         nd
                                      er
                                             co                  s
                                                                                                                                                           WWTP Effectiveness




                                                                           (2
                                                  m                           )
                                                   po
                                                     un
                                                                 ds
                                                                           (1
                                                                              )
                        Concentration (ng/L)
D
    is
       ch




                            1000
                                   2000
                                          3000
                                                      4000
                                                                  5000
                                                                            6000




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                U
                    V
                                                                                   DEET (insect repellent)




         Ef
           fu
              en
                t

                D
                    S
                                                                         March
                                                             January
                                                 October




                U
                    S
                                              Tris(2-chloroethyl)phophate (TCEP)
Concentration (ng/L)




                                                         (fire retardant)                            March
                           800
                           700                                                                       January
                           600
                                                                                                     October
                           500
                           400
                           300
                           200
                           100
                             0
                                                      nt




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                                  200
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                                                     800
                                                           1000
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                                                                           1400
                                                                                     1600
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                          t
                                                                                                   Diltiazem (antihypertensive) Cardizem®




                      D
                          S
                                                                  March
                                                                           January




                      U
                          S
                             Concentration (ng/L)
D
    isc
       ha




                               0
                              50
                             100
                             150
                             200
                             250
                             300
                             350
                             400
                             450
                             500
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                                                                   Bisphenol A (plasticizer)




          Ef
            fu
              en
                        t

                   D
                       S

                   U
                                       March




                       S
                                               January
                                                         October
                Log Concentration (ng/L)
D
    is
       ch




                                                               10000




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                            10
                                 100
                                               1000
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         Ef
                                                                       Triethyl Citrate (fragrance)




           fu
              en
                t

                D
                    S
                                       March
                                                January
                                                          October




                U
                    S
                               Log Concentration (ng/L)
D
    is
       ch




                                       100
                                             1000
                                                        10000
                                                                                    100000




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         Ef
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              en
                t
                                                                                             Nonylphenol (detergent metabolite)




                D
                    S
                                                    March
                                                                January




                U
                                                                          October




                    S
             Log Concentration (ng/L)
Di
   s   ch




                                                                             1000000




                                         1000
                                                    10000
                                                                100000




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                              10
                                   100
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                UV
                                                                                       Caffeine (stimulant)




         Ef
           fu
             en
                t
                                                March




                DS
                                                            January
                                                                         October




                US
             Log Concentration (ng/L)
Di
   s   ch




                                         1000
                                                    10000
                                                                      100000
                                                                                     1000000




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                              10
                                   100
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                UV
                                                                                               Triclosan (antimicrobial)




          Ef
            fu
              en
                 t

                DS
                                            March
                                                            January
                                                                               October




                US
               Log Concentration (ng/L)
Di
  sc




                                          1000
                                                  10000
                                                           100000
                                                                    1000000




                           1
                               10
                                    100
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              da
                ry

             Fi
                                                                       Acetaminophen




               lte
                       r


                   UV

        Ef
           fu
                  en
                       t
                                                           March
                                                 January




                   DS


                   US
                               Log Concentration (ng/L)
D
 is
    cha




                                                 10000
                                                               100000
                                                                                  1000000




                               10
                                    100
                                          1000




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                    U
                     V
                                                                                            Coprostanol (fecal steroid)




         Ef
            fu
                 en
                      t


                    D
                     S
                                                    March
                                                            January
                                                                        October




                    U
                     S
                      Concentration (ng/L)
D
  is
     ch




                       1000
                       1500
                       2000
                       2500
                       3000
                       3500
                       4000




                          0
                        500
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                                                                     Estradiol




                 r

              U
                  V
        Ef
                                                            (natural female hormone)




          fu
             en
               t

              D
                  S
                                March
                                        January
                                                  October




              U
                  S
              Log Concentration (ng/L)
D
    is
       ch




                                                            10000




                            10
                                 100
                                               1000




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           ge
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    is
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                U
                    V
         Ef
                                                                     Benzophenone (fragrance)




           fu
              en
                t

                D
                    S

                U
                                       March




                    S
                                                 January
                                                           October
                     Concentration (ng/L)
D
  is
     ch




                      100
                      150
                      200
                      250
                      300
                      350
                      400
                      450




                        0
                       50
       ar
         ge
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                 r

             U
                 V
        Ef
          fu
             en
               t
                                                         Tributyl Phosphate (fire retardant)




             D
                             March




                 S
                                     January
                                               October




             U
                 S
                          Concentration (ng/L)
Di
   s   ch




                               200
                                     400
                                           600
                                                 800
                                                       1000
                                                                 1200
                                                                 1400




                           0
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            ge
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   s   ch
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                                                         March




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                                                                  January




              n
   Se
     co
        nd
            ar
               y

           Fi
                lte
                      r


                UV

          Ef
            fu
                                                                            Sulfamethoxazole (antibiotic)




              en
                 t

                DS


                US
                            Concentration (ng/L)
D
    isc
       ha




                                 100
                                       200
                                             300
                                                   400
                                                         500
                                                               600
                                                                       700




                             0
            rg
D              e
    isc            #1
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            rg
               e
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                    e   nt
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                   U
                       V
          Ef
            fu
              en
                                                                                 Carbamazepine (antiepileptic)




                        t

                   D
                       S
                                                               March




                   U
                                                                       January




                       S
                Conclusions
• In regards to the compounds in this study…
  – By mass, the San Marcos WWTP removed
    >99.9%
  – The aeration process is the most effective at
    removal
  – The effluent is having an effect on the river
  – The hospital is contributing to the WW collection
    system
Questions?

				
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