specific identification of organic pollutants in the catawba watershed wastewater treatment plant...
TRANSCRIPT
Specific Identification of Organic Pollutants in the Catawba Watershed
Wastewater Treatment Plant Effluents
John Turner
Faculty Mentor: Dr. Pat Owens
Faculty Committee Members: Dr. Pat Owens,Dr. Cliff Calloway, Dr. Peter Phillips
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
From The Charlotte ObserverOctober 4th, 2004
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)
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
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
WWTP Locations
• Rock Hill WWTP (Manchester)
• Fort Mill WWTP
Research Design and Methods
• Organic Extraction– The Basic Apparatus
Glass Funnel
Membrane Filter
Vacuum Hose
Erlenmeyer Vacuum Flask
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
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.
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.
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.
Research Design and Methods
• Organic Extraction– Analytical Plan
500 mL of Water
10 mL of extract
1 mL of extract
1/50th
1/500th
1 μL analyzed
1 μL analyzed
Research Design and Methods
• 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.
•Run Gas Chromatography-Mass Spectrometry
Results
• Siloxanes
• Phenol
• Phthalates
Siloxanes – D5
• Rock Hill WWTP
• 8.044 min with Ethyl Acetate
• 8.043 min with Methanol
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100% 73
133193 223
268
356
Spect 18.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBCBP 73 (47400=100%) rhetha10.sms
7.8 7.9 8.0 8.1 8.2 8.3minutes
0
50
100
150
200
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kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100% 73
133193 223
268
356
Spect 18.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBCBP 73 (47400=100%) rhetha10.sms
7.8 7.9
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100% 73
133193 223
268
356
Spect 18.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBCBP 73 (47400=100%) rhetha10.sms
7.8 7.9 8.0 8.1 8.2 8.3minutes
0
50
100
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kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
D5 (cyclopentasiloxane)
CH3
CH3
CH3CH3
CH3
CH3
CH3
CH3CH3
CH3
Si
Si
Si
Si
O
SiO
O
O
O
Library Match for D5
Hit 4 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 448
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 50 - 360Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 4 Fit: 841 RFit: 793 Purity: 783
50 100 150 200 250 300 350m/z
0%
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61
73
88 102 118 133 163 179 193 207 223 237
251268
310 323 340
356
Target8.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBCBP 73 (47400=100%) rhetha10.sms
0%
25%
50%
75%
100%
45 59
73
133 162 179 193 207 223 237 251
267
309 323 339
355
Cyclopentasiloxane, decamethyl-CAS No. 541-02-6, C10H30O5Si5, MW 370BP 355 (100000=100%) 20952 in nist98r.lbr
-100%
-50%
0%
50%
100%
Diff 8.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBCTarget - Cyclopentasiloxane, decamethyl-Normalized
Target Spectrum from c:\saturnws1\jaturner\rhetha10.smsScan No: 520, Time: 8.044 minutesNo averaging. Background corrected (E).Comment: 8.044 min. Scan: 520 Chan: 1 Ion: 1285 us RIC: 253782 EBC Pair Count: 139 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 50 19 0 | 134 210 0 | 208 270 1 | 268 11011 23 | | 51 73 0 | 135 105 0 | 209 407 1 | 269 5819 12 | | 52 103 0 | 147 271 1 | 210 243 1 | 270 1731 4 | | 55 1098 2 | 148 167 0 | 212 365 1 | 271 856 2 | | 58 399 1 | 149 83 0 | 213 123 0 | 272 344 1 | | 59 1869 4 | 154 252 1 | 220 165 0 | 282 491 1 | | 60 382 1 | 155 354 1 | 221 462 1 | 283 187 0 | | 61 2882 6 | 161 94 0 | 222 536 1 | 284 194 0 | | 64 168 0 | 162 181 0 | 223 1558 3 | 285 155 0 | | 65 41 0 | 163 828 2 | 224 1337 3 | 293 252 1 |
CH3
CH3
CH3
Si+
CH3
CH3
CH3CH3
CH3CH3
CH3
SiH+
SiH
Si
O
SiO
O CH3
CH3
CH3CH3
CH3
CH3
CH3CH3
CH3
Si
Si+
Si
Si
O
SiO
O
O
O
Siloxanes – D6 (cyclohexasiloxane)
• Rock Hill WWTP
• 11.915 min with Ethyl Acetate
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
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73
115
147
191 223 252 295
342
429
Spect 111.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBCBP 342 (12115=100%) rhetha10.sms
11.5 11.6 11.7 11.8 11.9 12.0minutes
10
20
30
40
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70
80
90
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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73
115
147
191 223 252 295
342
429
Spect 111.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBC
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
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73
115
147
191 223 252 295
342
429
Spect 111.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBCBP 342 (12115=100%) rhetha10.sms
11.5 11.6 11.7 11.8 11.9 12.0minutes
10
20
30
40
50
60
70
80
90
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Library Match for D6
Hit 7 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 657
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 50 - 435Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 7 Fit: 811 RFit: 758 Purity: 754
50 100 150 200 250 300 350 400m/z
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57
73
115147
166 191 208 223 252 295326
342
398 414
429
Target11.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBCBP 342 (12115=100%) rhetha10.sms
0%
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45
73
117
147
191 207 267
325
341
397 413
429
Cyclohexasiloxane, dodecamethyl-CAS No. 540-97-6, C12H36O6Si6, MW 444BP 73 (100000=100%) 27931 in nist98m.lbr
-100%
-50%
0%
50%
100%
Diff 11.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBCTarget - Cyclohexasiloxane, dodecamethyl-Normalized
Target Spectrum from c:\saturnws1\jaturner\rhetha10.smsScan No: 787, Time: 11.915 minutesNo averaging. Background corrected (E).Comment: 11.915 min. Scan: 787 Chan: 1 Ion: 5455 us RIC: 56782 EBC Pair Count: 150 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 50 25 0 | 104 35 0 | 191 90 1 | 294 41 0 | | 52 8 0 | 105 18 0 | 193 72 1 | 295 192 2 | | 53 48 0 | 110 17 0 | 194 37 0 | 296 73 1 | | 54 102 1 | 111 2 0 | 204 36 0 | 311 100 1 | | 55 266 2 | 115 156 1 | 205 54 0 | 312 100 1 | | 56 147 1 | 116 30 0 | 206 45 0 | 313 50 0 | | 57 787 6 | 117 57 0 | 207 60 0 | 325 128 1 | | 58 48 0 | 119 70 1 | 208 87 1 | 326 1090 9 | | 59 301 2 | 120 12 0 | 210 42 0 | 327 269 2 | | 62 10 0 | 123 18 0 | 221 12 0 | 328 206 2 |
Loss of 88
CH3
CH3
CH3
CH3
Si
Siloxanes – D7(cycloheptasiloxante)
• Rock Hill WWTP
• 16.512 min with Ethyl Acetate
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
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103
147
222
251
281
342
416
504
Spect 116.512 min. Scan: 1104 Chan: 1 Ion: 1702 us RIC: 273954 EBCBP 416 (31362=100%) rhetha10.sms
16.2 16.3 16.4 16.5 16.6 16.7 16.8minutes
0
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300
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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50%
75%
100%
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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103
147
222
251
281
342
416
504
Spect 116.512 min. Scan: 1104 Chan: 1 Ion: 1702 us RIC: 273954 EBCBP 416 (31362=100%) rhetha10.sms
16.2 16.3 16.4 16.5 16.6 16.7 16.8minutes
0
50
100
150
200
250
300
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Library Match for D7
Hit 22 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 605
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 50 - 510Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 22 Fit: 781 RFit: 703 Purity: 701
100 200 300 400m/z
0%
25%
50%
75%
100%73
103
147
222251
281
342
416
439
504
Target16.512 min. Scan: 1104 Chan: 1 Ion: 1702 us RIC: 273954 EBCBP 416 (31362=100%) rhetha10.sms
0%
25%
50%
75%
100%73
147
221
281
327 415 503
Cycloheptasiloxane, tetradecamethyl-CAS No. 107-50-6, C14H42O7Si7, MW 518BP 73 (100000=100%) 27714 in nist98m.lbr
-100%
-50%
0%
50%
100%
Diff 16.512 min. Scan: 1104 Chan: 1 Ion: 1702 us RIC: 273954 EBCTarget - Cycloheptasiloxane, tetradecamethyl-Normalized
Target Spectrum from c:\saturnws1\jaturner\rhetha10.smsScan No: 1104, Time: 16.512 minutesNo averaging. Background corrected (E).Comment: 16.512 min. Scan: 1104 Chan: 1 Ion: 1702 us RIC: 273954 EBC Pair Count: 192 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 53 40 0 | 187 102 0 | 265 625 2 | 370 235 1 | | 55 63 0 | 189 149 0 | 266 472 2 | 371 176 1 | | 57 85 0 | 190 275 1 | 267 313 1 | 376 102 0 | | 58 213 1 | 191 515 2 | 268 303 1 | 383 325 1 | | 59 1598 5 | 192 277 1 | 270 190 1 | 384 1630 5 | | 60 170 1 | 193 356 1 | 275 220 1 | 385 1028 3 | | 61 261 1 | 194 454 1 | 276 220 1 | 386 1424 5 | | 63 46 0 | 195 158 1 | 277 543 2 | 387 279 1 | | 69 79 0 | 197 117 0 | 278 925 3 | 389 102 0 | | 70 200 1 | 203 256 1 | 279 1615 5 | 399 740 2 |
Siloxanes – D8 (cyclooctasiloxane)
• Rock Hill WWTP
• 21.165 min with Ethyl Acetate
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
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73
147 221281
326
356
415
489577
Spect 121.165 min. Scan: 1425 Chan: 1 Ion: 1183 us RIC: 468472 EBCBP 356 (100997=100%) rhetha10.sms
20.8 20.9 21.0 21.1 21.2 21.3 21.4minutes
0
100
200
300
400
500
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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100%
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
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73
147 221281
326
356
415
489577
Spect 121.165 min. Scan: 1425 Chan: 1 Ion: 1183 us RIC: 468472 EBCBP 356 (100997=100%) rhetha10.sms
20.8 20.9 21.0 21.1 21.2 21.3 21.4minutes
0
100
200
300
400
500
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Siloxanes – D9 (cyclononasiloxane)
• Rock Hill WWTP
• 25.317 & 35.826 min with Ethyl Acetate
Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
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100%
73
148 222
282
356
402
430
475
531 563
Spect 125.371 min. Scan: 1715 Chan: 1 Ion: 1307 us RIC: 474838 EBCBP 430 (99451=100%) rhetha10.sms
25.0 25.1 25.2 25.3 25.4 25.5 25.6minutes
0
100
200
300
400
500
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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50%
75%
100%
Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100%
73
148 222
282
356
402
430
475
531 563
Spect 125.371 min. Scan: 1715 Chan: 1 Ion: 1307 us RIC: 474838 EBCBP 430 (99451=100%) rhetha10.sms
25.0 25.1 25.2 25.3 25.4 25.5 25.6minutes
0
100
200
300
400
500
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
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
Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100% 73
147221
282
356
430
476
504
549
Spect 129.171 min. Scan: 1977 Chan: 1 Ion: 1725 us RIC: 316048 EBCBP 73 (28943=100%) rhetha10.sms
28.7 28.8 28.9 29.0 29.1 29.2 29.3minutes
0
100
200
300
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
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Overlaid Chromatogram Plots
Plot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
0%
25%
50%
75%
100% 73
147221
282
356
430
476
504
549
Spect 129.171 min. Scan: 1977 Chan: 1 Ion: 1725 us RIC: 316048 EBCBP 73 (28943=100%) rhetha10.sms
28.7 28.8 28.9 29.0 29.1 29.2 29.3minutes
0
100
200
300
kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Library Match for D10
Hit 5 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 511
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 35 - 650Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 5 Fit: 795 RFit: 503 Purity: 477
100 200 300 400 500 600 700 800m/z
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100% 73
147222
295
356
430
503
623
Target37.174 min. Scan: 2529 Chan: 1 Ion: 6585 us RIC: 30535 EBCBP 430 (2099=100%) fmetha11.sms
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74
147221
281
355 429
503
577 651 873
Tetracosamethyl-cyclododecasiloxaneC24H72O12Si12, MW 888BP 147 (100000=100%) 66337 in nist98m.lbr
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Diff 37.174 min. Scan: 2529 Chan: 1 Ion: 6585 us RIC: 30535 EBCTarget - Tetracosamethyl-cyclododecasiloxaneNormalized
Target Spectrum from c:\saturnws1\jaturner\fmetha11.smsScan No: 2529, Time: 37.174 minutesNo averaging. Background corrected (E).Comment: 37.174 min. Scan: 2529 Chan: 1 Ion: 6585 us RIC: 30535 EBC Pair Count: 468 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 50 19 1 | 207 148 7 | 368 45 2 | 510 37 2 | | 51 30 1 | 208 101 5 | 369 343 16 | 511 13 1 | | 52 15 1 | 209 62 3 | 370 115 5 | 512 5 0 | | 53 37 2 | 211 3 0 | 371 128 6 | 513 9 0 | | 54 27 1 | 212 3 0 | 372 64 3 | 514 26 1 | | 55 93 4 | 214 11 1 | 374 15 1 | 516 7 0 | | 56 51 2 | 215 34 2 | 376 34 2 | 517 7 0 | | 57 326 16 | 216 12 1 | 377 9 0 | 518 41 2 | | 58 10 0 | 218 56 3 | 379 16 1 | 519 53 3 | | 59 97 5 | 219 2 0 | 380 13 1 | 522 16 1 |
Risks Associated with Siloxanes
• Bioaccumulation in tissues and organs
• Capable of inhibiting estrogen, leading to reproductive problems
Phenol
• Rock Hill WWTP
• 17.699 min with Ethyl Acetate
• 17.672 min with Methanol
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
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57
91163
191
281355
Spect 117.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBCBP 191 (20274=100%) rhetha10.sms
17.3 17.4 17.5 17.6 17.7 17.8 17.9minutes
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40
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kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
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57
91163
191
281355
Spect 117.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBCBP 191 (20274=100%) rhetha10.sms
17.3 17.4 17.5 17.6 17.7 17.8 17.9minutes
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40
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwetha11.sms RIC allPlot 2: c:\saturnws1\jaturner\fmetha11.sms RIC allPlot 3: c:\saturnws1\jaturner\rhetha10.sms RIC allPlot 4: c:\saturnws1\jaturner\methaceblank1.sms RIC all
100 200 300 400 500 600m/z
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57
91163
191
281355
Spect 117.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBCBP 191 (20274=100%) rhetha10.sms
17.3 17.4 17.5 17.6 17.7 17.8 17.9minutes
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kCounts dwetha11.sms RIC allfmetha11.sms RIC allrhetha10.sms RIC allmethaceblank1.sms RIC all
Library Match for Phenol
Hit 1 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 419
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 50 - 510Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 1 Fit: 989 RFit: 922 Purity: 917
50 100 150 200 250 300m/z
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57
77 91 107 135 147 163 175
191
206
281 355
Target17.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBCBP 191 (20274=100%) rhetha10.sms
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57
74 91 107 128 147 163 175
191
206
Phenol, 2,4-bis(1,1-dimethylethyl)-CAS No. 96-76-4, C14H22O, MW 206BP 191 (100000=100%) 17896 in nist98r.lbr
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Diff 17.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBCTarget - Phenol, 2,4-bis(1,1-dimethylethyl)-Normalized
Target Spectrum from c:\saturnws1\jaturner\rhetha10.smsScan No: 1186, Time: 17.699 minutesNo averaging. Background corrected (E).Comment: 17.699 min. Scan: 1186 Chan: 1 Ion: 5670 us RIC: 48351 EBC Pair Count: 116 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 50 307 2 | 79 202 1 | 112 17 0 | 149 163 1 | | 51 394 2 | 80 3 0 | 115 443 2 | 150 43 0 | | 52 107 1 | 81 41 0 | 116 217 1 | 151 16 0 | | 53 169 1 | 82 21 0 | 117 218 1 | 160 66 0 | | 54 51 0 | 83 17 0 | 118 84 0 | 161 177 1 | | 55 156 1 | 86 34 0 | 119 224 1 | 162 212 1 | | 56 43 0 | 87 84 0 | 120 113 1 | 163 1611 8 | | 57 3922 19 | 88 278 1 | 121 407 2 | 164 260 1 | | 58 290 1 | 89 156 1 | 122 68 0 | 165 26 0 | | 59 8 0 | 90 48 0 | 123 72 0 | 168 36 0 |
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
Bis (2-ethylhexyl) phthalate
• Rock Hill WWTP
• 42.699 min with Methanol
• Fort Mill• 42.726 min
with Methanol
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwblankmeth1ml1.sms RIC allPlot 2: c:\saturnws1\jaturner\fmmeth1ml1st0.sms RIC allPlot 3: c:\saturnws1\jaturner\2000.40106.sms RIC allPlot 4: c:\saturnws1\jaturner\methanolblank1.sms RIC all
100 200 300 400 500 600m/z
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55
104
149
193 221
279
326 358 416 492 520 551 609 638
Spect 142.699 min. Scan: 2910 Chan: 1 Ion: 22351 us RIC: 4700 EBCBP 149 (625=100%) 2000.40106.sms
42.00 42.25 42.50 42.75minutes
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7.5
10.0
12.5
kCounts dwblankmeth1ml1.sms RIC allfmmeth1ml1st0.sms RIC all2000.40106.sms RIC allMethanolBlank1.SMS RIC all
Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwblankmeth1ml1.sms RIC allPlot 2: c:\saturnws1\jaturner\fmmeth1ml1st0.sms RIC allPlot 3: c:\saturnws1\jaturner\2000.40106.sms RIC allPlot 4: c:\saturnws1\jaturner\methanolblank1.sms RIC all
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Overlaid Chromatogram PlotsPlot 1: c:\saturnws1\jaturner\dwblankmeth1ml1.sms RIC allPlot 2: c:\saturnws1\jaturner\fmmeth1ml1st0.sms RIC allPlot 3: c:\saturnws1\jaturner\2000.40106.sms RIC allPlot 4: c:\saturnws1\jaturner\methanolblank1.sms RIC all
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55
104
149
193 221
279
326 358 416 492 520 551 609 638
Spect 142.699 min. Scan: 2910 Chan: 1 Ion: 22351 us RIC: 4700 EBCBP 149 (625=100%) 2000.40106.sms
42.00 42.25 42.50 42.75minutes
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kCounts dwblankmeth1ml1.sms RIC allfmmeth1ml1st0.sms RIC all2000.40106.sms RIC allMethanolBlank1.SMS RIC all
Library Match for a Phthalate
Hit 1 of Saturn Fit SearchSaturn Fit Search Results
Hits Found: 25Pre-Search Hits Found: 653
Saturn Fit Search ParametersThreshold: 700Target Ion Range: 35 - 650Library MW Range: 0 - 2000Library Ion Range: All of Library EntryLocal Normalization: OnRequested Pre-Search: 250Requested Final Search: 25Search 3 Libraries: A. c:\saturnws1\satlib\tutorial.lbr
B. c:\saturnws1\satlib\nist98r.lbrC. c:\saturnws1\satlib\nist98m.lbr
Hit 1 Fit: 948 RFit: 538 Purity: 538
100 200 300 400 500 600m/z
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55
104
149
193 221
279
326 358 416 492 520 551 609 638
Target42.699 min. Scan: 2910 Chan: 1 Ion: 22351 us RIC: 4700 EBCBP 149 (625=100%) 2000.40106.sms
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57
113
149
279
Bis(2-ethylhexyl) phthalateCAS No. 117-81-7, C24H38O4, MW 390BP 149 (100000=100%) 15623 in nist98r.lbr
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Diff 42.699 min. Scan: 2910 Chan: 1 Ion: 22351 us RIC: 4700 EBCTarget - Bis(2-ethylhexyl) phthalateNormalized
Target Spectrum from c:\saturnws1\jaturner\2000.40106.smsScan No: 2910, Time: 42.699 minutesNo averaging. Background corrected (E).Comment: 42.699 min. Scan: 2910 Chan: 1 Ion: 22351 us RIC: 4700 EBC Pair Count: 192 MW: 0 Formula: None CAS No: None Acquired Range: 50 - 650
Ion Int %BP Ion Int %BP Ion Int %BP Ion Int %BP | 50 106 17 | 101 14 2 | 166 25 4 | 278 20 3 | | 51 21 3 | 102 1 0 | 167 413 66 | 279 140 22 | | 52 8 1 | 104 124 20 | 168 53 8 | 280 25 4 | | 53 49 8 | 105 3 0 | 172 7 1 | 281 20 3 | | 54 29 5 | 106 2 0 | 174 13 2 | 283 6 1 | | 55 447 72 | 107 1 0 | 176 10 2 | 285 12 2 | | 56 112 18 | 108 4 1 | 179 4 1 | 299 10 2 | | 57 183 29 | 109 5 1 | 181 3 0 | 313 8 1 | | 58 12 2 | 110 10 2 | 182 6 1 | 323 6 1 | | 59 13 2 | 111 4 1 | 183 8 1 | 325 9 1 |
Risks Associated withBis (2-ethylhexyl) phthalate
• Has been shown to bioaccumulate in tissue
• Affects the abilities of males to father babies
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