kevin d. daniels, christiane hoppe-jones, guillermo s
TRANSCRIPT
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Advanced LC-MS/MS Methods for the Detection of Trace Organic Compounds throughout
Advanced Water Treatment
Kevin D. Daniels, Christiane Hoppe-Jones, Guillermo S. Flores, Alec B. Nienhauser, Juliana S. Ordine, and Shane A. Snyder
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“We forget that the water cycle and the life cycle are one.”
Jacques Cousteau 1910 - 1997
Why Water is Important
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Schaum, C., Lensch, D., Cornel, P., 2015. J. Water Reuse Desalin. 5, 83–94.
Energy Requirements
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Indirect Potable Reuse Direct Potable Reuse
Water Reuse
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Humic Acids
Fulvic Acids
Cl-
Na+
Chlorine
Sodium
How do we Monitor DPR
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IntroductionWastewater
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IntroductionTrace Organic Compounds
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Targeted Chemical Analysis
Conventional SPE
1 L
0.01-10 ng/L
36 CECs
5 hrs
No Extraction
1 mL
1-100 ng/L
45 CECs
15 min
Online SPE
0.1-20 ng/L
33 CECs
20 min
15 mL
Extraction Methods
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ExperimentalPurpose
Overall Goal: Evaluate the performances of advanced LC-QQQ methods for trace organic compounds during advanced water treatment
Labor and time requirements
Selectivity
Accuracy
Sensitivity
Objectives:
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- 80 uL injection volume
- 3 samples per hour
- Column: ZORBAX Eclipse Plus 95Å C-8 (2.1 x 100 mm, 1.8 μm)
- Mobile Phases: H2O + 0.1% Acetic Acid and Acetonitrile
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Collected Sample
Filter Sample
LC Column
QQQ
Direct Water Injection
Sample is directly injected onto the analytical column
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Sample gets extracted using a cartridge incorporated before separation
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Collected Sample
Filter Sample
Online SPE LC Column QQQ
Online-SPE
- 1.7 mL injection volume
- 3 samples per hour
- Column: Poroshell 120 EC C-18 (2.1 x 50 mm, 2.7 μm)
- Mobile Phases:H2O + 0.1% Acetic Acid and Acetonitrile
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ExperimentalTargeted Compounds
Benzotriazole Caffeine Carbamazepine
Meprobamate Sulfamethoxazole TCPP
HC: Household chemical; I/CC: Industrial/commercial chemical; Pharm.: Pharmaceutical
I/CC
Restrainer in photographic emulsions
Pharm
Antiepileptic, analgesic
Pharm
Anxiolytic drug, tranquilizer
PCP
Fire retardant
HC
Stimulant
Pharm
Antibiotic
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Utility 1
Utility 2
Secondary Effluent
SecondaryEffluent
Microfiltration UVAOPReverse Osmosis
Granular Media Filtration
Ultrafiltration
Ozone BAC Lake Biofiltration
AWTEffluent
Ozone
AWT Effluent
ExperimentalExperimental
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DOC ResultsDOC Results
Jul-16
Sep-16
Nov-16
Dec-16
Jan-17
Mar-17
Apr-17
Aug-16
Dissolved Organic Carbon
Standard Method: 5310 B
Shimadzu TOC Analyzer
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EEM Results
Sec-Eff MF-Inf MF-Eff RO-Eff UV-Eff
Sec-Eff UF-Eff GMF-Eff Oz1-Inf
Oz1-Eff BAC-Eff Oz2-Eff Lk-Inf BF-Eff
EEM Results
Ex/Em Matrix
Published Method: Lakowicz, 2006
Horiba Aqualog
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Utility 1
Secondary Effluent
MicrofiltrationEffluent
UVAOPEffluent
Reverse OsmosisEffluent
6/6 6/6 1/1 <MRLs
Utility 2
Secondary Effluent
Granular Media FiltrationEffluent
UltrafiltrationEffluent
OzoneEffluent
BACEffluent
Lake BiofiltrationEffluent
OzoneEffluent
6/6 6/6 6/6 5/5 3/3 <MRLs <MRLs
CEC OverviewOSPE/DWI
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Most Prevalent CECsSecondary Effluent Concentrations
OSPE/DWI
Meprobamate
Caffeine
Carbamazepine
Benzotriazole
Sulfamethoxazole
TCPP
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Most Prevalent CECsSecondary Effluent Concentrations
OSPE/DWI
Meprobamate
Caffeine
Carbamazepine
Benzotriazole
Sulfamethoxazole
TCPP
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Most Prevalent CECsCaffeine Results
+ 250
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Most Prevalent CECsCaffeine Results
+ 250
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Most Prevalent CECsBenzotriazole Results
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Most Prevalent CECsBenzotriazole Results
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Most Prevalent CECsMeprobamate Results
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Most Prevalent CECsMeprobamate Results
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Most Prevalent CECsMRLs at Utility 1
DWI O-SPE
Benzotriazole 800 130
Caffeine 60 44
Carbamazepine 120 31
Meprobamate 110 69
Sulfamethoxazole 51 54
TCPP 290 720
Secondary EffDWI O-SPE DWI O-SPE
Benzotriazole 800 130 760 100
Caffeine 60 44 51 41
Carbamazepine 120 31 130 32
Meprobamate 110 69 99 73
Sulfamethoxazole 51 54 44 42
TCPP 290 720 260 600
Secondary Eff MF EffDWI O-SPE DWI O-SPE DWI O-SPE
Benzotriazole 800 130 760 100 340 8
Caffeine 60 44 51 41 17 5
Carbamazepine 120 31 130 32 26 4
Meprobamate 110 69 99 73 29 5
Sulfamethoxazole 51 54 44 42 15 5
TCPP 290 720 260 600 200 57
Secondary Eff MF Eff RO EffDWI O-SPE DWI O-SPE DWI O-SPE DWI O-SPE
Benzotriazole 800 130 760 100 340 8 320 8
Caffeine 60 44 51 41 17 5 18 6
Carbamazepine 120 31 130 32 26 4 27 4
Meprobamate 110 69 99 73 29 5 29 5
Sulfamethoxazole 51 54 44 42 15 5 16 5
TCPP 290 720 260 600 200 57 200 71
Secondary Eff MF Eff RO Eff UVAOP EFF
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Most Prevalent CECsMRLs at Utility 2
DWI OSPE
Benzotriazole 640 150
Caffeine 27 63
Carbamazepine 110 20
Meprobamate 74 37
Sulfamethoxazole 38 51
TCPP 150 610
Sec EFFDWI OSPE DWI OSPE
Benzotriazole 640 150 550 110
Caffeine 27 63 39 46
Carbamazepine 110 20 86 20
Meprobamate 74 37 62 34
Sulfamethoxazole 38 51 31 48
TCPP 150 610 140 740
Sec EFF GMF EFFDWI OSPE DWI OSPE DWI OSPE
Benzotriazole 640 150 550 110 620 150
Caffeine 27 63 39 46 40 56
Carbamazepine 110 20 86 20 100 21
Meprobamate 74 37 62 34 69 41
Sulfamethoxazole 38 51 31 48 36 52
TCPP 150 610 140 740 170 980
Sec EFF GMF EFF UF EFFDWI OSPE
240 86
14 26
89 22
18 26
11 28
35 400
Oz1 EFFDWI OSPE DWI OSPE
240 86 200 43
14 26 12 17
89 22 24 12
18 26 16 17
11 28 10 18
35 400 31 190
Oz1 EFF BAC EFFDWI OSPE DWI OSPE DWI OSPE
240 86 200 43 180 54
14 26 12 17 13 22
89 22 24 12 22 10
18 26 16 17 17 18
11 28 10 18 10 18
35 400 31 190 30 180
Oz1 EFF BAC EFF Oz2 EFFDWI OSPE DWI OSPE DWI OSPE DWI OSPE
240 86 200 43 180 54 120 53
14 26 12 17 13 22 11 13
89 22 24 12 22 10 23 3
18 26 16 17 17 18 13 8
11 28 10 18 10 18 9 11
35 400 31 190 30 180 29 180
Oz1 EFF BAC EFF Oz2 EFF LK INFDWI OSPE DWI OSPE DWI OSPE DWI OSPE DWI OSPE
240 86 200 43 180 54 120 53 130 33
14 26 12 17 13 22 11 13 11 6
89 22 24 12 22 10 23 3 21 3
18 26 16 17 17 18 13 8 12 5
11 28 10 18 10 18 9 11 9 8
35 400 31 190 30 180 29 180 29 120
Oz1 EFF BAC EFF Oz2 EFF LK INF BF EFF
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Various TOrCs were present in the secondary effluent and throughout the treatment trains
All TOrCs were reduced to below detection limits in the final advanced water treatment effluents
Both analytical methods displayed similar concentrations for the different effluents
O-SPE demonstrated lower MRLs for most of the indicator compounds analyzed
Both methods offer similar labor intensity and run times, as well as comparable costs
Conclusion
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Many thanks to Dr. Armando Durazo for instrument assistance
Project Members:Dr. Christiane Hoppe-Jones
Israel Lopez
Guillermo FloresAlec NienhauserJuliana OrdineErica Clevenger
Acknowledgments
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Questions
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Thank You
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