Evaluation of Ozone Waste Water Treatments and Studies … point/Amadeo.pdf · 2020. 9. 1. ·...

1

INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN

Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN

Evaluation of Ozone Waste WaterTreatments and Studies

Evaluating the Reuse of Treated Effluents




-Analysis of wastewater

-Advanced Oxidative Water Teatments( ozone and Ozone + H2O2)

-Life cicle assesment

2



LC-MSLCLC--MSMSGC-MSGCGC--MSMS

ANALYSIS



ANALYSIS

LC-QqQ-MS/MS and LC-LiT-MS/MS

GC-MS(MS)

LC-QqQ-MS/MS and LC-LiT-MS/MS

GC-MS(MS)

LC-TOF-MS

GC-Q-MS

LC-TOF-MS

GC-Q-MS

Target compoundsTarget compounds Non target compoundsNon target compounds

MS/MS mode (Low mass acc.) Full scan mode (High mass acc.)

3



TARGET ANALYSISTARGET ANALYSIS



Disinfectants87. Biphenylol88. Chlorophene

Metabolites68. 4-Acetoaminoantipyrine69. 4-Formylaminoantipyrin70. 4-Methylaminoantipyrine 71. 4-Dimethylaminoantipyrine 72. 4-Aminoantipyrine 73. Paraxanthine74. Carbamaz.10,11-epoxide75. Antipyrine76. Fenofibric Acid77. Clofibric acid78. Cotinine

Pesticides79. Atrazine80. Clorpyriphos81. Clorfenvinphos82. Diuron83. Isoproturon84. Simazine85. Permetrina

Others89. Nicotine90. Caffeine

Lipid regulators53. Fenofibrate54. Bezafibrate55. Gemfibrozil56. Pravastatin

Beta Blockers35. Atenolol36. Propranolol37. Sotalol38. Metoprolol39. Nadolol

Analgesic/ Anti-Inflammatory20. Acetaminophen 21. Indomethacine 22. Fenoprofen23. Codeine 24. Mefenamic Ac. 25. Ibuprofen26. Ketorolac27. Naproxen28. Diclofenac29. Ketoprofen30.Salicilic acid31.Propyphenazone32.Urbason

Antibiotics1. Metronidazole2. Sulfamethoxazole3. Trimethoprim 4. Ciprofloxacin5. Cefotaxime6. Ofloxacin7. Erythromycin 8. Tetraciclyne10.Norfloxacin11.Clarithromycin12.Lincomycin13.Sulfamethazine14.Sulfapyridine15.Sulfadiazine16.Sulfathiazole17.Azithromycin18.Mevastatin19.Simvastatin

AntiepilepticPsychiatric drug59. Carbamazepine60. Diazepan61. Primidone

Sympathomimetics57. Salbutamol58. Terbutaline

Antidepressants47. Fluoxetine48. Paroxetine49. Venlafaxine50. Citalopram51. Amitriptyline52. Clomipramine

Diuretics45. Furosemide46. Hydrochlorothiazide

EDCs86. Bisfenol-A

TARGET ANALYSIS

LIST OF CONTAMINANTS ANALYSED

Contrast media33. Iopromide34. Iopamidol

Antineoplastics62. Ifosfamide63. Cyclophosphamide64. Tamoxifen

Anesthetics65. Mepivacaine

Corticosteroides66. Methylprednisolone

Antihistamines40. Famotidine, 41. Lansoprazole42. Ranitidine43. Omeprazole44. Loratadine

Anti-Infective67. Clotrimazole

4



SPE

OASIS HLB hydrophilic-lypophilic polymer

200 ml wastewater effluent, pH 7-8400 ml river water, pH 7-8

WashMIliQ water, pH = 7-8

Elution4 + 4 ml MeOH

Drying~ 5min N2 Evaporation

AnalysisLC-ESI(+/-)MSor GC-MS

Reconstitution:• 1ml MeOH:H2O, 10:90 (v/v)•Filtro PTFE 0.45 µm

FiltrationFiltros de fibra de vidrio

0.7 μm

SAMPLE TREATMENT

TARGET ANALYSIS



Nº

11%19%

70%Problematic compounds:- Very polar and soluble in water (ej. Omeprazole)- Stability depends on the pH (ej. Cefotaxime, tetraciclyne)

TARGET ANALYSIS

SAMPLE TREATMENT

RECOVERIESRECOVERIES

5



POLAR TARGET COMPOUNDSLC-QqQ-MS/MSLCLC--QqQQqQ--MS/MS/MSMS



Identification criteriaCompound tR (min)

(%RSD) Precursor Ion (m/z) SRM 1* SRM 2** SRM 3** [SRM2]/[SRM1]

(%RSD)

Positive Ionization Carbamazepine 28.9 (0.2) 237.2 194.3 192.1 - 0.34 (3) Simazine 29.0 (0.1) 202.2 132.0 124.2 104.1 0.88 (7) Fluoxetine 29.7 (0.2) 310.3 44.2 148.2 - 0.22 (20) Ketorolac 30.4 (0.2) 256.2 105.1 178.1 - 0.01 (10) Methylprednisolone 31.3 (0.2) 475.3 321.1 339.3 457.2 0.80 (11) Isoproturon 32.4 (0.2) 207.3 72.1 165.1 134.2 0.20 (13) Atrazine 32.6 (0.2) 216.1 174.1 104.1 132.1 0.41 (4) Ketoprofen 33.3 (0.2) 255.2 209.2 105.1 177.2 0.78 (12) Naproxen 33.6 (0.3) 231.2 185.3 170.1 - 0.36 (12) Diazepan 35.6 (0.2) 285.2 193.2 154.2 222.3 0.98 (4) Biphenylol 35.8 (0.3) 171.2 153.1 152.0 127.2 0.63 (5) Indomethacine 37.7 (0.3) 358.2 139.1 174.3 - 0.10 (16) Fenofibric Acid 37.9 (0.3) 319.1 233.1 139.1 121.0 0.33 (8) Mefenamic Ac. 40.4 (0.3) 242.2 180.2 224.2 209.2 0.58 (12) Chlorfenvinphos 40.7 (0.3) 359.1 155.2 127.1 205.1 0.96 (10) Chlorpyriphos methyl 43.4 (0.3) 322.1 125.1 290.1 109.1 0.88 (13) Fenofibrate 46.6 (0.2) 361.2 233.1 139.1 121.1 0.98 (6)

Negative Ionization Furosemide 5.0 (2.4) 329.1 205.1 285.1 126.2 0.86 (3) Hydrochlorothiazide 5.7 (0.3) 296.0 269.1 205.0 126.0 0.97 (5) Clofibric acid 5.9 (1.3) 213.0 127.1 85.0 - 0.25 (3) Bezafibrate 7.9 (1.2) 360.1 274.2 154.1 85.0 0.62 (2) Diclofenac 10.9 (0.7) 294.0 250.0 214.1 - 0.10 (6) Diuron 11.6 (0.5) 231.1 186.1 149.8 122.1 0.24 (12) Fenoprofen 11.8 (0.3) 241.1 197.1 93.1 - 0.67 (4) Ibuprofen 12.5 (0.7) 205.1 161.2 - - - Chlorophene 13.0 (0.3) 217.0 181.2 153.0 101.0 0.65 (10) Gemfibrozil 13.4 (0.4) 249.2 121.0 127.1 - 0.10 (13)

Compound tR (min) (%RSD)

Precursor Ion (m/z) SRM 1* SRM 2** SRM 3** [SRM2]/[SRM1]

(%RSD)

Positive Ionization Nicotine 6.1 (5.6) 163.1 117.2 84.1 130.1 0.42 (14) Salbutamol 7.1 (0.4) 240.3 148.2 166.2 222.2 0.28 (8) Atenolol 7.2 (0.2) 267.3 145.2 190.2 116.1 0.72 (4) Terbutaline 7.3 (0.1) 226.3 152.2 107.1 125.2 0.31 (2) Ranitidine 7.9 (1.2) 315.3 176.2 130.1 224.2 0.66 (10) Sotalol 8.3 (1.2) 273.3 133.2 213.2 255.2 0.73 (9) 4-MAA 9.7 (0.7) 218.2 56.1 97.2 159.2 0.38 (13.) 4-DAA 10.4 (0.5) 232.2 113.2 98.2 111.2 0.31 (19) 4-AA 10.8 (1.4) 204.2 56.2 159.2 94.2 0.21 (11) Paraxanthine 11.0 (1.2) 181.2 124.2 69.2 96.1 0.17 (12) Acetaminophen 11.1 (1.0) 152.1 110.1 64.8 93.0 0.19 (16) Metronidazole 12.1 (1.2) 172.1 128.1 82.1 111.1 0.51 (11) Codeine 13.0 (3.4) 300.2 165.2 215.3 199.2 0.88 (7) Caffeine 17.1 (0.3) 195.1 138.2 110.2 123.1 0.30 (8) 4-AAA 17.4 (0.1) 246.2 228.1 83.1 104.2 0.98 (6) 4-FAA 17.6 (0.3) 232.2 214.2 104.1 83.1 0.96 (7) Trimethoprim 18.2 (0.3) 291.3 230.2 123.2 261.2 0..85 (12) Cefotaxime 18.5 (0.3) 456.1 396.1 324.1 241.3 0.95 (4) Ofloxacin 18.7 (0.1) 362.3 318.3 261.3 - 0.95 (5) Ciprofloxacin 19.1 (0.3) 332.3 231.2 314.3 245.1 0.78 (16) Mepivacaine 19.6 (0.3) 247.4 98.1 70.1 - 0.30 (9) Metoprolol 21.0 (0.2) 268.2 116.2 133.2 159.2 0.64 (10) Antipyrine 21.6 (0.3) 189.2 77.1 104.1 106.2 0.52 (7) Omeprazole 22.3 (0.2) 346.3 198.2 136.2 151.2 0.60 (15) Propanolol 24.9 (0.4) 260.0 116.2 183.2 155.2 0.71 (12) Sulfamethoxazole 25.1 (0.4) 254.2 108.2 156.1 147.2 0.88 (6) Carbam.10,11-epoxide 25.3 (0.2) 253.2 180.2 236.2 210.2 0.68 (11) Erythromycin 25.5 (0.2) 734.6 158.3 576.5 316.1 0.24 (3) Paroxetine 27.7 (0.1) 330.3 192.2 123.2 151.2 0.30 (14)

133 transitionsIn the same time

segment!!In positive mode

POLAR TARGET COMPOUNDS

LC-QTRAPLCLC--QTRAPQTRAP

6



Nicotina Cotinina

Velafaxime Propyphenazole

POLAR TARGET COMPOUNDS

Effluent Wastewater

LC-QqQ-MS/MSLCLC--QqQQqQ--MS/MS/MSMS



0.1 (8)127, [M – H – C8H9OH]–121, [M – H – CO2C6H12]–12.3 (0.4)Gemfibrozil

0.6 (11)153 181, [M – H – Cl]–12.2 (0.2)Chlorophene

0.2 (8)149, [M – H – NH(CH3)2 -Cl]–186, [M – H – NH(CH3)2]–10.9 (0.1)Diuron

--161, [M – H – CO2]–10.1 (1.1)Ibuprofen

0.1 (8)180, [M – C2H5O2]–196, [M– H – CO2]–9.8 (0.7)Mefenamic Acid

0.5 (9)297, [M – C2H4O2]–312, [M – H – CO2]–9.1 (0.9)Indomethacine

0.8 (4)93, [M – H – C9H8O2]–197, [M – H – CO2]–9.0 (1.2)Fenoprofen

0.1 (2)214, [M – H – CO2Cl]–250, [M – H – CO2]–8.8 (0.9)Diclofenac

0.4 (12)185, [M– H – CO2]–170, [M – C2H4O2]–6.9 (2.7)Naproxen

0.1 (7)197, [M – H – C2O2]–209, [M– H – CO2]–6.3 (1.2)Ketoprofen

0.9 (3)269, [ M – H – NCH] –205, [M – H – SO2NCH]–5.1 (0.2)Hydroclhlorothiazide

0.7 (3)154, [M – H –C12H14O3]–274, [M – H – CO2-C(CH3)2]–4,0 (0.8)Bezafibrate

0.2 (8)85, [M – H – C6H4ClO]–127, [M – H – CO2-C(CH3)2]–3.8 (0.7)Clofibric Acid

0.9 (5)285, [M – H – CO2]–205, [M – H – CO2SO2NH2]–3.7 (1.5)Furosemide

[SRM2]/[SRM1](%RSD)

Product Ion (m/z)SRM 2

Product Ion (m/z)SRM 1

tR (min)(%RSD)Compound

Identification criteria for the SRM method by LC-QqQ-MS/MS

TARGET ANALYSIS

LC-QqLIT-MS/MS

IDENTIFICATION CRITERIA:IDENTIFICATION CRITERIA:tR2 SRM transitions per compoundSRM2/SRM1 ratio

SRM METHODSRM METHOD

7



QTrap instruments allows improving confirmatory information:

- Application of additional operation modes based on the use of the linear ion trap (LIT) mode.

Automated Information Dependent Acquisition (IDA) software.

Sequentially collect multiple SRM transitions and full scan MS/MS (Enhanced Product Ion, EPI mode) and/ or MS3 spectra in one single run.

Compounds for which the second transition:- Not detected-Present at low intensity

Additional structural information is required for a suitable confirmation

QUALITATIVE ANALYSISLC-LiT-MS



Information Dependent Acquisition (IDA) softwareQUALITATIVE ANALYSISLC-QTRAP

161.0

205.1 161.2

205.1

EPI

XICSRM

159.1161.2

Estructuras??CH

CH2

CH3

H3C

-

205.2 161.2

TIC

XIC SRM

EPICH

CH3

CH3

H3C

-2

[M-H]-

ESI (-) Ibuprofen

205.2

159.1161.2

Accurate quantification

Reliable confirmation

Single run

8



ResultsResultsExamples for common transitions:Examples for common transitions:

specificspecific

specificspecific

2x10

0

1

2

3

4

+ MRM (223.00000 -> 86.00000) 50 ppb std chromatogram 0.1%HCOOH

2x10

0

1

2

3

4+ MRM (223.00000 -> 148.00000) 50 ppb std chromatogram 0.1%HCOOH

2x10

0

0.5

1

1.5


2x10

0

0.5

1

1.5+ MRM (223.00000 -> 166.00000) 50 ppb std chromatogram 0.1%HCOOH

Counts vs. Acquisit ion Time (min)0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14

223.0/86.0

223.0/148.0

223.0/106.0

223.0/166.0

Aldicarb sulfone=Aldoxycarb

2x10

0

1

2

3

4


2x10

0

1

2

3


2x10

0

0.5

1

1.5


2x10

0

0.5

1



223.0/86.0

223.0/148.0

223.0/106.0

223.0/166.0

2x10

0

1

2

3

4


2x10

0

1

2

3


2x10

0

0.5

1

1.5


2x10

0

0.5

1



223.0/86.0

223.0/148.0

223.0/106.0

223.0/166.0

Aldicarb sulfone=Aldoxycarb

butoxycarboxin – aldicarb sulfonebutoxycarboxin – aldicarb sulfone

scanned – unscanned transitions are commonscanned – unscanned transitions are common

Counts vs. Acquisition Time (min)

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH

2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5Counts vs. Acquisition Time (min)

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4


2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4


2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5

223.0/72.0

223.0/160.0

Counts vs. Acquisition Time (min)

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4


2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5Counts vs. Acquisition Time (min)

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4


2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5

3x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4


2x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4


14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5

223.0/72.0

223.0/160.0

fluometuron - diuronfluometuron - diuron

both scanned transitions are common

both scanned transitions are common

specific

specific



QUANTITATIVE ANALYSIS

LODs (ng/L)

9



NONNON--TARGET ANALYSISTARGET ANALYSIS



ESI+

Inte

nsity

, cou

nts

85 125 165m/z, amu

8.0e4

1.6e5

2.4e5

3.2e5

110.0606

152.0710

Time, min240 280 320 360

2500.00

6500.00

1.05e4

Inte

nsity

, cou

nts

300.1595

Time, min2 6 10 14 18 22 26 30 34 38 42

1.0e6

5.0e6

9.0e6

1.3e7

1.7e7

Inte

nsity

, cps

TIC

1.0 5.0 9.0 13.0 17.0 21.0Time, min

8.0e4

2.4e5

4.0e5

5.6e5

Inte

nsi ty

, cps

XIC8.33

Acetaminophen

Codeine

m/z, amu1.0 5.0 9.0 13.0

5000.0

1.3e4

2.1e4

Inte

nsity

, cp s

15.39

4.15 15.66

XIC

10.80

[M+H2-COCH3]

HO

NH3

2

CONFIRMATIONLC-TOF-MS

10



Effluent wastewater LC-TOF-MSLCLC--TOFTOF--MSMS

5x 1 0

0

0 .2

0 .4

0 .6

0 .8

1

+ E S I S c a n (7 .8 8 6 m in ) F ra g = 1 9 0 .0 V 1 0 0 p p b M ix _ M t .d S u b t ra c t

2 3 7 .1 0 1 9(M + H )+

6 1 1 .3 4 3 63 1 5 .1 7 8 1 4 4 7 .2 9 5 9

3 7 3 .2 2 0 2 6 7 6 .4 4 7 45 4 4 .3 7 0 5

7x10

0.2

0.4

0.6

0.8

1

1.2

+ESI TIC Scan Frag=190.0V 100ppbMix_Mt.d

4x10

2

4

6

8

+ESI EIC(237.1000) Scan Frag=190.0V 100ppbMix_Mt.d

Counts vs. Acquisition Time (min)4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5

Total ion chromatogram

Extracted ion chromatogram

Carbamazepine: C15H12N2OTheorethical Mass: 237.10197Error: 1.4 ppm

Carbamazepine

Carbamazepine F1: C14H11NTheorethical Mass: 194.0949Error: 1.32 ppm

7.886

[M+H]+

237.1019



Preparación de Standardsy Análisis

PreparaciPreparacióón de n de StandardsStandardsy Any Anáálisislisis

Tabla de Datos ExcelTabla de Datos ExcelTabla de Datos Excel

Creación de la Base de DatosCreaciCreacióón de la Base de Datosn de la Base de Datos Integración en el Software del equipoIntegraciIntegracióón en el Software del equipon en el Software del equipo

Screening Automático de StandardsScreeningScreening AutomAutomáático de tico de StandardsStandards

Screening Automáticode Muestras FortificadasScreeningScreening AutomAutomááticotico

de Muestras Fortificadasde Muestras Fortificadas

Screening Automáticode Muestras Reales

ScreeningScreening AutomAutomááticoticode Muestras Realesde Muestras Reales

Procedure:Procedure:

LC-QTOF-MSAccurate-Mass Database

LCLC--QTOFQTOF--MSMSAccurateAccurate--MassMass DatabaseDatabase

300 pesticides + in source fragments

93 pharmaceuticals + in source fragments

11



DATABASE

300 Pesticides + 618 Fragments= 918 entries in the database

ScreeningScreening DatabaseDatabase



LC-TOF-MSLCLC--TOFTOF--MSMS

COMPOUND RT (min)

TheoreticalMass

Exp. Mass Score Error (ppm) FORMULA [M+H +]

… … … … … … …

AZOXYSTROBIN 10.15 403.1168 403.1168 95.56 0.01 C22H17N3O5

AZOXYSTROBIN F1 10.15 371.0901 371.0906 80.8 -1.47 C2H9NO2PS

… … … … … … …

12



DATABASE SEARCH

10

0.15

PESTICIDES in solvent (20-500ppb)



10

0.15

DATABASE SEARCHPESTICIDES in solvent (20-500ppb)

13



Effluent wastewater LC-TOF-MSLCLC--TOFTOF--MSMS

5x 1 0

0

0 .2

0 .4

0 .6

0 .8

1

+ E S I S c a n (7 .8 8 6 m in ) F ra g = 1 9 0 .0 V 1 0 0 p p b M ix _ M t .d S u b t ra c t

2 3 7 .1 0 1 9(M + H )+

6 1 1 .3 4 3 63 1 5 .1 7 8 1 4 4 7 .2 9 5 9

3 7 3 .2 2 0 2 6 7 6 .4 4 7 45 4 4 .3 7 0 5

7x10

0.2

0.4

0.6

0.8

1

1.2

+ESI TIC Scan Frag=190.0V 100ppbMix_Mt.d

4x10

2

4

6

8

+ESI EIC(237.1000) Scan Frag=190.0V 100ppbMix_Mt.d

Counts vs. Acquisition Time (min)4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5

Total ion chromatogram

Extracted ion chromatogram

Carbamazepine: C15H12N2OTheorethical Mass: 237.10197Error: 1.4 ppm

Carbamazepine

Carbamazepine F1: C14H11NTheorethical Mass: 194.0949Error: 1.32 ppm

7.886

[M+H]+

237.1019



NON TARGETSearching for UNKNOWN pesticides in food by LC/TOF-MS (Using the chlorine isotope signature)

8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0 25.0 26.0 27.0 28.0 29.0 30.0Time [min]

0.02.0e64.0e66.0e68.0e61.0e7

1.2e71.4e71.6e71.8e72.0e72.2e72.4e72.6e72.8e73.0e73.2e73.4e73.6e73.8e74.0e74.2e7

4.4e74.6e74.8e75.0e75.2e75.4e75.6e75.8e76.0e7

Intensity, cps

26.73

26.09

25.7128.11

18.0122.98 28.4221.66 23.24 25.04

28.8520.70 24.13 29.0619.39

20.26

230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390m/z, amu

0.05000.0

1.0e41.5e42.0e42.5e43.0e43.5e44.0e44.5e45.0e45.5e46.0e46.5e47.0e47.5e48.0e48.5e49.0e49.5e41.0e51.1e51.1e51.2e51.2e51.3e51.3e51.4e51.4e51.5e51.5e51.6e5

Intensity, counts

311.0716

313.0687

297.0556

299.0529

312.0741

315.0662

298.0588301.0510

316.0684

Imazalil

14.0160 + CH2

Methyl substituted Imazalil

DBE 7.5

DBE 7.5Cl

Cl

O

NN

-CH3

Imazalil methyl-derivate

An impurity from commercialformulations containing imazalil

Ion Trap MS/MS

m/z 311 269

m/z 297 255

14



INFLUENT (ng/L) EFFLUENT (ng/L)

pKa Log kow Max. Min. Average Max. Min. Average RemovalEfficiency (%)

Acetaminophen 9.4 0.46 37458 1571 23202 < LOQ < LOQ < LOQ 100

Effluent wastewaterTOF-MS REPORT



7x10

0.2

0.4

0.6

0.8

1

1.2

+ESI TIC Scan Frag=190.0V elejido_dic_07_E.d

4x10

0

2

4

6

+ESI EIC(110.0600) Scan Frag=190.0V elejido_dic_07_E.d Smooth

1.255

7.0161.020

Counts vs. Acquisition Time (min)0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8 5 5.2 5.4 5.6 5.8 6 6.2 6.4 6.6 6.8 7 7.2 7.4 7.6 7.8 8 8.2 8.4

4x10

0

2

4

6

+ESI Scan (1.272 min) Frag=190.0V elejido_dic_07_E.d Subtract

110.0608(M+H)+

Counts vs. Mass-to-Charge (m/ z)109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131

LC-TOF Chromatogram

Total Ion Chromatrogram

Extracted Ion Chromatrogram 110.0608

P-aminophenol

[C6H7N O]+

HN

HO

CH3

O

NH2

HO

P-aminophenol

Acetaminophen

Effluent Wastewater

15



7x10

0.5

1

1.5

2

2.5

+ESI TIC Scan Frag=90.0V Alin 071211 O3.d

1 1

4x10

0

1

2

3

4

+ESI EIC(749.5158) Scan Frag=90.0V Alin 071211 O3.d

5.534

11.41813.2675.068

1 1

4x10

0

0.5

1

1.5

2

+ESI EIC(591.4221) Scan Frag=90.0V Alin 071211 O3.d

4.216

12.286

5.5346.917

1 1

Counts vs. Acquisition Time (min)0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15 15.5 16 16.5

LC-TOF Chromatogram

Azithromycin

4x10

0

1

2

3

+ESI Scan (5.550 min) Frag=90.0V Alin 071211 O3.d Su…

749.5155(M+H)+

748 749 750 751 752 753 754

4x10

0

1

2

+ESI Scan (4.232 min) Frag=90.0V Alin 071211 O3.d Su…

591.4218(M+H)+

590 591 592 593 594 595 596

Total Ion Chromatrogram

Effluent Wastewater treated with O3



QUANTITATIVE ANALYSIS

LODs (ng/L)

16



1989 (2002). 374.090 h.e. 3000 m3h-1

Sedimentación primaria. Fangos Activados con eliminación de nutrientes. Nitrificación/desnitrificación

EDAR ALCALA OESTE (Aguas urbanas)

CARACTERIZACIÓN

WATER TREATMENTWATER TREATMENT



44 compuestos detectados al menos en 4 muestras del influente

17



0

10

20

30

40

50

60

70

80

90

100

-8.00 -6.00 -4.00 -2.00 0.00 2.00 4.00 6.00 8.00

log Dow

Rem

oval

effi

cien

cy (%

)

10

12

3 45

15

18

14

6

7

89

11

12

1621

17

19

2223

24

25

26

2728

29

3132

3534

36

39

4037

1 10 a

owow pH pK

KD −=+

(27) atenolol, (36) propanolol, (30) metoprolol, (28) sulfamethoxazole, (40) erythromycin, (33) trimethoprim, (29) fenofibric acid, (31) bezafibrate, (32) ketoprofen, (34) Diclofenac, (35) indomethacine, (37) mefenamic acid, (38) omeprazole, (39) carbamazepine



1 170M s− −3 2 2O OH HO O− −+ → +

6 1 12.2 10x M s− −3 2 2 3O HO HO O− • •−+ → +

a pH 7 y valores de H2O2 10-5 – 10-3 M valores significativos de descomposición de ozono

3 2 3 2O O O O•− •−+ → + 6 1 11.6 10x M s− −

3 2HO HO O• •→ + 5 1 11.1 10x M s− −

AOPProcesos oxidativos donde se generan radicales hidroxilo en cantidad suficiente para influir en el tratamiento del agua

k=7.9x105 s-1

-k=5x1010 M-1s-1HO2

• HO2+−• + pK=4.8

k=7.9x105 s-1

-k=5x1010 M-1s-1HO2

• HO2+−• + pK=4.8HO2

• HO2+−• + pK=4.8

k=3.3x102 s-1

-k=5.2x1010 M-1s-1HO3

• HO3+−• + pK=8.2

k=3.3x102 s-1

-k=5.2x1010 M-1s-1HO3

• HO3+−• + pK=8.2HO3

• HO3+−• + pK=8.2

18



TABLE 2 Ozonation time (min) LOQ* 0 2 4 6 10 15 Ozone doses for remotion kR (M-1 s-1) 3-(4-methylbenzylidene) camphor 39 55 50 65 39 72 54 Not removed 4-Aminoantipyrine 19 58 - - - - - < 50 μM 4-methylaminoantipyrne (4-MAA) 2 389 - - - - - < 50 μM Antipyrine 8 30 16 - - - - < 90 μM Atenolol 3 911 655 265 24 - - < 220μM Azithromycin 12 235 - - - - - < 50 μM Benzophenone-3 33 123 89 100 102 119 119 Not removed Bezafibrate 4 115 72 67 37 15 4 Still detected at 340 �M 3260 ± 780 Carbamazepine 1 106 17 2 - - - < 130 μM Carbamazepine epoxide 9 32 23 19 13 - - < 220 μM Ciprofloxacin 5 522 334 28 - - - < 130 μM Citalopram hydrobromide 2 60 31 4 - - - < 130 μM Clarithromycin 5 39 - - - - - < 50 μM Codeine 5 378 - - - - - < 50 μM Cotinine 12 100 61 54 48 38 28 28% remained for 340 μM 680 ± 29 Diclofenac 1 433 - - - - - < 50 μM Diuron 1 100 60 46 25 6 1 Still detected at 340 μM 3890 ± 200 Erythromycin 10 72 16 - - - - < 90 μM Ethylkexyl methoxycinnamate 15 234 274 322 231 214 204 Not removed Famotidine 14 1045 - - - - - < 50 μM Fluoxethine 2 17 - - - - - < 50 μM Furosemide 82 840 - - - - - < 50 μM Galaxolide 23 1486 749 552 178 196 173 83% for 340 μM Gemfibrozil 1 332 50 18 19 15 15 95% for 340 μM Hydrochlorothiazide 1 707 461 199 - - - < 130 μM Indomethacin 2 37 - - - - - < 50 μM Ketoprofen 2 162 156 102 68 18 3 Still detected at 340 μM 3040 ± 770 Ketorolac 2 533 165 - - - - < 90 μM Lansoprazole 9 337 162 84 32 - - < 220 μM Lincomycin 3 12 - - - - - < 50 μM Loratadine 1 29 18 7 2 - - < 220 μM Mefenamic acid 2 59 - - - - - < 50 μM Metoprolol 3 27 17 5 - - - < 130 μM Metronidazole 3 113 73 85 56 14 3 Still detected at 340 μM 3100 ± 780 Musk xylene 3 89 92 95 89 98 91 Not removed Musk ketone 36 123 125 140 95 105 76 38% for 340 μM N-acetyl-4-aminoantipyrine (4-AAA) 50 8605 2419 101 - - - < 130 μM Naproxen 12 109 - - - - - < 50 μM N-formyl-4-aminoanttipyrine (4-FAA)

17 1776 471 21 - - - < 130 μM

Nicotine 4 81 12 10 13 10 14 Still detected at 340 μM Norfloxacin 8 38 56 - - - - < 90 μM Octocrylene 16 114 115 113 81 95 91 20% for 340 μM Ofloxacin 3 3594 276 18 11 9 10 Still detected at 340 μM Omeprazole 3 1015 231 7 - - - < 130 μM Primidone 5 80 86 65 40 - - < 220 μM Propanolol 2 32 7 - - - - < 50 μM Propyphenazone 2 23 - - - - - < 90 μM Ranitidine 2 111 3 - - - - < 90 μM Sulfamethoxazole 8 95 39 19 15 - - < 220 μM Sulfapyridine 12 50 - - - - - < 50 μM Tonalide 19 188 131 130 53 67 53 72% for 340 μM Triclosan 52 246 55 72 79 70 53 Still detected at 340 μM Trimethoprim 2 73 7 - - - - < 90 μM Venlafaxine 6 179 127 21 - - - < 130 μM * LOQ calculated in ozonated samples. Cconcentration expressed as ng/L

TABLE 2 Ozonation time (min) LOQ* 0 2 4 6 10 15 Ozone doses for remotion kR (M-1 s-1) 3-(4-methylbenzylidene) camphor 39 55 50 65 39 72 54 Not removed 4-Aminoantipyrine 19 58 - - - - - < 50 μM 4-methylaminoantipyrne (4-MAA) 2 389 - - - - - < 50 μM Antipyrine 8 30 16 - - - - < 90 μM Atenolol 3 911 655 265 24 - - < 220μM Azithromycin 12 235 - - - - - < 50 μM Benzophenone-3 33 123 89 100 102 119 119 Not removed Bezafibrate 4 115 72 67 37 15 4 Still detected at 340 �M 3260 ± 780 Carbamazepine 1 106 17 2 - - - < 130 μM Carbamazepine epoxide 9 32 23 19 13 - - < 220 μM Ciprofloxacin 5 522 334 28 - - - < 130 μM Citalopram hydrobromide 2 60 31 4 - - - < 130 μM Clarithromycin 5 39 - - - - - < 50 μM Codeine 5 378 - - - - - < 50 μM Cotinine 12 100 61 54 48 38 28 28% remained for 340 μM 680 ± 29 Diclofenac 1 433 - - - - - < 50 μM Diuron 1 100 60 46 25 6 1 Still detected at 340 μM 3890 ± 200 Erythromycin 10 72 16 - - - - < 90 μM Ethylkexyl methoxycinnamate 15 234 274 322 231 214 204 Not removed Famotidine 14 1045 - - - - - < 50 μM Fluoxethine 2 17 - - - - - < 50 μM Furosemide 82 840 - - - - - < 50 μM Galaxolide 23 1486 749 552 178 196 173 83% for 340 μM Gemfibrozil 1 332 50 18 19 15 15 95% for 340 μM Hydrochlorothiazide 1 707 461 199 - - - < 130 μM Indomethacin 2 37 - - - - - < 50 μM Ketoprofen 2 162 156 102 68 18 3 Still detected at 340 μM 3040 ± 770 Ketorolac 2 533 165 - - - - < 90 μM Lansoprazole 9 337 162 84 32 - - < 220 μM Lincomycin 3 12 - - - - - < 50 μM Loratadine 1 29 18 7 2 - - < 220 μM Mefenamic acid 2 59 - - - - - < 50 μM Metoprolol 3 27 17 5 - - - < 130 μM Metronidazole 3 113 73 85 56 14 3 Still detected at 340 μM 3100 ± 780 Musk xylene 3 89 92 95 89 98 91 Not removed Musk ketone 36 123 125 140 95 105 76 38% for 340 μM N-acetyl-4-aminoantipyrine (4-AAA) 50 8605 2419 101 - - - < 130 μM Naproxen 12 109 - - - - - < 50 μM N-formyl-4-aminoanttipyrine (4-FAA)

17 1776 471 21 - - - < 130 μM


Ozonation time (min) LOQ* 0 2 4 6 10 15 Ozone doses for remotion kR (M-1 s-1) 3-(4-methylbenzylidene) camphor 39 55 50 65 39 72 54 Not removed 4-Aminoantipyrine 19 58 - - - - - < 50 μM 4-methylaminoantipyrne (4-MAA) 2 389 - - - - - < 50 μM Antipyrine 8 30 16 - - - - < 90 μM Atenolol 3 911 655 265 24 - - < 220μM Azithromycin 12 235 - - - - - < 50 μM Benzophenone-3 33 123 89 100 102 119 119 Not removed Bezafibrate 4 115 72 67 37 15 4 Still detected at 340 �M 3260 ± 780 Carbamazepine 1 106 17 2 - - - < 130 μM Carbamazepine epoxide 9 32 23 19 13 - - < 220 μM Ciprofloxacin 5 522 334 28 - - - < 130 μM Citalopram hydrobromide 2 60 31 4 - - - < 130 μM Clarithromycin 5 39 - - - - - < 50 μM Codeine 5 378 - - - - - < 50 μM Cotinine 12 100 61 54 48 38 28 28% remained for 340 μM 680 ± 29 Diclofenac 1 433 - - - - - < 50 μM Diuron 1 100 60 46 25 6 1 Still detected at 340 μM 3890 ± 200 Erythromycin 10 72 16 - - - - < 90 μM Ethylkexyl methoxycinnamate 15 234 274 322 231 214 204 Not removed Famotidine 14 1045 - - - - - < 50 μM Fluoxethine 2 17 - - - - - < 50 μM Furosemide 82 840 - - - - - < 50 μM Galaxolide 23 1486 749 552 178 196 173 83% for 340 μM Gemfibrozil 1 332 50 18 19 15 15 95% for 340 μM Hydrochlorothiazide 1 707 461 199 - - - < 130 μM Indomethacin 2 37 - - - - - < 50 μM Ketoprofen 2 162 156 102 68 18 3 Still detected at 340 μM 3040 ± 770 Ketorolac 2 533 165 - - - - < 90 μM Lansoprazole 9 337 162 84 32 - - < 220 μM Lincomycin 3 12 - - - - - < 50 μM Loratadine 1 29 18 7 2 - - < 220 μM Mefenamic acid 2 59 - - - - - < 50 μM Metoprolol 3 27 17 5 - - - < 130 μM Metronidazole 3 113 73 85 56 14 3 Still detected at 340 μM 3100 ± 780 Musk xylene 3 89 92 95 89 98 91 Not removed Musk ketone 36 123 125 140 95 105 76 38% for 340 μM N-acetyl-4-aminoantipyrine (4-AAA) 50 8605 2419 101 - - - < 130 μM Naproxen 12 109 - - - - - < 50 μM N-formyl-4-aminoanttipyrine (4-FAA)

17 1776 471 21 - - - < 130 μM

Nicotine 4 81 12 10 13 10 14 Still detected at 340 μM Norfloxacin 8 38 56 - - - - < 90 μM Octocrylene 16 114 115 113 81 95 91 20% for 340 μM Ofloxacin 3 3594 276 18 11 9 10 Still detected at 340 μM Omeprazole 3 1015 231 7 - - - < 130 μM Primidone 5 80 86 65 40 - - < 220 μM Propanolol 2 32 7 - - - - < 50 μM Propyphenazone 2 23 - - - - - < 90 μM Ranitidine 2 111 3 - - - - < 90 μM Sulfamethoxazole 8 95 39 19 15 - - < 220 μM Sulfapyridine 12 50 - - - - - < 50 μM Tonalide 19 188 131 130 53 67 53 72% for 340 μM Triclosan 52 246 55 72 79 70 53 Still detected at 340 μM Trimethoprim 2 73 7 - - - - < 90 μM Venlafaxine 6 179 127 21 - - - < 130 μM

Ozonation time (min) LOQ* 0 2 4 6 10 15 Ozone doses for remotion kR (M-1 s-1) 3-(4-methylbenzylidene) camphor 39 55 50 65 39 72 54 Not removed 4-Aminoantipyrine 19 58 - - - - - < 50 μM 4-methylaminoantipyrne (4-MAA) 2 389 - - - - - < 50 μM Antipyrine 8 30 16 - - - - < 90 μM Atenolol 3 911 655 265 24 - - < 220μM Azithromycin 12 235 - - - - - < 50 μM Benzophenone-3 33 123 89 100 102 119 119 Not removed Bezafibrate 4 115 72 67 37 15 4 Still detected at 340 �M 3260 ± 780 Carbamazepine 1 106 17 2 - - - < 130 μM Carbamazepine epoxide 9 32 23 19 13 - - < 220 μM Ciprofloxacin 5 522 334 28 - - - < 130 μM Citalopram hydrobromide 2 60 31 4 - - - < 130 μM Clarithromycin 5 39 - - - - - < 50 μM Codeine 5 378 - - - - - < 50 μM Cotinine 12 100 61 54 48 38 28 28% remained for 340 μM 680 ± 29 Diclofenac 1 433 - - - - - < 50 μM Diuron 1 100 60 46 25 6 1 Still detected at 340 μM 3890 ± 200 Erythromycin 10 72 16 - - - - < 90 μM Ethylkexyl methoxycinnamate 15 234 274 322 231 214 204 Not removed Famotidine 14 1045 - - - - - < 50 μM Fluoxethine 2 17 - - - - - < 50 μM Furosemide 82 840 - - - - - < 50 μM Galaxolide 23 1486 749 552 178 196 173 83% for 340 μM Gemfibrozil 1 332 50 18 19 15 15 95% for 340 μM Hydrochlorothiazide 1 707 461 199 - - - < 130 μM Indomethacin 2 37 - - - - - < 50 μM Ketoprofen 2 162 156 102 68 18 3 Still detected at 340 μM 3040 ± 770 Ketorolac 2 533 165 - - - - < 90 μM Lansoprazole 9 337 162 84 32 - - < 220 μM Lincomycin 3 12 - - - - - < 50 μM Loratadine 1 29 18 7 2 - - < 220 μM Mefenamic acid 2 59 - - - - - < 50 μM Metoprolol 3 27 17 5 - - - < 130 μM Metronidazole 3 113 73 85 56 14 3 Still detected at 340 μM 3100 ± 780 Musk xylene 3 89 92 95 89 98 91 Not removed Musk ketone 36 123 125 140 95 105 76 38% for 340 μM N-acetyl-4-aminoantipyrine (4-AAA) 50 8605 2419 101 - - - < 130 μM Naproxen 12 109 - - - - - < 50 μM N-formyl-4-aminoanttipyrine (4-FAA)

17 1776 471 21 - - - < 130 μM


Grupo 27 - 40

Benzafibrato (4 ngl-1) y ketoprofeno (3 ngl-1) se detectan a dosis de ozono de 16 mgl-1

No elimina

3-(4-methylbenzylidene) camphor 54 ngl-1

Benzophenone-3 119 ngl-1

Ethylkexyl methoxycinnamate 204 ngl-1

Musk xylene 91 ngl-1

2.4 mgl-1 – 16.33 mgl-1



EFFLUENT O3 O3/H2O2

Tota

l cha

rge

(ng/

l)

79%91%

5,000.0

10,000.0

15,000.0

20,000.0

25,000.0

OthersHydrochlorothiazide4AAA4FAANaproxenAtenololCiprofloxacinCaffeine

-

100.0

200.0

300.0

400.0

500.0

600.0

700.0

97%

99%

EFFLUENT O3 O3/H2O2

Tota

l cha

rge

(ng/

l)

79%91%

79%91%

5,000.0

10,000.0

15,000.0

20,000.0

25,000.0



-

100.0

200.0

300.0

400.0

500.0

600.0

700.0

97%

99%

EFFLUENT O3 O3/H2O2

Tertiary Treatment

19



-10

-5

0

5

10

15

20

25

0 100 200 300 400 500 600 700 800 900

tiempo de reaccion (s)

INH

(%)

O3/AR+t-butanol+pCBA+compuestos emergentes

O3/AR+pCBA+compuestos emergentes

O3+H2O2/AR+pCBA+compuestos emergentes

AR

Inhibición de bioluminiscencia de Vibrio fischeri 30 min

Norma ISO 11348-3



62.7559.1043.04IC (mgl-1)270200230Alcalinidad (mgl-1 CaCO3)

5.845.094.36TOC (mgl-1)3.88.101.99DBO5 (mgO2l-1)

0.540.380.5P-PO43- (mgl-1)

<1613.41.3N-NH4+ (mgl-1)

<0.54.85.2N-NO3¯ (mgl-1)

586126DQO (mgO2l-1)7.317.087.83pH962855797Conduct. (μscm-1)

6.304.932.35Turbidez (NTU)410.00ST (mgl-1)

6.353.951.85SS (mgl-1)U080506U080311Río HenaresPARAMETROS

20



COMPUESTO CONCENTRACIONES (ppb)SULFAMETOXAZOL 2ERITROMICINA 4DICLOFENACO 10IBUPROFENO 4HIDROCLOROTIAZIDA 34-AAA 20ATENOLOL 4GEMFIBROZIL 1CARBAMAZEPINA 2TRICLOSAN 1CAFEINA 2DIURON 1BEZAFIBRATO 1PCBA 1 ppmt-BUTANOL (sólo en muestras 22-05-09) 10 mM



-2 0 2 4 6 8 10 12 14 16

40

60

80

100

Referencia toxicidad

Agua residual dopada

10mM TB +1ppm PCBA1ppm PCBA1ppm PCBA+H2O2

INH

%

tiempo tratamiento

Ecotoxicidad sobre P. subcapitataEvaluada sobre veloc de crecimientoEnsayo en microplacasAgua residual sin diluir

Agua residual sin dopar

21



Oxidation Technologies for Water and Wastewater Treatment, Berlin, april 2009

5th Specialist Conference/10th IOA-EA3 Berlin Conference

S. Shaefer, M. Sievers, A. Ried



0.880.142950.0160.06Bio-

O3/H2O2

TOC + PPCPsewagAlcala

15

3/15

10/30

15

25

Time (min)

0.003

0.8

5

56

180

144

Ozone(kgO3/h)

16

3/15

10/20

120/25

12

Dos. (mg/l)

0.07

0.01

0.01

0.02

0.08

0.01

gen.O3(€/m3)

0.0642Bio-O3EDCsewagIlkeston (UK)

2007

0.450.02Bio-O3PPCPsewagAlcala

0.053

0.042

0.15

0.017

gen.O3+O2+ invest(€/m3)

300Bio-O3-sandfil.

EDC +Phar.

+dissewagRegensforf(S) 2007

2000Bio-O3COD + decolo.sewag

WWTPRanica (I)

2006

1200Bio-O3-

bioCOD +

dis.Ind. + sew

*WWTPKalumburg(D) 2003

8333Bio-O3Dis.sewag

Tubli TseBaharin 2002

Flow(m3/h)

Proc.Obj.Wastw

* 20 % urbana, 80% industrial. Multinacional farmacéutica de fabricación de insulina

7.5 kWhkg-1O3 - 12 – 15 kWhkg-1O3 (producción O3 + O2 + transporte O2) //0.07 €kWh-1

22



REUSE EVALUATIONREUSE EVALUATION



1974 HOY19741974 HOY

23



• Reusing wastewater in irrigation of agricultural land involves lessenvironmental impact than obtaining water from other sources, takinginto account a life cycle perspective?

• Reference technologies considered: ozonation and seawaterdesalination

Emissions to air , water, and soil

WWTP WWTP WWTP

Ozone

Irrigation

Desalination

Irrigation Irrigation Discharge

Syst

em b

ound

arie

s

No reusescenario

Direct reusescenario

Ozone reusescenario

Life Cycle Assessment of ozonationand wastewater reuse



• We include the environmental impact of: – Oxygen production– Production of electricity for the ozonisator– Production of cooling water for the ozonisator– Transport of chemicals to the plant site (100 km)– Production of desalinated water from seawater– Pollutants in treated and untreated wastewater

Life Cycle Assessment of ozonation andwastewater reuse

24



• Effect of ozone on the pollution load of a wastewatereffluent from a urban WWTP

02468

1012141618

0 5 10 15 20 25 30

min

µg/L

02468

1012141618

0 5 10 15 20 25 30

min

µg/L

Total concentration of organic pollutants analyzed vs. time

After 5 minutes there is little additional degradation




• RESULTS for environmental impacts assessed, per m3 water– Aquatic ecotoxicity– Terrestrial ecotoxicity– Human toxicity– Greenhouse effect

DesalinationEffluentPeroxideOzonisatorTransportCooling waterOxygen

Aquatic ecotoxicity

0

1

2

3

4

5

6

7

No reuse Direct reuse Ozone reuse

Terrestrial ecotoxicity

0.000.020.040.060.080.100.120.140.160.180.20


Human toxicity

00.10.20.30.4

0.50.60.70.80.9


Greenhouse effect

0.00.20.40.60.81.01.21.41.61.82.0


Kg

eq. C

O2

Kg

1,4-

dich

loro

benz

ene-

eq.

Kg

1,4-

dich

loro

benz

ene-

eq.

Kg

1,4-

dich

loro

benz

ene-

eq.


25



TABACO



TOMATE

26





27





THANK YOUTHANK YOU

28



InitialInitial selectedselected compoundscompounds

ANTIOXIDANT

Butylated hydroxytoluene- (BHT)

UV-FILTERS

Oxybenzone

2-Octyl-methoxycinnamate

4-methylbenzyledene camphor

Octocrylene

SYNTHETIC FRAGANCES

Celestolide

Phantolide

Traseolide

Galaxolide

Musk xylene

Musk ketone

Tonalide.ANTISEPTICTriclosan

DIOXIN

2,3,7,8-tetrachlolodibenzo-p-dioxinINSECTICIDES

Endosulfan α

Endosulfan β

Endosulfan sulfate.

FIRE RETARDANT

TCPP oekanal.

GC-MSGCGC--MSMS



BHT

Cel

esto

lide

Phan

tolid

eTC

PPTr

aseo

lide

Gal

axol

ide

Mus

k xi

lene

Tona

lide

Mus

k ke

tone

Cam

phor

Tric

losa

n

Oxy

benz

one

Endo

sulfa

nI

Endo

sulfa

nII

Endo

sulfa

nsu

lfate

Cin

nam

ate

2,3,

7,8-

TCD

D

Oct

ocry

lene

Scan

SIM

GC-MSGCGC--MSMSScreeningScreening andand quantificationquantification of of targettarget compoundscompounds andand

““screeningscreening”” of nonof non--targettarget compoundscompounds10 ppb effluent wastewater matrix

29



Compound Linearity MDL (ng/L) Repeatability(RSD, %)

n= 4 Wastewater River

Range (ng/L)

R2 SIM Scan SIM Scan

BHT 25-1000 0,9999 16 16 6 6 6Celestolide 10-1000 1,0000 7 7 3 3 6Phantolide 25-1000 0,9996 7 7 3 3 4TCPP Oekanal 50-1000 0,9976 36 66 14 27 7Traseolide 25-1000 1,0000 18 22 7 9 7Galaxolide 25-500 0,9932 17 20 7 8 7Musk Xylene 10-1000 0,9999 1 4 0.4 2 6Tonalide 25-1000 0,9998 16 22 6 9 8Musk Ketone 25-1000 1,0000 21 21 11 11 4EUSOLEX 6300 50-1000 0,9996 30 43 12 17 3Oxybenzone 50-1000 0,9969 24 63 10 25 6Triclosan 50-1000 0,9963 44 82 18 33 6Endosulfan α 100-1000 0,9996 68 72 27 41 7Endosulfan β 50-1000 0,9980 32 71 13 29 122-Octyl methoxycinnamate 25-1000 0,9976 10 17 4 7 5Endosulfan Sulfate 50-1000 0,9993 35 35 14 14 62,3,7,8-TCDD 25-1000 1,0000 8 51 3 21 8Octocrylene 25-1000 0,9977 11 47 5 19 2

VALIDATION RESULTS OF THE ANALYTICAL METHODVALIDATION RESULTS OF THE ANALYTICAL METHOD



BHT- Butylated hydroxytolueneAntioxidant

OxybenzoneUV-Filter

OctocryleneUV-Filter

4- Methylbenzylidene camphorUV-Filter

TCPP OekanalFire retardant

2-Octyl methoxycinnamateUV-Filter

GalaxolideSynthetic fragance

IntroducciIntroduccióón de compuestos en la base de datos AMDISn de compuestos en la base de datos AMDIS

934 compuestos

GC-MSGCGC--MSMS

30



Scan

SIM

Effluent wastewater

BH

T

TCPP G

alax

olid

eM

usk

xile

ne

Cam

phor

Cin

nam

ate

Oct

ocry

lene

DRSReport in 90 seconds

TCPP OekanaltR = 7.16

TARGET COMPOUNDS IDENTIFICATION AND CONFIRMATIONTARGET COMPOUNDS IDENTIFICATION AND CONFIRMATION



Amount (ug/L) AMDIS NIST

R.T. Cas # Compound NameChemstation

Amount (ng/L)Match

R.T. Diffsec.

Reverse Match

Hit Num.

2.9006 98533 Spiroxamine metabolite (4-tert-butylcyclohexanone) 77 69 63.1250 3228033 Promecarb artifact [5-isopropyl-3-methylphenol] 71 -4.73.1250 3056642 4-tert-Butylphenyl acetate 76 13.1290 89838 Thymol 79 8.9 69 213.4469 88062 2,4,6-Trichlorophenol 48 6.2 59 604.1566 25013165 Butylated hydroxyanisole 85 5.14.1566 121006 3-tert-Butyl-4-hydroxyanisole 80 14.3379 33704619 Cashmeran 77 4.04.3379 64451769 2-(4-(But-2-yl)phenyl)propanoic acid 69 14.3558 128370 BHT, Butylated hydroxytoluene 83 -0.7 81 14.4208 90437 o-Phenylphenol 65 4.2 78 24.4891 90153 1-naphthalenol 55 21.1 74 324.8899 134623 N,N-Diethyl-m-toluamide 93 2.2 90 14.9780 84662 Diethyl phthalate 97 0.4 92 15.3543 119619 Benzophenone 94 3.0 90 15.4719 126738 Tributyl phosphate 75 2.0 74 16.0154 2631370 Promecarb 51 7.16.0154 13743210 3-Buten-2-one, 3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)- 71 16.6321 15323350 Phantolide 50 -9.8 60 157.0589 24691803 Fenfuram 49 -29.97.0589 0000 Cis-8-thiabicyclo[4.3.0]nonane S,S-dioxide 71 17.0888 53112280 Pyrimethanil 71 3.27.1674 13674845 TCPP Oekanal 87 0.2 89 17.3040 106025 Exaltolide [15-Pentadecanolide] 63 -30.07.3040 629801 Hexadecanal 91 17.7754 1506021 Tonalide 74 -24.2 84 47.8110 1222055 Galaxolide 87 -1.9 91 17.9526 81152 Musk xylene 68 -0.9 74 27.9760 84695 Diisobutyl phthalate 75 3.4 89 98.2727 2164092 Chloranocryl 47 -11.59.2224 84742 Di-n-butylphthalate 98 1.8 92 29.6223 2921882 Chlorpyrifos 49 0.7 36 2710.5181 38102644 EUSOLEX 6300, 4-methylbenzylidene camphor 63 1.610.5181 0000 1,7,7-Trimethyl-3-phenethylidenebicyclo[2.2.1]heptan-2-one 59 110.9303 470906 Chlorfenvinphos 86 18.4 71 110.9353 18708866 Chlorfenvinphos, trans- 84 18.0 74 113.2971 5466773 Octinoxanate, 2-Ethylexyl methoxycinnamate 81 2.5 78 213.5214 85687 Butyl benzyl phthalate 68 2.7 71 113.5249 84753 Di-n-hexyl phthalate 49 9.9 52 7413.9729 51036 Piperonyl butoxide 69 3.3 84 214.0235 78513 Tris(2-butoxyethyl) phosphate 59 6.0 58 114.8555 117817 Bis(2-ethylhexyl)phthalate 96 4.4 90 315.5770 6197304 Octocrylene 81 -0.115.5770 35871159 8-Phenylquinoline-6-carboxylic acid 63 1

31



DRSReport in 90 seconds

SCREENINGSCREENINGDRS NON TARGET COMPOUNDSDRS NON TARGET COMPOUNDS Effluent wastewater

Scan

GC-MSGCGC--MSMS



Amount (ng/L)

AMDIS NIST

R.T. Cas # Compound Name Chemstation

Match R.T. Diffsec.

Reverse Match

HitNum.

3.1232 3228033 Promecarb artifact 72 -5.0

3.1232 89838 Thymol 73 8.2

3.1232 98544 Phenol, p-tert-butyl- 86 1

4.0483 25013165 Butylated hydroxyanisole 68 -1.9

4.0483 0000 Undecane 72 1

4.3101 33704619 Cashmeran 78 0.7 77 9

4.3540 128370 BHT, Butylated hydroxytoluene 205 54 -0.9 65 1

4.8832 134623 N,N-Diethyl-m-toluamide 78 1.4 79 2

4.9778 84662 Diethyl phthalate 89 0.4 88 1

5.3506 119619 Benzophenone 86 2.5 89 1

5.4591 126738 Tributyl phosphate 62 0.5 71 1

6.0143 2631370 Promecarb 48 7.0

6.0143 13743210 3-Buten-2-one 77 1

7.1447 13674845 TCPP Oekanal 25 96 -2.6 90 1

7.2180 333415 Diazinon 69 -1.6 63 1

7.8065 1222055 Galaxolide 44 88 -2.5 92 1

7.9687 84695 Diisobutyl phthalate 82 2.6 90 1

8.1999 1506021 Tonalide 21 53 26.7

8.1999 52389158 Epistephamiersine 72 1

9.1963 84742 Di-n-butylphthalate 99 -1.3 94 1

9.5255 81141 Musk Ketone 33 49 -1.6 84 9

13.2728 5466773 2-Ethylexyl methoxycinnamate 62 83 -0.4 83 1

13.4991 85687 Butyl benzyl phthalate 72 -0.0 73 2

14.8361 117817 Bis(2-ethylhexyl)phthalate 96 2.1 88 3

15.5649 6197304 Octocrylene 22 69 -1.6

15.5649 6132872 Benzocarbazole, 5,6-dihydro-3-methoxy- 57 1

GC-MSGCGC--MSMS

32



N,N-Diethyl-m-toluamide

Extracted spectrum

Library spectrum

AMDIS AMDIS DatabaseDatabase GC-MSGCGC--MSMS



DECONVOLUTIONDECONVOLUTION

Triclosan

11.147

11.147

SIM

ScanIon 290

False negative

33



Triclosan

Extracted spectrum

Library spectrum

DECONVOLUTIONDECONVOLUTION

Extracted spectrum

Library spectrum



NON TARGET COMPOUNDSNON TARGET COMPOUNDSCompoundsCompounds notnot includedincluded in AMDIS in AMDIS oror NIST NIST databasedatabasessRetrospectiveRetrospective analysisanalysis

Effluent wastewater

SIM

Scan

34



Ion 2524-Amino Musk Xylene

252

218

267

NON TARGET COMPOUNDSNON TARGET COMPOUNDSCompoundsCompounds notnot includedincluded in AMDIS in AMDIS oror NIST NIST databasedatabasessRetrospectiveRetrospective analysisanalysis

SIM

Scan ?

Synthesized standard4-Amino Musk Xylene

Gatermann et col., 1998

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