INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Evaluation of Ozone Waste Water Treatments and Studies Evaluating the Reuse of Treated Effluents Amadeo R. Fernández-Alba University of Almería, SPAIN
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
-Analysis of wastewater
-Advanced Oxidative Water Teatments ( ozone and Ozone + H2O2)
-Life cicle assesment
Amadeo R. Fernández-Alba University of Almería, SPAIN
1
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
ANALYSIS GCGC-MS GC-MS
LCLC-MS LC-MS
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
ANALYSIS
Target compounds
Non target compounds
LC-QqQ-MS/MS and LC-LiT-MS/MS GC-MS(MS) MS/MS mode (Low mass acc.)
LC-TOF-MS GC-Q-MS Full scan mode (High mass acc.)
Amadeo R. Fernández-Alba University of Almería, SPAIN
2
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
TARGET ANALYSIS
Amadeo R. Fernández-Alba University of Almería, SPAIN
TARGET ANALYSIS
INNOVA-MED CONFERENCE
LIST OF CONTAMINANTS ANALYSED 8-9 October 2009, Girona, SPAIN
Antibiotics 1. Metronidazole 2. Sulfamethoxazole 3. Trimethoprim 4. Ciprofloxacin 5. Cefotaxime 6. Ofloxacin 7. Erythromycin 8. Tetraciclyne 10.Norfloxacin 11.Clarithromycin 12.Lincomycin 13.Sulfamethazine 14.Sulfapyridine 15.Sulfadiazine 16.Sulfathiazole 17.Azithromycin 18.Mevastatin 19.Simvastatin
Analgesic/ Beta Blockers Antidepressants Atenolol 47. Fluoxetine Anti-Inflammatory 35. 36. Propranolol 48. Paroxetine 20. Acetaminophen 21. Indomethacine 22. Fenoprofen 23. Codeine 24. Mefenamic Ac. 25. Ibuprofen 26. Ketorolac 27. Naproxen 28. Diclofenac 29. Ketoprofen 30.Salicilic acid 31.Propyphenazone 32.Urbason
37. Sotalol 38. Metoprolol 39. Nadolol
Contrast media 33. Iopromide 34. Iopamidol
49. Venlafaxine 50. Citalopram 51. Amitriptyline 52. Clomipramine
Antihistamines Lipid regulators
Antiepileptic Psychiatric drug 59. Carbamazepine 60. Diazepan 61. Primidone
Antineoplastics 62. Ifosfamide 63. Cyclophosphamide 64. Tamoxifen
40. Famotidine, 41. Lansoprazole 42. Ranitidine 43. Omeprazole 44. Loratadine
53. Fenofibrate 54. Bezafibrate 55. Gemfibrozil 56. Pravastatin
Diuretics
SympathomimeticsCorticosteroides
45. Furosemide 46. Hydrochlorothiazide
57. Salbutamol 58. Terbutaline
Metabolites 68. 4-Acetoaminoantipyrine 69. 4-Formylaminoantipyrin 70. 4-Methylaminoantipyrine 71. 4-Dimethylaminoantipyrine 72. 4-Aminoantipyrine 73. Paraxanthine 74. Carbamaz.10,11-epoxide 75. Antipyrine 76. Fenofibric Acid 77. Clofibric acid 78. Cotinine
Anesthetics 65. Mepivacaine
66. Methylprednisolone
Anti-Infective 67. Clotrimazole
Pesticides 79. Atrazine 80. Clorpyriphos 81. Clorfenvinphos 82. Diuron 83. Isoproturon 84. Simazine 85. Permetrina
Disinfectants 87. Biphenylol 88. Chlorophene
Others 89. Nicotine 90. Caffeine
EDCs 86. Bisfenol-A
Amadeo R. Fernández-Alba University of Almería, SPAIN
3
TARGET ANALYSIS
INNOVA-MED CONFERENCE SAMPLE TREATMENT 8-9 October 2009, Girona, SPAIN
OASIS HLB
hydrophilic-lypophilic polymer
200 ml wastewater effluent, pH 7-8 400 ml river water, pH 7-8 Elution 4 + 4 ml MeOH
Drying ~ 5min N2
Evaporation
Filtration Filtros de fibra de vidrio 0.7 μm
Wash MIliQ water, pH = 7-8
SPE Reconstitution:
Analysis LC-ESI(+/-)MS or GC-MS
• 1ml MeOH:H2O, 10:90 (v/v) •Filtro PTFE 0.45 µm
Amadeo R. Fernández-Alba University of Almería, SPAIN
TARGET ANALYSIS
INNOVA-MED CONFERENCE SAMPLE TREATMENT 8-9 October 2009, Girona, SPAIN
RECOVERIES 70% Problematic compounds:
Nº
- Very polar and soluble in water (ej. Omeprazole) - Stability depends on the pH (ej. Cefotaxime, tetraciclyne)
19% 11%
Amadeo R. Fernández-Alba University of Almería, SPAIN
4
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -QqQ-MS/MS LC-QqQ-MS/MS
POLAR TARGET COMPOUNDS
Amadeo R. Fernández-Alba University of Almería, SPAIN
POLAR TARGET COMPOUNDS
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -QTRAP LC-QTRAP Identification criteria Compound Positive Ionization Nicotine Salbutamol Atenolol Terbutaline Ranitidine Sotalol 4-MAA 4-DAA 4-AA Paraxanthine Acetaminophen Metronidazole Codeine Caffeine 4-AAA 4-FAA Trimethoprim Cefotaxime Ofloxacin Ciprofloxacin Mepivacaine Metoprolol Antipyrine Omeprazole Propanolol Sulfamethoxazole Carbam.10,11-epoxide Erythromycin Paroxetine
tR (min) (%RSD) 6.1 (5.6) 7.1 (0.4) 7.2 (0.2) 7.3 (0.1) 7.9 (1.2) 8.3 (1.2) 9.7 (0.7) 10.4 (0.5) 10.8 (1.4) 11.0 (1.2) 11.1 (1.0) 12.1 (1.2) 13.0 (3.4) 17.1 (0.3) 17.4 (0.1) 17.6 (0.3) 18.2 (0.3) 18.5 (0.3) 18.7 (0.1) 19.1 (0.3) 19.6 (0.3) 21.0 (0.2) 21.6 (0.3) 22.3 (0.2) 24.9 (0.4) 25.1 (0.4) 25.3 (0.2) 25.5 (0.2) 27.7 (0.1)
Precursor Ion (m/z)
SRM 1*
163.1 240.3 267.3 226.3 315.3 273.3 218.2 232.2 204.2 181.2 152.1 172.1 300.2 195.1 246.2 232.2 291.3 456.1 362.3 332.3 247.4 268.2 189.2 346.3 260.0 254.2 253.2 734.6 330.3
117.2 148.2 145.2 152.2 176.2 133.2 56.1 113.2 56.2 124.2 110.1 128.1 165.2 138.2 228.1 214.2 230.2 396.1 318.3 231.2 98.1 116.2 77.1 198.2 116.2 108.2 180.2 158.3 192.2
SRM 2**
84.1 166.2 190.2 107.1 130.1 213.2 97.2 98.2 159.2 69.2 64.8 82.1 215.3 110.2 83.1 104.1 123.2 324.1 261.3 314.3 70.1 133.2 104.1 136.2 183.2 156.1 236.2 576.5 123.2
133 transitions
In the same time segment!! In positive mode
SRM 3**
130.1 222.2 116.1 125.2 224.2 255.2 159.2 111.2 94.2 96.1 93.0 111.1 199.2 123.1 104.2 83.1 261.2 241.3 245.1 159.2 106.2 151.2 155.2 147.2 210.2 316.1 151.2
[SRM2]/[SRM1] (%RSD) 0.42 (14) 0.28 (8) 0.72 (4) 0.31 (2) 0.66 (10) 0.73 (9) 0.38 (13.) 0.31 (19) 0.21 (11) 0.17 (12) 0.19 (16) 0.51 (11) 0.88 (7) 0.30 (8) 0.98 (6) 0.96 (7) 0..85 (12) 0.95 (4) 0.95 (5) 0.78 (16) 0.30 (9) 0.64 (10) 0.52 (7) 0.60 (15) 0.71 (12) 0.88 (6) 0.68 (11) 0.24 (3) 0.30 (14)
Compound Positive Ionization Carbamazepine Simazine Fluoxetine Ketorolac Methylprednisolone Isoproturon Atrazine Ketoprofen Naproxen Diazepan Biphenylol Indomethacine Fenofibric Acid Mefenamic Ac. Chlorfenvinphos Chlorpyriphos methyl Fenofibrate Negative Ionization Furosemide Hydrochlorothiazide Clofibric acid Bezafibrate Diclofenac Diuron Fenoprofen Ibuprofen Chlorophene Gemfibrozil
tR (min) (%RSD)
Precursor Ion (m/z)
SRM 1*
SRM 2**
SRM 3**
[SRM2]/[SRM1] (%RSD)
28.9 (0.2) 29.0 (0.1) 29.7 (0.2) 30.4 (0.2) 31.3 (0.2) 32.4 (0.2) 32.6 (0.2) 33.3 (0.2) 33.6 (0.3) 35.6 (0.2) 35.8 (0.3) 37.7 (0.3) 37.9 (0.3) 40.4 (0.3) 40.7 (0.3) 43.4 (0.3) 46.6 (0.2)
237.2 202.2 310.3 256.2 475.3 207.3 216.1 255.2 231.2 285.2 171.2 358.2 319.1 242.2 359.1 322.1 361.2
194.3 132.0 44.2 105.1 321.1 72.1 174.1 209.2 185.3 193.2 153.1 139.1 233.1 180.2 155.2 125.1 233.1
192.1 124.2 148.2 178.1 339.3 165.1 104.1 105.1 170.1 154.2 152.0 174.3 139.1 224.2 127.1 290.1 139.1
104.1 457.2 134.2 132.1 177.2 222.3 127.2 121.0 209.2 205.1 109.1 121.1
0.34 (3) 0.88 (7) 0.22 (20) 0.01 (10) 0.80 (11) 0.20 (13) 0.41 (4) 0.78 (12) 0.36 (12) 0.98 (4) 0.63 (5) 0.10 (16) 0.33 (8) 0.58 (12) 0.96 (10) 0.88 (13) 0.98 (6)
5.0 (2.4) 5.7 (0.3) 5.9 (1.3) 7.9 (1.2) 10.9 (0.7) 11.6 (0.5) 11.8 (0.3) 12.5 (0.7) 13.0 (0.3) 13.4 (0.4)
329.1 296.0 213.0 360.1 294.0 231.1 241.1 205.1 217.0 249.2
205.1 269.1 127.1 274.2 250.0 186.1 197.1 161.2 181.2 121.0
285.1 205.0 85.0 154.1 214.1 149.8 93.1 153.0 127.1
126.2 126.0 85.0 122.1 101.0 -
0.86 (3) 0.97 (5) 0.25 (3) 0.62 (2) 0.10 (6) 0.24 (12) 0.67 (4) 0.65 (10) 0.10 (13)
Amadeo R. Fernández-Alba University of Almería, SPAIN
5
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -QqQ-MS/MS LC-QqQ-MS/MS
POLAR TARGET COMPOUNDS Effluent Wastewater
Cotinina
Nicotina
Velafaxime
Propyphenazole
Amadeo R. Fernández-Alba University of Almería, SPAIN
TARGET ANALYSIS
INNOVA-MED CONFERENCE LC-QqLIT-MS/MS 8-9 October 2009, Girona, SPAIN
Identification criteria for the SRM method by LC-QqQ-MS/MS Compound
tR (min) (%RSD)
Product Ion (m/z)
1 SRMSRMMETHOD
3.7 (1.5)
205, [M – H – CO2SO2NH2]–
Clofibric Acid
3.8 (0.7)
127, [M – H –
CO2-C(CH3)2]–
Bezafibrate
4,0 (0.8)
Hydroclhlorothiazide
Product Ion (m/z) SRM 2
[SRM2]/[SRM1] (%RSD)
285, [M – H – CO2]–
0.9 (5)
85, [M – H – C6H4ClO]–
0.2 (8)
274, [M – H – CO2-C(CH3)2]–
154, [M – H –C12H14O3]–
0.7 (3)
5.1 (0.2)
205, [M – H – SO2NCH]–
269, [ M – H – NCH] –
0.9 (3)
Ketoprofen
6.3 (1.2)
209, [M– H – CO2]–
197, [M – H – C2O2]–
0.1 (7)
Naproxen
6.9 (2.7)
Diclofenac
8.8 (0.9)
Furosemide
Fenoprofen Indomethacine Mefenamic Acid
170, [M – C H O ] 185, [M– H – CO ] IDENTIFICATION CRITERIA:
9 tR 9.0 (1.2)
2
4
2
–
2
–
0.4 (12)
250, [M – H – CO2]–
214, [M – H – CO2Cl]–
0.1 (2)
197, [M – H – CO2]–
93, [M – H – C9H8O2]–
0.8 (4)
9 SRM 9.1 2 (0.9) 312, transitions [M – H – CO2]– per compound 297, [M – C2H4O2]– – 9 ratio 9.8 SRM2/SRM1 (0.7) 196, [M– H – CO ] 180, [M – C2H5O2]– 2
0.5 (9) 0.1 (8)
Ibuprofen
10.1 (1.1)
161, [M – H – CO2]–
-
Diuron
10.9 (0.1)
186, [M – H – NH(CH3)2]–
149, [M – H – NH(CH3)2 -Cl]–
Chlorophene
12.2 (0.2)
181, [M – H – Cl]–
153
0.6 (11)
Gemfibrozil
12.3 (0.4)
121, [M – H – CO2C6H12]–
127, [M – H – C8H9OH]–
0.1 (8)
0.2 (8)
Amadeo R. Fernández-Alba University of Almería, SPAIN
6
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC-LiT-MS
QUALITATIVE ANALYSIS
QTrap instruments allows improving confirmatory information: - Application of additional operation modes based on the use of the linear ion trap (LIT) mode.
Compounds for which the second transition: - Not detected -PresentInformation at low intensity Automated Dependent Acquisition (IDA) software. Additional structural information is required for a suitable confirmation Sequentially collect multiple SRM transitions and full scan MS/MS (Enhanced Product Ion, EPI mode) and/ or MS3 spectra in one single run.
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC-QTRAP
QUALITATIVE ANALYSIS Information Dependent Acquisition (IDA) software
Ibuprofen
ESI (-)
TIC
SRM SRM 205.1 Æ 161.2 205.2 161.2
XIC XIC Accurate quantification
Single run 159.1
Reliable confirmation CH3
CH2
-
CH
H3C
161.2 161.2 159.1
161.0
Estructuras?? CH3
CH3
CH 2
-
EPI EPI [M-H] 205.1
-
205.2
H3C
Amadeo R. Fernández-Alba University of Almería, SPAIN
7
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Results Examples for common transitions: fluometuron - diuron
butoxycarboxin – aldicarb sulfone x10 3
x10 2 + MRM (223.00000 -> 86.00000) 50 ppb std chromatogram 0.1%HCOOH
2.4
223.0/86.0
4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%H COOH
223.0/72.0
2.2 2
3
1.8
2
1.6
1
1.2
1.4 1
0
0.8 0.6
x10 2 + MRM (223.00000 -> 148.00000) 50 ppb std chromatogram 0.1%HCOOH 4
Al dicarb sulfone=Al doxycarb
223.0/148.0
3
0
specific specific
2 1
x10 2
223.0/160.0
1.2 1
x10 2 + MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%H COOH 1.5
0.5
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%H COOH
1.4
0
1
0.4 0.2
0.8 0.6
223.0/106.0
specific specific
0.4 0.2 0 14.5
0
15
15.5
16
16.5
17 17.5 18 Counts vs. Acquisition Time (min)
18.5
19
19.5
20
20.5
x10 2 + MRM (223.00000 -> 166.00000) 50 ppb std chromatogram 0.1%H COOH 1.5
223.0/166.0 1
both scanned transitions are common
0.5 0 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 Counts vs. Acquisition Time (min)
9
9.5
10 10.5
11 11.5
12 12.5
13 13.5 14
scanned – unscanned transitions are common Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
QUANTITATIVE ANALYSIS LODs (ng/L)
Amadeo R. Fernández-Alba University of Almería, SPAIN
8
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
NON-TARGET ANALYSIS
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE
LC-TOF-MS 1.7e7
8-9 October 2009, Girona, SPAIN
ESI+
CONFIRMATION
TIC
Intensity, cps
1.3e7 9.0e6 5.0e6 1.0e6
2
6
10
14
18
22
Time, min
26
30
34
10.80 1.05e4
XIC
Codeine 1.3e4
6500.00
15.39
5000.0
2500.00
4.15
1.0
15.66
5.0 m/z, amu
9.0
13.0
240
320
360
2
3.2e5
Acetaminophen
4.0e5
2.4e5
Intensity, counts
Intensity, cps
280 Time, min
NH3 152.0710
8.33
XIC
5.6e5
42
Intensity, counts
Intensity, cps
2.1e4
38
300.1595
HO 2.4e5
[M+H2-COCH3] 1.6e5
110.0606
8.0e4 8.0e4 1.0
5.0
9.0
13.0
17.0
21.0
Time, min Amadeo R. Fernández-Alba
85
125 m/z, amu
165
University of Almería, SPAIN
9
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -TOF-MS LC-TOF-MS
Effluent wastewater x10
7
+ESI TIC Scan Frag=190.0V 100ppbMix_Mt.d
Total ion chromatogram
1.2 1 0.8 0.6 0.4 0.2 x10 4
7.886
+ESI EIC(237.1000) Scan Frag=190.0V 100ppbMix_Mt.d
Extracted ion chromatogram
8 6
Carbamazepine
4 2
4.5
x1 0
5
5
5.5
6
6.5
7
7.5 8 8.5 Counts vs. Acquisition Time (min)
+ 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
[M+H]
Carbamazepine F1: C14H11N Theorethical Mass: 194.0949 0 .8 Error: 1.32 ppm 1
0 .6 0 .4
9
9.5
10
10.5
11
11.5
S u b t ra c t
2 3 7 .1 0 1 9 (M + H )+
237.1019 Carbamazepine: C15H12N2O Theorethical Mass: 237.10197 Error:3 1.4 1 5 . 1 7ppm 81 4 4 7 .2 9 5 9 3 7 3 .2 2 0 2
0 .2
6 1 1 .3 4 3 6 5 4 4 .3 7 0 5
6 7 6 .4 4 7 4
0
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Procedure:
LC -QTOF-MS LC-QTOF-MS Accurate -Mass Database Accurate-Mass Preparació ón de Preparaci Preparación de Standards Standards yy Aná álisis An Análisis
Tabla Tabla de de Datos Datos Excel Excel
Creació ón de Creaci Creación de la la Base Base de de Datos Datos
Integració ón en Integraci Integración en el el Software Software del del equipo equipo
Screening ático de Autom Screening Automá Automático de Standards Standards
ts fragmen in source rce fragments + s e id c u ti 300 pes ls + in so aceutica 93 pharm
Amadeo R. Fernández-Alba
Screening ático Autom Screening Automá Automático de de Muestras Muestras Fortificadas Fortificadas
Screening ático Autom Screening Automá Automático de de Muestras Muestras Reales Reales
University of Almería, SPAIN
10
Screening Database INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
300 Pesticides + 618 Fragments= 918 entries in the database
DATABASE
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -TOF-MS LC-TOF-MS COMPOUND
RT (min)
Theoretical Mass
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
…
…
…
…
…
…
…
Amadeo R. Fernández-Alba University of Almería, SPAIN
11
INNOVA-MED CONFERENCE DATABASE SEARCH
8-9 October 2009, Girona, SPAIN PESTICIDES in solvent (20-500ppb)
10 0.15
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE DATABASE SEARCH
8-9 October 2009, Girona, SPAIN
PESTICIDES in solvent (20-500ppb)
10 0.15
Amadeo R. Fernández-Alba University of Almería, SPAIN
12
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC -TOF-MS LC-TOF-MS
Effluent wastewater x10
7
+ESI TIC Scan Frag=190.0V 100ppbMix_Mt.d
Total ion chromatogram
1.2 1 0.8 0.6 0.4 0.2 x10 4
7.886
+ESI EIC(237.1000) Scan Frag=190.0V 100ppbMix_Mt.d
Extracted ion chromatogram
8 6
Carbamazepine
4 2
4.5 x1 0
5
5
5.5
6
6.5
7
7.5 8 8.5 Counts vs. Acquisition Time (min)
+ 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
[M+H]
Carbamazepine F1: C14H11N Theorethical Mass: 194.0949 0 .8 Error: 1.32 ppm 1
9
9.5
10
10.5
11
11.5
S u b t ra c t
2 3 7 .1 0 1 9 (M + H )+
237.1019 Carbamazepine: C15H12N2O Theorethical Mass: 237.10197 Error:3 1.4 1 5 . 1 7ppm 81 4 4 7 .2 9 5 9
0 .6 0 .4
6 1 1 .3 4 3 6
3 7 3 .2 2 0 2
0 .2
6 7 6 .4 4 7 4
5 4 4 .3 7 0 5
0
Amadeo R. Fernández-Alba University of Almería, SPAIN
Searching for UNKNOWN pesticides in food by LC/TOF-MSINNOVA-MED CONFERENCE NON TARGET 8-9 October 2009, Girona, SPAIN (Using the chlorine isotope signature) 26.73 6.0e7 1.6e5 5.8e7
311.0716
An impurity from commercial Methyl substituted Imazalil formulations containing imazalil DBE 7.5
-CH3
1.5e5 5.6e7 1.5e5 5.4e7 1.4e5 5.2e7
O
1.4e5 5.0e7 1.3e5 4.8e7 1.3e5 4.6e7 1.2e5 4.4e7 1.2e5 4.2e7 1.1e5 4.0e7 1.1e5 3.8e7 1.0e5
Cl
N N
Ion Trap MS/MS
Cl 313.0687
Intensity, cps
Intensity, counts
m/z 311 Æ 269
Imazalil methyl-derivate
3.6e7 9.5e4 3.4e7 9.0e4 3.2e7 8.5e4 3.0e7 8.0e4 2.8e7 7.5e4
m/z 297 Æ 255
Imazalil
2.6e7 7.0e4 6.5e4 2.4e7
DBE 7.5
6.0e4 2.2e7 5.5e4 2.0e7
25.71
5.0e4 1.8e7 4.5e4 1.6e7
28.11
299.0529 18.01
4.0e4 1.4e7 3.5e4 1.2e7
3.0e4 1.0e7 2.5e4 8.0e6 2.0e4 6.0e6 1.5e4 4.0e6 1.0e4 2.0e6 5000.0 0.0 0.0 8.0
26.09
14.0160 Æ + CH2
297.0556
21.66 312.0741 19.39
22.9823.24
20.70
25.04
28.42 28.85
24.13
29.06
20.26
315.0662 298.0588 301.0510 316.0684
9.0
10.0
11.0
12.0
13.0
14.0
15.0 290 16.0 300 17.0
230 240 250 260 270 280 Amadeo R. Fernández-Alba
University of Almería, SPAIN
18.0 23.0 310 19.0 320 20.0 330 21.034022.0 350 Time m/z, amu [min]
24.0 360
25.0 370 26.0 380 27.039028.0
29.0
30.0
13
INNOVA-MED CONFERENCE
TOF-MS REPORT Effluent wastewater
8-9 October 2009, Girona, SPAIN
INFLUENT (ng/L)
EFFLUENT (ng/L)
pKa
Log kow
Max.
Min.
Average
Max.
Min.
9.4
0.46
37458
1571
23202
< LOQ
< LOQ
Acetaminophen
Average Removal Efficiency (%) < LOQ 100
Amadeo R. Fernández-Alba University of Almería, SPAIN
LC-TOF Chromatogram INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Effluent Wastewater Total Ion Chromatrogram
x10 7 +ESI TIC Scan Frag=190.0V elejido_dic_07_E.d 1.2 1 0.8 0.6 0.4 0.2 x10 4 +ESI EIC(110.0600) Scan Frag=190.0V elejido_dic_07_E.d Smooth 6
Acetaminophen H N
NH2
4 2 0
Extracted Ion Chromatrogram 110.0608
P-aminophenol
1.255
O 7.016
HO
1.020
CH3
HO
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 Counts vs. Acquisition Time (min)
x10 4 +ESI Scan (1.272 min) Frag=190.0V elejido_dic_07_E.d Subtract 110.0608 (M+H)+
6
P-aminophenol [C6H7N O]+
4 2 0 109
110
111
112
113
114
115
Amadeo R. Fernández-Alba
116
117
118 119 120 121 122 Counts vs. Mass-to-Charge (m/ z)
123
124
125
126
127
128
129
130
131
University of Almería, SPAIN
14
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
LC-TOF Chromatogram
Effluent Wastewater treated with O3 Scan Frag=90.0V Alin 071211 O3.d x10 7 +ESI TIC Total Ion Chromatrogram 2.5 1
1
2 1.5 1 0.5
Azithromycin Scan Frag=90.0V Alin 071211 O3.d x10 4 +ESI EIC(749.5158) 5.534
4 1
1
x10 4 +ESI Scan (5.550 min) Frag=90.0V Alin 071211 O3.d Su… 3 749.5155 (M+H)+ 2
3 2
1
1 0
11.418
0
5.068
748
749
750
751
752
753
13.267
754
x10 4 +ESI EIC(591.4221) Scan Frag=90.0V Alin 071211 O3.d 2
4.216
1
591.4218 (M+H)+
2
1.5
12.286
1
1 0.5
5.534
0 590 6.917
0 0.5
1
1.5
2
2.5
3
3.5
4
4.5
1
x10 4 +ESI Scan (4.232 min) Frag=90.0V Alin 071211 O3.d Su…
5
5.5
Amadeo R. Fernández-Alba
6
6.5
7
591
592
593
594
595
596
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 Counts vs. Acquisition Time (min)
University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
QUANTITATIVE ANALYSIS LODs (ng/L)
Amadeo R. Fernández-Alba University of Almería, SPAIN
15
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
CARACTERIZACIÓN EDAR ALCALA OESTE (Aguas urbanas)
WATER TREATMENT
1989 (2002). 374.090 h.e. 3000 m3h-1 Sedimentación primaria. Fangos Activados con eliminación de nutrientes. Nitrificación/desnitrificación
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
44 compuestos detectados al menos en 4 muestras del influente
Amadeo R. Fernández-Alba University of Almería, SPAIN
16
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
100
1
90
3
4 5
2
26 25
80
23
Removal efficiency (%)
22
24
17
70 60
8 9
11 10 12
18 19 14
7 (27) atenolol, 50 (36) propanolol, (30) metoprolol, 21(28) sulfamethoxazole, (40) erythromycin, (33) 15 trimethoprim, (29) fenofibric acid, (31) 16 bezafibrate, (32) ketoprofen, (34) Diclofenac, (35) 6 indomethacine, (37) mefenamic acid, (38) omeprazole, (39) carbamazepine 40
30 20
28 32 31
27
10 0 -8.00
29
-6.00
-4.00
-2.00
35
39
34
40
37
36
0.00
2.00
4.00
6.00
log Dow
Dow =
Amadeo R. Fernández-Alba
8.00
K ow 1 + 10 pH − pKa
University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
AOP Procesos oxidativos donde se generan radicales hidroxilo en cantidad suficiente para influir en el tratamiento del agua
O3 + OH − → HO2− + O2 70 M −1s −1 O3 + HO2− → HO2• + O3•− HO
• 2
k=7.9x105 s-1 -k=5x1010
M-1s-1
O
•− 2
+H
+
pK=4.8
2.2 x106 M −1s −1
HO
• 3
k=3.3x102 s-1 -k=5.2x1010 M-1s-1
O
•− 3
+H
O3 + O2•− → O3•− + O2
1.6 x106 M −1s −1
HO3• → HO • + O2
1.1x105 M −1s −1
+
pK=8.2
a pH 7 y valores de H2O2 10-5 – 10-3 M valores significativos de descomposición de ozono Amadeo R. Fernández-Alba University of Almería, SPAIN
17
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
2.4 mgl-1 – 16.33 mgl-1 TABLE 2 Ozonation time (min) 3-(4-methylbenzylidene) camphor 4-Aminoantipyrine 4-methylaminoantipyrne (4-MAA) Antipyrine Atenolol Azithromycin Benzophenone-3 Bezafibrate Carbamazepine Carbamazepine epoxide Ciprofloxacin Citalopram hydrobromide Clarithromycin Codeine Cotinine Diclofenac Diuron Erythromycin Ethylkexyl methoxycinnamate Famotidine Fluoxethine Furosemide Galaxolide Gemfibrozil Hydrochlorothiazide Indomethacin Ketoprofen Ketorolac Lansoprazole Lincomycin Loratadine Mefenamic acid Metoprolol Metronidazole Musk xylene Musk ketone N-acetyl-4-aminoantipyrine (4-AAA) Naproxen N-formyl-4-aminoanttipyrine (4FAA) Nicotine Norfloxacin Octocrylene Ofloxacin Omeprazole Primidone Propanolol Propyphenazone Ranitidine Sulfamethoxazole Sulfapyridine Tonalide Triclosan Trimethoprim Venlafaxine
Grupo 27 - 40
LOQ* 39 19 2 8 3 12 33 4 1 9 5 2 5 5 12 1 1 10 15 14 2 82 23 1 1 2 2 2 9 3 1 2 3 3 3 36 50 12 17
0 55 58 389 30 911 235 123 115 106 32 522 60 39 378 100 433 100 72 234 1045 17 840 1486 332 707 37 162 533 337 12 29 59 27 113 89 123 8605 109 1776
2 50 16 655 89 72 17 23 334 31 61 60 16 274 749 50 461 156 165 162 18 17 73 92 125 2419 471
4 65 265 100 67 2 19 28 4 54 46 322 552 18 199 102 84 7 5 85 95 140 101 21
6 39 24 102 37 13 48 25 231 178 19 68 32 2 56 89 95 -
10 72 119 15 38 6 214 196 15 18 14 98 105 -
15 54 119 4 28 1 204 173 15 3 3 91 76 -
4 8 16 3 3 5 2 2 2 8 12 19 52 2 6
81 38 114 3594 1015 80 32 23 111 95 50 188 246 73 179
12 56 115 276 231 86 7 3 39 131 55 7 127
10 113 18 7 65 19 130 72 21
13 81 11 40 15 53 79 -
10 95 9 67 70 -
14 91 10 53 53 -
Ozone doses for remotion Not removed < 50 μM < 50 μM < 90 μM < 220μM < 50 μM Not removed Still detected at 340 M < 130 μM < 220 μM < 130 μM < 130 μM < 50 μM < 50 μM 28% remained for 340 μM < 50 μM Still detected at 340 μM < 90 μM Not removed < 50 μM < 50 μM < 50 μM 83% for 340 μM 95% for 340 μM < 130 μM < 50 μM Still detected at 340 μM < 90 μM < 220 μM < 50 μM < 220 μM < 50 μM < 130 μM Still detected at 340 μM Not removed 38% for 340 μM < 130 μM < 50 μM < 130 μM
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
kR (M-1 s-1)
3260 ± 780
680 ± 29 3890 ± 200
3040 ± 770
3100 ± 780
Still detected at 340 μM < 90 μM 20% for 340 μM Still detected at 340 μM < 130 μM < 220 μM < 50 μM < 90 μM < 90 μM < 220 μM < 50 μM 72% for 340 μM Still detected at 340 μM < 90 μM < 130 μM
* LOQ calculated in ozonated samples. Cconcentration expressed as ng/L
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Tertiary Treatment
Total charge (ng/l)
25,000.0
20,000.0 700.0
15,000.0
Others Hydrochlorothiazide
97%
600.0
4AAA 4FAA
500.0 400.0 300.0
10,000.0
99%
200.0 100.0 -
5,000.0
Naproxen Atenolol Ciprofloxacin Caffeine
79% 91% EFFLUENT EFFLUENT
O33 O
O OO 3/H 3/H 2O22 2
Amadeo R. Fernández-Alba University of Almería, SPAIN
18
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
Norma ISO 11348-3
Inhibición de bioluminiscencia de Vibrio fischeri 30 min 25
O3/AR+t-butanol+pCBA+compuestos emergentes O3/AR+pCBA+compuestos emergentes
20
O3+H2O2/AR+pCBA+compuestos emergentes AR
INH (%)
15 10 5 0 0
100
200
300
400
500
600
700
800
900
-5 -10
tiempo de reaccion (s)
Amadeo R. Fernández-Alba University of Almería, SPAIN
INNOVA-MED CONFERENCE 8-9 October 2009, Girona, SPAIN
PARAMETROS
Río Henares
U080311
SS (mgl-1)
1.85
(mgl-1)
410.00
ST
Turbidez (NTU) Conduct.
(μscm-1)
pH DQO (mgO2l-1) N-NO3
U080506
3.95
6.35
2.35
4.93
6.30
797
855
962
7.83
7.08
7.31
26
61
58
¯ (mgl-1)
5.2
4.8
