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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
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
-Analysis of wastewater
-Advanced Oxidative Water Teatments( ozone and Ozone + H2O2)
-Life cicle assesment
2
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
LC-MSLCLC--MSMSGC-MSGCGC--MSMS
ANALYSIS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
TARGET ANALYSISTARGET ANALYSIS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
POLAR TARGET COMPOUNDSLC-QqQ-MS/MSLCLC--QqQQqQ--MS/MS/MSMS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
Nicotina Cotinina
Velafaxime Propyphenazole
POLAR TARGET COMPOUNDS
Effluent Wastewater
LC-QqQ-MS/MSLCLC--QqQQqQ--MS/MS/MSMS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
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
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
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
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
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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
+ 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
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
QUANTITATIVE ANALYSIS
LODs (ng/L)
9
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
NONNON--TARGET ANALYSISTARGET ANALYSIS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
DATABASE
300 Pesticides + 618 Fragments= 918 entries in the database
ScreeningScreening DatabaseDatabase
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
DATABASE SEARCH
10
0.15
PESTICIDES in solvent (20-500ppb)
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
10
0.15
DATABASE SEARCHPESTICIDES in solvent (20-500ppb)
13
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
QUANTITATIVE ANALYSIS
LODs (ng/L)
16
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
44 compuestos detectados al menos en 4 muestras del influente
17
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
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
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
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
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
OthersHydrochlorothiazide4AAA4FAANaproxenAtenololCiprofloxacinCaffeine
OthersHydrochlorothiazide4AAA4FAANaproxenAtenololCiprofloxacinCaffeine
-
100.0
200.0
300.0
400.0
500.0
600.0
700.0
97%
99%
EFFLUENT O3 O3/H2O2
Tertiary Treatment
19
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
-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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
-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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
Oxidation Technologies for Water and Wastewater Treatment, Berlin, april 2009
5th Specialist Conference/10th IOA-EA3 Berlin Conference
S. Shaefer, M. Sievers, A. Ried
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
REUSE EVALUATIONREUSE EVALUATION
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
1974 HOY19741974 HOY
23
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
• 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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
• 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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
• 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
Life Cycle Assessment of ozonationand wastewater reuse
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
• 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
No reuse Direct reuse Ozone reuse
Human toxicity
00.10.20.30.4
0.50.60.70.80.9
No reuse Direct reuse Ozone reuse
Greenhouse effect
0.00.20.40.60.81.01.21.41.61.82.0
No reuse Direct reuse Ozone reuse
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.
Life Cycle Assessment of ozonationand wastewater reuse
25
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
TABACO
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
TOMATE
26
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
27
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
THANK YOUTHANK YOU
28
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
DRSReport in 90 seconds
SCREENINGSCREENINGDRS NON TARGET COMPOUNDSDRS NON TARGET COMPOUNDS Effluent wastewater
Scan
GC-MSGCGC--MSMS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
N,N-Diethyl-m-toluamide
Extracted spectrum
Library spectrum
AMDIS AMDIS DatabaseDatabase GC-MSGCGC--MSMS
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
DECONVOLUTIONDECONVOLUTION
Triclosan
11.147
11.147
SIM
ScanIon 290
False negative
33
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
Triclosan
Extracted spectrum
Library spectrum
DECONVOLUTIONDECONVOLUTION
Extracted spectrum
Library spectrum
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
NON TARGET COMPOUNDSNON TARGET COMPOUNDSCompoundsCompounds notnot includedincluded in AMDIS in AMDIS oror NIST NIST databasedatabasessRetrospectiveRetrospective analysisanalysis
Effluent wastewater
SIM
Scan
34
INNOVA-MED CONFERENCE8-9 October 2009, Girona, SPAIN
Amadeo R. Fernández-AlbaUniversity of Almería, SPAIN
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