Analysis of EDCs and Pharmaceuticals By LC-MS/MS

Analysis of EDCs and
Pharmaceuticals
By LC-MS/MS
Brett Vanderford & Shane Snyder
Southern Nevada Water Authority
Water Quality Research and Development

What is SNWA Water Quality
Research and Development (R&D)?
Established in 2000
Group of scientists, engineers, post-graduate
researchers, technicians, and undergraduate/
graduate interns
Goals
• Compete for externally funded grants
• Awarded over $3,000,000 in competitive grants
• Collaborate with other utilities and research groups
• Proactively study emerging contaminants
• Method development
• Occurrence and fate
• Improve treatment processes
• Minimize DBPs
• Increase efficiency
• Publish/present findings to share knowledge with others
• Published 40+ manuscripts in peer-reviewed journals
• Presented findings at numerous conferences

F
F
F
Tandem Mass Spectrometry
O
Fluoxetine (Prozac)
MW: 309
F
F
F
O
N
H
(MS/MS)
N
H 2
Precursor (310 m/z)
(From source)
Precursor/product ion transition (310 → 44) – very selective!
F
F
F
O
Neutral
+
N
H
Product (44 m/z)

Matrix Effects
• Analytes need to be charged to enter MS
• Limited pool of charge available
• Non-target compounds can prevent
compounds of interest from becoming
charged
• Leads to lower recoveries, uncertainty
• NOM…?

1000
900
800
700
600
500
400
300
200
100
0
Consequences of Matrix Effects
On Data Interpretation
75%
50%
Raw Water Treatment
Process 1
10%
Treatment
Process 2
True Concentration (ng/L)
Observed Concentration (ng/L)
5%
Treatment
Process 3
0%
Finished Water

Isotope Dilution
N
O NH 2
Carbamazepine
Treatment for epilepsy
D
D
D
D
D D
N
O NH 2
Carbamazepine-d10
Non-radioactive isotope label
Very low prob. of natural occurrence
Chemically very similar
Add to all samples
Corrects for extraction losses
Corrects for matrix effects
D
D
D
D

Surface Water Impacted by Wastewater
Spike @ 25 ng/L
130%
120%
110%
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Norfluoxetine
Sulfamethoxazole
Atenolol
Trimethoprim
Fluoxetine
Meprobamate
Dilantin
Carbamazepine
Atrazine
Isotope Dilution
External Calibration Method
Diazepam
Linuron
Atorvastatin
o-Hydroxy atorvastatin
p-Hydroxy atorvastatin
Risperidone
Enalapril
Gemfibrozil
Bisphenol A
Simvastatin - H2O
Simvastatin hydroxy acid
Diclofenac
Naproxen
Triclosan

Depth (m)
Depth (m)
-10
-30
-50
-70
-90
-110
-130
-150
-10
-30
-50
-70
-90
-110
-130
-150
Meprobamate (ng/L)
0 2 4 6 8 10 12 14 16
LV Wash LV Basin (Km) Hoover Dam
O
N
O
H 2N
O
O
HN S O
NH 2
O
O
NH2
Sulfamethoxazole (ng/L)
0 2 4 6 8 10 12 14 16
LV Wash LV Basin (Km) Hoover Dam
50
40
30
20
10
0
30
25
20
15
10
5
0

Drinking Water/Wastewater
Treatment Processes
(>60 EDCs/PPCPs
EDCs/ PPCPs)
Project 2758 “Removal of EDCs/PPCPs”

Wastewater Ozonation
Projects 04-007 & 06-012 “Advanced Oxidation”

Toxicological Relevance of
AwwaRF #3085
Pharmaceuticals and
EDCs in Drinking Water
WRF 04-003

???????????

Thank you!
Brett Vanderford
brett.vanderford@snwa.com