Sociedade Brasileira de Espectrometria de Massas – BrMASS
Poster
Assessing emerging contaminants in Brazilian surface waters
using ESI-LC-MS/MS in triple quadrupole.
Cassiana C. Montagner, Igor C. Pescara, Fernando F. Sodré, Wilson F. Jardim
montagner@iqm.unicamp.br
Environmental Chemistry Laboratory, Institute of Chemistry, UNICAMP.
This work describes a method development and validation for the simultaneous
determination of 14 emerging contaminants in surface waters using solid-phase
extraction (SPE) followed by liquid chromatography-mass spectrometry in a triple
quadupole (Agilent 6410B Series) with electrospray ionisation (ESI) in both positive
and negative modes. Target compounds consist of natural and synthetic hormones
(estrone, 17β-estradiol, estriol, progesterone, testosterone, 17α-etynylestradiol,
mestranol and norgestrel), industrial chemicals (bisphenol A, 4n-octylphenol and 4nnonylphenol), and some anthropogenic indicators (caffeine, triclosan and
phenolphthalein). Filtered samples of 1 L were extracted using OASIS HLB cartridges
(500 mg) at 10 mL min-1. Acetonitrile, methanol and reagent water were used in the
conditioning and elution steps. Optimal multiple reaction monitoring (MRM) parameters
were select for each compound as shown in Table 1. Spiked-sample recoveries higher
than 60 % were obtained for all compounds. Quantification limits (LOQ) varied
between 5 and 60 ng L-1. Results for samples collected in the Atibaia River Basin
revealed that 43 % of the investigated compounds were detected at least once.
Concentrations varied from 6.4 (estriol) to 117 ng L-1 (caffeine).
Table 1: LC-MS/MS experimental parameters
Compounds
tR
(min)
Exact
mass
(g mol-1)
Fragmentor
(V)
Precursor
ion (m/z)
Product
ion (Q)*
(m/z)**
Collision
energy
(V)
Product
ion (C)*
(m/z)**
Collision
energy
(V)
LOQ
(ng L-1)
8.10
7.52
8.33
7.73
1.78
314.3
288.3
310.2
312.3
194.1
130
130
110
130
110
315.3
289.3
311.2
313.3
195.1
97.2
97.1
121.0
91.2
138.1
15
20
20
60
15
109.1
109.1
159.2
109.1
110.1
25
25
50
20
20
5
5
5
5
60
270.3
100
272.3
90
288.3
110
296.4
100
288.1
70
318.1
90
206.3
120
220.3
120
228.2
110
= confirmation
269.3
271.1
287.0
295.0
287.0
317.1
205.0
219.0
227.0
144.9
144.9
170.9
144.9
35.1
93.1
106.0
106.0
132.9
30
30
30
30
5
5
15
15
25
182.9
183.0
144.9
158.9
37.1
272.0
132.0
119.0
210.9
35
35
35
30
5
15
25
35
30
5
10
20
10
10
5
5
5
10
ESI (+)
progesterone
testosterone
mestranol
norgestrel
caffeine
ESI (-)
estrone
7.19
17β-estradiol
7.26
estriol
5.93
17α-etynylestradiol
7.17
triclosan
7.11
phenolphthalein
5.33
4n-octylphenol
8.60
4n-nonylphenol
8.97
bisphenol A
6.61
* Q = quantification and C
** m/z ± 0.1
3º Congresso BrMass – 12 a 15 de Dezembro de 2009