Evaluation of Analytical Chemical Methods for Detection of Estrogens in the Environment
Compounds
Samples
Sample preparation
Analytical method
LOD/LOQ
Ref
E1-3S, E1-3G,
E2-3S, E2-3G,
E2-17S, E2-
3S17G, E2-
3G17S, E2-
3,17DiS, E3-3S,
E3-3G, E1, α-E2,
ß-E2, E3, EE2
River, lake water,
effluent (STP)
Detection:
E1-3S: 0.3-2.2 ng/L
E2-3S: 0.2-1 ng/L
Filtration (1L)
pH-adjustment to 3.5-5 with acetic acid
SPE: Autoprep EDS-1
Elution: Free: ethyl acetate; Conjugates:
5mM TEA in MeOH
Florisil clean-up (free)
Dissolved in 100 µL-1mL
LC-MS/MS, ESI (-)
StP: Zorbax Extend-C18
column (150 mm x 1 mm
I.D., 3.5 µm, Agilent)
MP: A: Acetonitrile; B:
H2O, C: 100 mM TEA in
H2O (pH 12.2)
Temp: 30 ºC, FR:
40µL/min; IV: 10 µL
MDL:
Free: 0.1-1.5 ng/L;
Conjugates: 0.1-3.1 ng/L
(105)
E1-3S, E1-3G,
E2-3S, E2-3G,
E2-17G, E3-3S,
E3-3G,E3-16G
E1, α-E2, ß-E2,
E3, EE2
Female urine, septic
tank collecting
domestic
wastewater, influent
and effluent (STP)
Preservation with formaldehyde (1%, v/v)
Filtration (Whatman GF/C glass fiber, 1.5
µm), washing filter with 3 mL MeOH, added to
the aqueous extract
SPE (0.5 g Carbograph 4, GCB) washing
After loading of the water samples, the
cartridges were washed sequentially with: 50
mL of distilled water, 10 mL MeOH acidified
with formic acid 50 mM and 5 mL MeOH
Elution of the free: 12 mL methylene
chloride:MeOH ( 80:20, v/v)
After elution of the free estrogens from the
SPE the cartridges were reversed(?), eluted
with 20 mL methylene chloride/MeOH (60:40,
v/v) containing 10 mM NaAcetate
Reconstituted with 200 µL H2O:MeOH (50:50,
v/v) after solvent evaporation
LC-MS/MS, ESI (-)
StP: Alltima C18 column
(25x4.6 mm I.D., 3.5 µm)
MP: A Acetonitril: B: Water
both 10 mM formic acid
FR: 1 mL/min; IV: 50 µL
LOQ (ng/L):
Urine: Free: 16-40;
conjugates: 20-600;
Wastewater: F:2-4; C: 2-
60;
STP influent: F: 1-2; C:
0.8-30;
STP effluent: F: 0.5-1;
C: 0.3-12
(106;107)
E1-3S, E1-3G,
E2-3S, E2-3G,
E2-17G, E3-3S,
E3-3G,E3-16G
Raw sewage,
treated sewage,
river water
Filtration (Whatman GF/C glass fiber, 1.5
µm), washing filter with 3 mL MeOH, added to
the aqueous extract
SPE (0.5 g Carbograph 4, GCB) cartridges
LC-MS/MS, ESI (-)
StP: Alltima C18 column
(250 x 4.6 mm I.D., 3.5
µm)
LOD (ng/L):
STP influent (100 mL)
F: 0.4-0.85, C: 0.2-15
STP effluent (250 mL)
(108)
E1, α-E2, ß-E2,
E3, EE2
washing with 10 mL dichloromethane:MeOH
(80:20, v/v) containing 5mM TMACI
(tetraethylammonium Chlorid), 5 mL MeOH,
20 mL water acidified (pH 2) with HCl, distilled
water 5 mL
Loading on the SPE
After the loading the SPE were sequentially
washed with 50 mL distilled water, 10 mL
MeOH acidified with 50 mM formic acid and
10 mL MeOH
Elution: F: 10 mL dichloromethane: MeOH
(80:20, v/v) into glass vials with conical
bottom; C: were back eluted from the SPE
with 10 mL dichloromethane: MeOH (80:20,
v/v) containing 5mM TMACl into glass vials.
Extracts were evaporated at 30 ºC under N2.
Re-dissolved in 200 µL Water:MeOH (50:50;
v/v)
MP: Free: A: Acetonitril: B:
Water both 10 mM formic
acid; Post column addition
of MeOH containing 40
mM NH3, at FR:0.1mL/min
Conjugated: Acetonitril: B:
Water both 10 mM formic
acid;
FR: 1 mL/min;
IV: 50 µL
F: 0.04-024, C: 0,04-6
River water (2 L)
F: 0.005-0.03, C: 0.05-0
E1-3S,E32-3S,
E3-3S, E2-17S,
E2-3,17DiS
d4-E2-3S (IS)
Human urine
Robotic SPE extraction in the 96.Well Disk
Plate
LC-MS/MS, ESI (-)
StP: Keystone Betasil C18
column (150 x 2 mm, 5
µm)
MP: 5 mM ammonium
sacetate, pH = 5.4/MeOH
(50:50)
FR: 200 µL/min; IV: 20 µL
LOQ:
C: 0.2 ng/mL
(109)
Human urine
HPLC-UV
(110)
FR: flow rate; MDL: method detection limit; IV: injection volume; MP: mobile phase; StP: stationary phase.
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