1. The removal of Selected
Pharmaceuticals on WWTP
in the Czech Republic
F. Wanner, M. Váňa, L. Matoušová, J. K. Fuksa, D. Pospíchalová
1st Bulgarian National YWP Conference, 17.5. 2012, Sofia

2. Introduction
Removal of organic pollution on WWTPs has been practically solved.
Improving removal efficiency of Nitrogen and Phosphorus on WWTP.
Attention of public now focusing on new specific pollutants.
PPCP (pharmaceuticals and personal care products)
The consumption of these substances is rising.
Wastewaters→ WWTPs→ Receiving waters
Removing?

3. Research project in the Czech Republic
The possibilities of removing selected specific pollutants
(PPCP) on WWTP
The goals of the project is to describe:
Concentrations of selected PPCP in the wastewaters
Treatment efficiency of classical biological WWTP
Propose and verify optimal technologies for PPCP removing
The main work packages of the project:
1. Literature research of up-to-date knowledge about removing
selected PPCP on WWTP.
2. Monitoring of PPCP concentrations in the influent and
effluent on selected WWTP in the Czech republic.
3. Model of WWTP for verifying advanced technologies for
better PPCP remove.

4. Observed substances
• Analgesic and Non-steroidal anti-inflammatory
drug (NSAID). About 70% used as liniment
Diclofenac (over-the-counter), except Europe used per
(CAS 15307-86-5) orally.
• Consumption in the CR c. 20 tons per year.
• Non-steroidal anti-inflammatory drug (NSAID).
Ibuprofen Generally used per orally.
(CAS 15687-27-1) • Consumption in the CR c. 200 tons per year.
• Anti-epileptic, antidepressant etc. Used purely
Carbamazepine per orally and only for prescription.
(CAS 298-46-4) • Consumption in the CR c. 7,5 tons per year.

5. Observed substances
• Basic metabolite of Acetylsalicylic Acid
Salicylic Acid (Aspirin). Direct usage only for eyes
(CAS 69-72-7) applications.
• Consumption in the CR c. 600 tons per year.
• Basic metabolite of fibrates used for level
Clofibric Acid control of lipoproteins (cholesterol) in blood.
(CAS 882-09-7) • Consumption in the CR c. 10 tons per year.

6. Observed substances
Kidney Aspirin
Salicylic Acid
Diclofenac
Ibuprofen Clofibric Acid Carbamazepine

7. Observed WWTP
Range of Population
WWTP Technological scheme
Equivalent
Mechanical-biological WWTP with biological
Over
A nitrogen and phosphorus removal,
80 000
anaerobic sludge stabilization.
Mechanical-biological WWTP with bio-filters,
B 10 000 – 50 000 chemical precipitation, aerobic sludge
stabilization.
Mechanical-biological WWTP with biological
C 50 000 – 80 000 nitrogen and phosphorus removal,
anaerobic sludge stabilization.
Mechanical-biological WWTP (carrousel
D 10 000 – 50 000 type) with biological nitrogen removal and,
aerobic sludge stabilization..

8. Sampling and Analyses
• Standart Spot Samples collected into 2l glass sample containers
• Conserved by adding sulphuric acid (2 ml per l)
• Samples filtered trough cellulose membrane filters (0,45 μm)
• Added mixture of internal standards 5 ml
• Pre-concentrated by on-line SPE (solid phase extraction)
• Determination method LC/MS on liquid chromatograph Agilent 1200 RR
• Mobile phase methanol/water acidified 0,2% of acetic acid in the
gradient elution.
• Analyzed only original substances, not metabolites or conjugates.

9. WWTP A Results
Clofibric Salicylic Carba-
Diclofenac Ibuprofen
Profile Acid Acid mazepine
(ng/l) (ng/l)
(ng/l) (ng/l) (ng/l)
Influent n. a. 308 21 900 67 000 514
n. a. 410 21 300 35 700 694
Effluent n. a. 246 372 3660 648
n. a. 893 309 1410 691

10. WWTP B Results
Clofibric Salicylic Carba-
Diclofenac Ibuprofen
Profile Acid Acid mazepine
(ng/l) (ng/l)
(ng/l) (ng/l) (ng/l)
16.3 600 8360 20 900 192
15.6 765 9330 28 200 358
Influent 13.9 625 12 100 48 100 238
< 10 1000 14 300 45 700 261
< 10 602 5310 12 500 237
< 10 786 477 471 290
< 10 828 144 607 424
Effluent < 10 914 634 3900 277
n. a. 1580 7150 20 500 1220
<10 813 2480 1300 274

11. WWTP C Results
Clofibric Salicylic Carba-
Diclofenac Ibuprofen
Profile Acid Acid mazepine
(ng/l) (ng/l)
(ng/l) (ng/l) (ng/l)
n. a. 187 4670 11 000 184
18.4 541 7530 20 400 350
Influent 14.5 538 10 900 34 900 505
n. a. 758 11 200 14 400 1050
n. a. 357 7360 19 500 542
n. a. 351 46,0 825 264
18.3 534 283,0 384 435
Effluent n. a. 617 47,5 666 553
n. a. 900 62,3 684 958
n. a. 536 129 1600 745

12. WWTP D Results
Clofibric Salicylic Carba-
Diclofenac Ibuprofen
Profile Acid Acid mazepine
(ng/l) (ng/l)
(ng/l) (ng/l) (ng/l)
19.6 995 19 200 42 800 1270
10.2 790 19 900 32 600 816
Influent n. a. 833 16 300 28 500 1610
n. a. 1280 27 200 28 600 1890
n. a. 740 15 000 16 100 2050
n. a. 671 62,7 1230 932
n. a. 769 169 520 701
Effluent n. a. 1070 205 529 1690
n. a. 1520 532 1440 1830
n. a. 1320 318 684 1860

13. WWTP C - Ibuprofen
14000
12000
10000
8000
ng/l
6000
4000
2000
0
Influent Mechanical Denitrification Nitrification Regeneration Effluent
Treatment

14. WWTP C - Salicylic Acid
40000
35000
30000
25000
ng/l
20000
15000
10000
5000
0
Influent Mechanical Denitrification Nitrification Regeneration Effluent
Treatmnet

15. WWTP C - Diclofenac
1000
900
800
700
600
ng/l
500
400
300
200
100
0
Influent Mechanical Denitrification Nitrification Regeneration Effluent
Treatment

16. WWTP C - Carbamazepine
1200
1000
800
ng/l
600
400
200
0
Influent Mechanical Denitrification Nitrification Regeneration Effluent
Treatment

17. Total Treatment Efficiency
Clofibric Salicylic
No. of Diclofenac Ibuprofen Carbamazepine
Acid Acid
Sample [%] [%] [%]
[%] [%]
A1 n. a. 20 98 95 -26
A2 n. a. -118 99 96 0
B1 ≥ 59 -31 94 98 -51
B2 ≥ 57 -8 98 98 -18
B3 ≥ 52 -46 95 92 -16
B4 n. a. -58 50 55 -367
B5 n. a. -28 64 95 -14

18. Total Treatment Efficiency
Clofibric Salicylic
No. of Diclofenac Ibuprofen Carbamazepine
Acid Acid
Sample [%] [%] [%]
[%] [%]
C1 n. a. -88 99 93 -44
C2 2 1 96 98 -24
C3 ≥ 54 -15 99 98 -10
C4 n. a. -19 99 95 9
C5 n. a. -40 98 90 -36
D1 ≥ 66 33 99 97 27
D2 ≥ 35 3 99 98 14
D3 n. a. -25 98 99 -2
D4 n. a. -19 98 95 3
D5 n. a. -78 98 96 9

19. Total Treatment Efficiency
100
50
0
%
-50
-100
-150
A1 A2 B1 B2 B3 B4 B5 C1 C2 C3 C4 C5 D1 D2 D3 D4 D5
Clofibric Acid Diclofenac Ibuprofen Salicylic Acid Carbamazepine

20. Discussion of the results
Ibuprofen, Salicylic Acid
• Biologically degradable
• Total treatment efficiency up to 99%.
• Significant Concentrations on the Effluent.
Diclofenac, Carbamazepine
• Resistant toward biological treatment process.
• Low treatment efficiency (max. 33 % for DIC and max. 27 % for CAR).
• Often noticed increase of the concentrations after passing WWTP.
Clofibric Acid
• For evaluation more detailed data missing.

21. Conclusions
Various Treatment Efficiency for selected PPCP
The main factors of high removal efficiency of IBU and SAL:
Hydraulic retention time
Sludge age
Specific setting of technological line and usage of wastewater
treatment technology is not so important as supposed.
Mechanical pretreatment is not important for removing
pharmaceuticals at all.
Tertiary Treatment must be added for higher removal.

22. The next phase of the project
Assembled WWTP pilot plant with real wastewater.
Testing of various settings of WWTP line and main
technological parameters.
Adding tertiary treatment:
1. Ozonization
2. UV radiation
3. PAC (Powdered Activated carbon)

23. Thank you for your attention!
T. G. Masaryk Water Research Institute, p.r.i.
Podbabská 2582/30, 160 00 Prague 6, Czech Republic | +420 220 197 111 | info@vuv.cz, www.vuv.cz
Brno Branch | Mojmírovo náměstí 16, 612 00 Brno | +420 541 126 311 | info_brno@vuv.cz
Ostrava Branch | Macharova 5, 702 00 Ostrava | +420 595 134 800 | info_ostrava@vuv.cz