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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
Removing?
Wastewaters→ WWTPs→ Receiving waters
The consumption of these substances is rising.
PPCP (pharmaceuticals and personal care products)
Attention of public now focusing on new specific pollutants.
Improving removal efficiency of Nitrogen and Phosphorus on WWTP.
Removal of organic pollution on WWTPs has been practically solved.
Introduction
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.
Research project in the Czech Republic
•Analgesic and Non-steroidal anti-inflammatory drug (NSAID). About 70% used as liniment (over-the-counter), except Europe used per orally.
•Consumption in the CR c. 20 tons per year.
Diclofenac (CAS 15307-86-5)
•Non-steroidal anti-inflammatory drug (NSAID). Generally used per orally.
•Consumption in the CR c. 200 tons per year.
Ibuprofen (CAS 15687-27-1)
•Anti-epileptic, antidepressant etc. Used purely per orally and only for prescription.
•Consumption in the CR c. 7,5 tons per year.
Carbamazepine (CAS 298-46-4)
Observed substances
•Basic metabolite of Acetylsalicylic Acid (Aspirin). Direct usage only for eyes applications.
•Consumption in the CR c. 600 tons per year.
Salicylic Acid(CAS 69-72-7)
• Basic metabolite of fibrates used for level control of lipoproteins (cholesterol) in blood.
•Consumption in the CR c. 10 tons per year.
Clofibric Acid (CAS 882-09-7)
Observed substances
Ibuprofen
Diclofenac
Carbamazepine
Aspirin
Salicylic Acid
Clofibric Acid
Kidney
Observed substances
Observed WWTP
WWTP
Range of Population Equivalent
Technological scheme
A Over 80 000
Mechanical-biological WWTP with biological nitrogen and phosphorus removal, anaerobic sludge stabilization.
B 10 000 – 50 000Mechanical-biological WWTP with bio-filters, chemical precipitation, aerobic sludge stabilization.
C 50 000 – 80 000
Mechanical-biological WWTP with biological nitrogen and phosphorus removal, anaerobic sludge stabilization.
D 10 000 – 50 000
Mechanical-biological WWTP (carrousel type) with biological nitrogen removal and, aerobic sludge stabilization..
•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.
Sampling and Analyses
WWTP A Results
ProfileClofibric
Acid(ng/l)
Diclofenac (ng/l)
Ibuprofen (ng/l)
Salicylic Acid(ng/l)
Carba-mazepine
(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
WWTP B Results
ProfileClofibric
Acid(ng/l)
Diclofenac (ng/l)
Ibuprofen (ng/l)
Salicylic Acid(ng/l)
Carba-mazepine
(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
WWTP C Results
ProfileClofibric
Acid(ng/l)
Diclofenac (ng/l)
Ibuprofen (ng/l)
Salicylic Acid(ng/l)
Carba-mazepine
(ng/l)
n. a. 187 4670 11 000 184
18.4 541 7530 20 400 350Influent 14.5 538 10 900 34 900 505
n. a. 758 11 200 14 400 1050n. a. 357 7360 19 500 542n. a. 351 46,0 825 264
18.3 534 283,0 384 435Effluent n. a. 617 47,5 666 553
n. a. 900 62,3 684 958n. a. 536 129 1600 745
WWTP D Results
ProfileClofibric
Acid(ng/l)
Diclofenac (ng/l)
Ibuprofen (ng/l)
Salicylic Acid(ng/l)
Carba-mazepine
(ng/l)
19.6 995 19 200 42 800 1270
10.2 790 19 900 32 600 816Influent n. a. 833 16 300 28 500 1610
n. a. 1280 27 200 28 600 1890n. a. 740 15 000 16 100 2050n. a. 671 62,7 1230 932
n. a. 769 169 520 701Effluent n. a. 1070 205 529 1690
n. a. 1520 532 1440 1830n. a. 1320 318 684 1860
WWTP C - Ibuprofen
Influent Mechanical Treatment
Denitrification Nitrification Regeneration Effluent0
2000
4000
6000
8000
10000
12000
14000
ng/l
WWTP C - Salicylic Acid
Influent Mechanical Treatmnet
Denitrification Nitrification Regeneration Effluent0
5000
10000
15000
20000
25000
30000
35000
40000
ng/l
WWTP C - Diclofenac
Influent Mechanical Treatment
Denitrification Nitrification Regeneration Effluent0
100
200
300
400
500
600
700
800
900
1000
ng/l
WWTP C - Carbamazepine
Influent Mechanical Treatment
Denitrification Nitrification Regeneration Effluent0
200
400
600
800
1000
1200
ng/l
Total Treatment Efficiency
No. of Sample
Clofibric Acid[%]
Diclofenac [%]
Ibuprofen [%]
Salicylic
Acid[%]
Carbamazepine[%]
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
Total Treatment Efficiency
No. of Sample
Clofibric Acid[%]
Diclofenac [%]
Ibuprofen [%]
Salicylic
Acid[%]
Carbamazepine[%]
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
Total Treatment Efficiency
A1 A2 B1 B2 B3 B4 B5 C1 C2 C3 C4 C5 D1 D2 D3 D4 D5-150
-100
-50
0
50
100
Clofibric Acid Diclofenac Ibuprofen Salicylic Acid Carbamazepine
%
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.
Discussion of the results
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.
Conclusions
Assembled WWTP pilot plant with real wastewater.
Testing of various settings of WWTP line and main technological parameters.
Adding tertiary treatment:1. Ozonization2. UV radiation3. PAC (Powdered Activated carbon)
The next phase of the project
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 | [email protected], www.vuv.czBrno Branch | Mojmírovo náměstí 16, 612 00 Brno | +420 541 126 311 | [email protected] Branch | Macharova 5, 702 00 Ostrava | +420 595 134 800 | [email protected]
