Presentation at the ESPP workshop Pharmaceuticals in sewage biosolids, Malmo, 27-10-2016 European Sustainable Phosphorus Platform (ESPP) www.phosphorusplatform.eu Sustainable management of nutrients is crucial for agriculture, food, industry, water and the environment. ESPP brings together companies and stakeholders to address the Phosphorus Challenge and its opportunities for the circular economy. Countries: Austria AT Belgium BE Bulgaria BG Cyprus CY Czech Republic CZ Germany DE Denmark DK Estonia EE Spain ES Finland FI France FR Greece EL Hungary HU Ireland IE Italy IT Lithuania LT Luxembourg LU Latvia LV Malta MT Netherlands NL Poland PL Portugal PT Romania RO Sweden SE Slovenia SI Slovakia SK United Kingdom UK Switzerland CH Phosphorus: Fosfor Fosfor Fòsfòr Фосфор Fosfor Фосфор Fosfor Fosfor Фосфор Фосфор Fosforas Fosfors Fuosfuors Fosfor Ffуsfforws Fosfar Fosfaras Fosfaar Fosforus Φωσφορος Ֆոսֆոր Fosfor Fosfor Фосфор Фосфор ফসফরাস فسفر ફૉસ્ફરસનો फास्फोरस Fosfor Fosfori Foszfor Фосфор Фосфор Паликандур Fosfor Fosfor Фосфор Фосфор Фосфор Фосфор Fosfor فوسفور Fosfor Fosforoa ფოსფორი [fūsfūr] זרחן Fosfru Lìn リン 인 ฟอสฟอรัส Photpho 磷 Posporo Fosfor Pūtūtae-whetū Fosforus ഫോസ്ഫറസ് பொஸ்பரசு Fosofo Fosforase Posfori Fósforo Phusphuru Fosforimi Fosforo Fosforon Pesticium

1. Removal of pharmaceuticals in different
activated sludge wastewater treatment
plants in comparison to biofilm and
ozonation
1
Kai Bester, Aarhus University
VERSITET

2. Micro-pollutants in activated sludge treatment
Inflow Sludge treatment effluent
sludge
Partitioning
Degra-
dation
Metabolites?

3. Micro-pollutants in activated sludge treatment II
Typically 10 g/L sludge are generated
If lg partition constant is 3: 50% of
compound is in sludge
If lg partition constant is 4: 90% of
compound is in sludge
lg partition constant = pKow

4. Degradation
O
OH
OH
O
OH
Ibuprofen
Hydroxy-Ibuprofen
CO2, H2O, Biomass

5. Degradation
Are all sludges similar?

6. Systematic comparison of different sludges
• Sludges were sampled at the respective WWTP
• They were used in lab for incubation studies under
normalised aerobic conditions
• Samples were taken and analysed for
pharmaceuticals – for kinetic data
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

7. WWTPs used:
Name PE COD
/
BOD
Temp
[oC]
SRT
[d]
HRT
[h]
VS
[g/L]
N P
Aalborg-
West
300.000 2.7 12 14 22 2.45 Alternating
DN in
aeration
Biological-
sidestream
hydrol.
Aalborg-
East
100.000 2.9 11 31 35 3.17 Alternating
DN in
aeration
Biological-
sidestream
hydrol.
Aabybro 11.000 2.1 11 47 21 4.51 Upstream DN FeSO4
Hirtshals 62.700 2.0 7 20 42 3.93 Alternating
DN in
aeration
Biological-
upstream hydrol.
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

8. First order reaction rate constants
WWTP Compounds Degradation rate k Half-Life R2
% h-1 [h-1]
Aalborg West
Naproxen 90 0.0196 15 0.85
Ketoprofen 90 0.0079 36 0.79
Fenoprofen 90 0.0407 7 0.90
Carbamazepine - - - -
Triclosan 85 0.0065 44 0.97
Dichlofenac - - - -
Aalborg East
Naproxen 46 0.0026 86 0.67
Ketoprofen 77 0.0082 27 0.85
Fenoprofen 55 0.0088 25 0.92
Carbamazepine 82 - 70 0.45
Triclosan 61 0.0022 100 0.94
Dichlofenac - - - -
Aalbybro
Naproxen 62 0.0278 6 0.77
Ketoprofen 78 0.0112 14 0.77
Fenoprofen 65 0.0087 18 0.84
Carbamazepine - - - -
Triclosan 85 0.0038 40 0.97
Dichlofenac - - - -
Hirtshals
Naproxen 90 0.0132 13 0.91
Ketoprofen 94 0.0125 14 0.96
Fenoprofen 90 0.0813 2 0.83
Carbamazepine - - - -
Triclosan 91 0.0044 40 0.98
Dichlofenac - - - -
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

9. Degradation of Fenoprofen in in sludge from four
different WWTPs (AAL : Aalborg).
-3.00
-2.50
-2.00
-1.50
-1.00
-0.50
0.00
0.50
0 5 10 15 20 25 30 35
Ln（C/C0) Time (hours)
Hirtshals AAL East Aabybro AALWest
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

10. Degradation rate k in dependence of biomass
expressed as volatile solids (VS).
0
0.01
0.02
0.03
0.04
2 3 4 5
DegradationRateK(h-1)
Volatile Solids (g/L)
Naproxen
Ketoprofen
Fenoprofen
Triclosan
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

11. Degradation rate k as a function of sludge retention
time (SRT).
0
0.01
0.02
0.03
0.04
0 10 20 30 40 50
DegradationRateK(h-1)
Sludge Retention Time (days)
Naproxen
Ketoprofen
Fenoprofen
Triclosan
Chen, Vollertsen, Lund Nielsen, Gieraltowska Dall, Bester, Ecotoxicology, 24, 2073–2080, 2015

12. Status on sludge
• Classical activated sludge can degrade some compounds
• It is difficult to predict which plant will be able to remove
how well.
• Some compounds cannot be removed (Diclofenac,
Carbamazepine, X-ray contrast media)
• Diclofenac and Carbamazepine can be removed with
polishing ozonation, while X-ray contrast media cannot
• Ozonation is energy craving
• What can be achieved with biofilms?

13. Biofilm reactors – porous media
Grains
Biofilm

14. Biofilm reactors – Moving bed biofilm reactor
(MBBR)

15. Staged aerobic MBBR
• 21/26 compounds
degraded >20%
• First order kinetics
for most compounds
• Two phase kinetics
for four compounds
• While M1 degrades
faster, has M3
usually the more
effective biomass
Escola Casas, Chhetri, Ooi, Hansen, Litty, Christensson, Kragelund, Andersen, Bester, Water Research, 83, 293-302, 2015
Including removal for Diclofenac, Carbamazepine, X-ray contrast compounds

16. Single stage denitrifying MBBR
0.0
0.2
0.4
0.6
0.8
1.0
Relativeconcentration
Sulfamethoxazole
Sulfamethizole
Trimethoprim
0.0
0.2
0.4
0.6
0.8
1.0
0
50
100
150
200
250
MeOH-fed MBBR
Ss depleted
Relativeconcentration
0
50
100
150
200
250
Erythromycin
Clarithromycin
sCOD
SS
EtOH-fed MBBR
Ss depleted
mgCODL-1
0.0
0.2
0.4
0.6
0.8
1.0
Relativeconcentration
Citalopram
Venlafaxine
Carbamazepine
0.0
0.5
1.0
1.5
Relativeconcentration
Acetyl-Sulfadiazine
Sulfadiazine
a
b
c
d
Torresi, Escola Casas, Polesel, Plósz,
Christensson, Bester 2016, Water
Research, in press

17. 0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Startexperim
ent
Time (d)
Relativeconcentration
0.2
0.4
0.6
0.8
1.0
Atenolol
Metoprolol
Sotalol
Propranolol
Startexperim
ent
Time (d)
0.0
0.2
0.4
0.6
0.8
1.0
Relativeconcentration
Iomeprol
Iohexol
Diatrizoic acid
Iopamidol
Iopromide
0.0
0.5
1.0
Relativeconcentr
Acetyl-Sulfadiazine
e
f
Single stage denitrifying MBBR
• Denitrifying MBBR is nearly as effective as aerobic
• MeOH reactor does a bit better than the EtOH reactor
• Diclofenac cannot be degraded under denitrifying conditions
• Carbamazepine and X-ray contrast compounds can be degraded under
denitrifying conditions
Torresi, Escola Casas, Polesel, Plósz, Christensson, Bester 2016, Water Research, in press

18. Conclusions:
• MBBRs might be a suitable alternative for removing
organic micro-pollutants
• Co-degradation and starvation are most probably the
most relevant process.
• Currently residence times of 20 h would be needed to
break down sufficient amounts of pollutants
• It is difficult to foresee reactor parameters for fully
optimised co-degradation/starvation reactors

19. Acknowledgement
All the students and collaborators that helped moving these themes forward:
Xijuan Chen, Monica Escola Casas, Haitham El-taliawy, Gordon Ooi, Kai Tang,
Elena Torresi
Founding: MST, MUDP, DFF-FTP, AUFF, Havs och Vatten Myndigheden
Collaboration partners: AAU, DTU, ANOX Kaldnes, Kruger, TI, Aarhus Vand,
Herning Vand, Biofos

20. 20
CAS Ozonation Biofilm
X-ray contrast
media
  
Beta-blockers   
Diclofenac/
Carbamazepine
   ?
Ibuprofen   
Sulfonamides :-/  
Macrocyclic
antibiotics
   ?
Persistence of compound groups in
wastewater treatment