Hydrodynamic cavitation: a technique for augmentation of removal of persistent pharmaceuticals?

Mojca Zupanc1,2, Tina Kosjek1, Boris Kompare3, eljko Blaeka4, Uro Jee5, Matev Dular5, Brane irok5, Ester Heath1,2
of Environmental Sciences, Jozef Stefan Institute, Ljubljana, Slovenia 2 Jozef Stefan International Postgraduate School, Ljubljana, Slovenia 3 Faculty of Civil and Geodetic Engineering, University of Ljubljana, Ljubljana, Slovenia 4 Ecological Engineering Institute Ltd, Maribor, Slovenia 5 Faculty of Mechanic Engineering, University of Ljubljana, Ljubljana, Slovenia
mojca.zupanc@ijs.si
1 Department

Abstract. Pharmaceutical residues enter the environment mainly due to insufficient wastewater treatment. Many pharmaceuticals are not readily degraded during conventional wastewater treatment, therefore advanced technologies to remove them need to be investigated. In our study we examined the removal of six pharmaceuticals (clofibric acid, ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac) using a combination of hydrodynamic cavitation and hydrogen peroxide. We performed the experiments in distilled water under different operating conditions (initial pressures set at 6, 5, 4 bar). The results showed good removal of naproxen (up to 86%) and satisfactory removal of both carbamazepine (up to 72%) and diclofenac (up to 77%), which are only moderately removed during biological water treatment (21% and 48%, respectively). Removal of clofibric acid, ibuprofen and ketoprofen by cavitation was lower and inconsistent (45%35%, 48%31% and 52%27%, respectively). Keywords: pharmaceuticals, hydrodynamic cavitation, removal

1 Introduction
Awareness of the presence of pharmaceuticals in the environment began around 30 years ago [1]. Since then the scientific community has made a significant effort into understanding fate, behaviour and the risks posed by pharmaceuticals in the environment [2], [3], [4]. Pharmaceuticals are developed for human and veterinary

use [5] and after their application they reach wastewater treatment plants mostly via the domestic sewage system [6]. Their concentrations detected in different environmental compartments are in the ng L-1 to g L-1 range [1], [3]. Since many pharmaceuticals are not readily degradable by conventional treatment schemes [6], research into and development of alternative methods like advanced oxidation processes is important [7]. Cavitation is a physical phenomenon where the formation, growth and subsequent collapse of small bubbles and bubble clusters occurs simultaneously releasing high amounts of energy [7]. Cavitation belongs to a group of advanced oxidation processes (AOP), the basis of which is in situ formation of hydroxyl radicals that can oxidise recalcitrant organic compounds [7], [8]. In hydrodynamic cavitation, the inception and collapse of small bubbles and bubble clusters is the result of an increase of the fluid velocity and the decrease of static pressure, which occurs when the fluid passes through a constriction [7]. The destruction of organic compounds can occur via two pathways: free radical attack and pyrolysis, and which of the two predominates depend on the properties of the compound and on cavitation intensity [7]. The addition of hydrogen peroxide enhances the amount of free radicals. The main objective of our study was to test a series of techniques that could be coupled to biological treatment to enhance overall removal efficiency. For this purpose we investigated the removal of six pharmaceuticals (clofibric acid: CLA, ibuprofen: IBP, naproxen: NP, ketoprofen: KTP, carbamazepine: CBZ and diclofenac: DF) with hydrodynamic cavitation under different operating conditions including the addition of hydrogen peroxide.

2 Experimental setup
The hydrodynamic cavitation reactor (HC-reactor) setup included two reservoirs connected by a symmetrical venturi pipe with a constriction of 1 mm height and 5 mm width. As the flow passes through the constriction, it accelerates, causing a drop in the static pressure resulting in cavitation. The sample is introduced into the left reservoir (Figure 1), while the right reservoir remains empty. The pressure in the left reservoir is then increased to the desired level, while the pressure in the right reservoir is kept at 1 bar. When the regulating valve is opened, the reactor

contents are transferred from the left reservoir to the right one in about 10s. The process is then reversed (cycled) for a given number of times. Figure 1 shows a schematic of the reactor set up.

Figure 1: HC-reactor set up and cavitation phenomenon In our experiments we observed the effects of cavitation in 1 L of distilled water spiked with a mixture of the model pharmaceuticals (clofibric acid, ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac) at environmentally relevant concentrations (1 g L-1). The operating conditions were selected in previous experiments (data not shown) and were as follows: cavitation time (30 minutes) and H2O2 addition (30%, 20 mL). As a variable, we selected initial pressure since this parameter defines flow velocity and the intensity of cavitation. Experiments were made at 4, 5, and 6 bar. In order to ascertain the repeatability of cavitation, we performed the experiments under optimum conditions (6 bar) in 10 parallels.

3 Results and discussion

The results show that highest removal of all six pharmaceuticals was achieved at 6 bar (Figure 2). This was in agreement with the presumption that a higher initial pressure results in an increase in cavitation intensity. The removal of pharmaceuticals at 5 bar was slightly better than at 4 bar.

Figure 2: Removals (%) of pharmaceuticals with hydrodynamic cavitation under different initial pressures (6, 5 and 4 bars) At 6 bar we achieved 86%8% removal of naproxen and 72%14% and 77%12% of carbamazepine and diclofenac, respectively. The removal efficiencies of clofibric acid, ibuprofen and ketoprofen were lower and inconsistent compared to naproxen. As mentioned before the destruction of organic compounds with hydrodynamic cavitation is dependent on their structure and chemical properties and the different chemical structure of the selected pharmaceuticals may be the reason for different removal efficiencies. Since carbamazepine and diclofenac are not readily and consistently removed during biological waste water treatment (21% and 48%, respectively), which we established in our previous work and is in accordance with the literature [8], [9], hydrodynamic cavitation could be a viable technique for augmenting their removal. To authors knowledge few data exist regarding the removal of pharmaceuticals using hydrodynamic cavitation. Since cavitation is a technique that is relatively easy to scale up [10], it should be given more attention.

In the future we will combine hydrodynamic cavitation and Fenton process to achieve better removal of recalcitrant pharmaceuticals (clofibric acid, ibuprofen and ketoprofen) and further augment the removal of naproxen, carbamazepine and diclofenac. After the determination of removal efficiencies and optimal operational conditions for this combination in distilled water, we will transfer the technology to more complex matrices (effluents of biological wastewater treatment plants). Last but not least, our aim is to determine the best combination of different processes considering removal of pharmaceuticals, feasibility and cost effectiveness, possibly coupling AOP sequentially to biological treatment.

References:
[1]J. P. Bound, K. Kitsou, N. Voulvoulis. Household disposal of pharmaceuticals and perception of risk to the environment. Environmental Toxicology and Pharmacology, 21: 301307, 2006 [2]Halling-Srensen B., Nors Nielsen S., Lanzky P.F:, Ingerslev F., Holten Ltzhft, Jrgensen. Occurence, Fate and Effects of Pharmaceutical Substances in the Environment A Review. Chemosphere, 36 : 357-393, 1998 [3]Ternes T.A., Giger W., Joss A. Introduction. In: Human Pharmaceuticals, Hormones and Fragrances: The challenge of micropollutants in urban water management. Ternes T.A., Joss A., 2006. [4]Farre M., Perez S., Kantiani L., Barcelo D. Fate and toxicity of emerging pollutants, their metabolites and transformation products in the aquatic environment. Trends in Analytical Chemistry, 27 : 991-1007, 2008 [5]O.V. Enick, M.M. Moore. Assessing the assessments: Pharmaceuticals in the environment. Environmental Impact Assessment Review , 27: 707729, 2007 [6] A. Joss, S. Zabczynski, A. Gbel, B. Hoffmann, D. Lffler, C. S. McArdell, T. A. Ternes, A. Thomsea, H. Siegrist. Biological degradation of pharmaceuticals in municipal wastewater treatment: Proposing a classification scheme. Water Research, 40: 1686 1696, 2006 [7]P.R. Gogate, A.B. Pandit. A review of imperative technologies for wastewater treatment I:oxidation technologies at ambient conditions. Advances in Environmental Research, 8: 501-551, 2004 [8]P. Braeutigam , M. Franke, R. J. Schneider , A. Lehmann , A. Stolle, B. Ondruschka. Degradation of carbamazepine in environmentally relevant concentrations in water by Hydrodynamic-Acoustic-Cavitation (HAC). Water Research, 46: 2469-2477, 2012 [9]M. Ravina, L. Campanella, J. Kiwi. Accelerated mineralization of the drug Diclofenac via Fenton reactions in a concentric photo-reactor. Water research, 36: 3553-3560, 2002 [10] A.G. Chakinala, P.R. Gogate, A.E. Burgess, D.H. Bremner. Treatment of industrial wastewater effluents using hydrodynamic cavitation and the advanced Fenton process. Ultrasonics Sonochemistry, 15: 49-54, 2008

For wider interest

To meet the ever growing demand for improved healthcare, pharmaceuticals are being produced in increasing amounts. As a consequence, pharmaceutical residues in the environment are becoming a concern. This is because many of these compounds have been proven to be resistant to conventional microbiological wastewater treatment. In response, new technologies are necessary to reach increasingly stringent regulation on water quality. In this study we investigated hydrodynamic cavitation which is a potent advanced oxidation process (AOP) and is relatively cost-effective and easy for scale up. Caviation is the term given to the formation and subsequent implosion of bubbles that result when the partial local pressure in a fluid drops below vapour pressure. The collapse of the bubbles can generate a significant increase in local pressures and temperatures, called hot spots. Such extreme conditions can result in the formation of free radicals, which are potent oxidising species capable of breaking down organic compounds. Our intention is to make use of these free radicals by deliberately cavitating the effluent flow from a wastewater plant. Additionally, our idea is to increase the amount of free radicals formed by adding hydrogen peroxide. Initial experiments have been carried out using a two reservoir system in which the fluid can be transferred from one to the other by varying the pressures in each. As the fluid passes from one reservoir to the other, it must pass through a constriction, which creates a pressure drop in the fluid resulting in cavitation. We tested the apparatus using six common pharmaceuticals: clofibric acid, ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac at various pressures 4, 5 and 6 bar. A pressure of six bars was optimum. In the case of carbamazepine and diclofenac, the results have been positive, improving the removal efficiency by 50% and 30 %, respectively, compared to conventional water treatment. In the case of clofibric acid, ibuprofen and ketoprofen the results are less conclusive. Further study will involve optimisation of cavitation process and its combination with biological water treatment in order to improve overall removal of resistant contaminants.