Removal of hazardous micropollutants from treated wastewater using cyclodextrin bead polymer – A pilot demonstration case

Journal of Hazardous Materials 383 (2020) 121181

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Removal of hazardous micropollutants from treated wastewater using cyclodextrin bead polymer – A pilot demonstration case

T

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Éva Fenyvesia, , Katalin Barkácsb, Katalin Gruizc, Erzsébet Vargaa, István Kenyeresd, Gyula Zárayb, Lajos Szentea a

CycloLab Cyclodextrin R&D Laboratory Ltd., Budapest, Hungary Cooperation Research Center of Environmental Sciences, Eötvös Loránd University, Budapest, Hungary c Budapest University of Technology and Economics, Budapest, Hungary d Biopolus Ltd., Budapest, Hungary b

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO

A B S T R A C T

Editor: Daniel C.W. Tsang

Increasing amount of micropollutants such as drugs, cosmetics and nutritional supplements detected in surface waters represents increasing risk to humans and to the whole environment. These hazardous materials deriving mostly from wastewaters often cannot be effectively removed by conventional water treatment technologies due to their persistence. Some of the innovative technologies use specific sorbents for their removal. Cyclodextrinbased sorbents have already proved to be efficient in laboratory-scale experiments, but no pilot-plant scale demonstration has been performed so far. We are the first who applied this sorption-technology as a tertiary treatment in a pilot-plant scale operating, biomachine-type municipal wastewater treatment plant. As a result of the treatment 7 of 9 typical micropollutants (estradiol, ethinyl estradiol, estriol, diclofenac, ibuprofen, bisphenol A and cholesterol) were removed with > 80% efficiency from effluent (reducing their concentration from ∼5 μg/L to < 0.001–1 μg/L). GC–MS analysis of water samples showed that many of the micropollutants were removed from the water within a short time, demonstrating the high potential of the applied cyclodextrin-based sorbent in micropollutant removal. The effect-based testing also confirmed the efficiency. There was a correlation between sorption efficacies and binding constants of micropollutant/cyclodextrin inclusion complexes, showing that among others also inclusion complex formation of pollutants with cyclodextrin played important role in sorption mechanism.

Keywords: Cyclodextrin polymer Direct toxicity assessment Emerging micropollutants Pilot plant-scale sorption technology

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Corresponding author. E-mail address: [email protected] (É. Fenyvesi).

https://doi.org/10.1016/j.jhazmat.2019.121181 Received 25 April 2019; Received in revised form 29 August 2019; Accepted 6 September 2019 Available online 09 September 2019 0304-3894/ © 2019 Published by Elsevier B.V.

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1. Introduction

and nutritional supplements (Cova et al., 2018; Crini et al., 2018; Morin-Crini and Crini, 2013; Morin-Crini et al., 2018). Cyclodextrins were found to be widely applicable in environmental risk management starting from air filtration through wastewater treatment to remediation of contaminated soil (Gruiz et al., 2011). Cyclodextrins are cyclic carbohydrates consisting of 6, 7 or 8 glucopyranose units coupled with α1-4 bonds (Szejtli, 1988). Cyclodextrin-based materials for water and wastewater treatment include crosslinked polymers, nanosponges, membranes, nanofibers, and functionalized silica and organic resins containing mostly the 7-membered β-cyclodextrin (Morin-Crini et al., 2018). Although the first such polymer sorbents were described 50 years ago (Wiedenhof et al., 1969), novel cyclodextrin-based sorbents using different crosslinking agents or grafted on various polymer backbones or integrated into membranes have been also recently developed (Alsbaiee et al., 2016; Moulahcene et al., 2015, 2019; Taka et al., 2017; Yu et al., 2018). Most of the studies published so far, however, used small scale laboratory experiments to demonstrate the applicability of cyclodextrincontaining sorbents. Even in a recent report published in Nature, as low volume as 8 mL of model solution was transferred through 0.3 mg of sorbent to reach 20–90% removal of contaminants from a mixture containing 8 emerging pollutants (bisphenol A, ethinyl estradiol and other drugs, pesticides and carcinogenic aromatic model compounds in 2.5–100 μg/L concentration) (Alsbaiee et al., 2016). The sorbent was a porous β-cyclodextrin polymer crosslinked by tetrafluoroterephthalonitrile. Two orders of magnitude higher volume (∼800 mL) with 20 g epichlorohydrin-crosslinked β-cyclodextrin polymer (BCDP) sorbent was successfully used by our group for binding 8 micropollutants (pharmaceuticals, hormones and industrial additives) at 5 μg/L level in fluidization experiment and in another experiment we have purified 3 L model solution of the same composition by letting it through BCDP column (Nagy et al., 2014). A modified cyclodextrin polymer (crosslinked with 1,4-butanediol diglycidyl ether and substituted by carboxymethyl groups) was efficient for decontamination of industrial effluents containing several pollutants including chlorinated phenols, polycyclic aromatic compounds, detergents and metals by treating 1 L and 25 L industrial effluent with 1 g/L sorbent concentration using batch technology with 60 min contact time (Charles et al., 2014). We aimed to demonstrate the applicability of BCDP sorption technology at pilot-plant scale. According to our knowledge, so far no similar scale experiment has been carried out with real, micropollutantscontaining municipal wastewater. Our objective in this study was to perform an experiment at pilot-plant scale to see how BCDP sorbent can eliminate selected micropollutants from a real physically and biologically treated wastewater effluent having a remaining complex organics content matrix with other organics present in several orders of magnitude higher concentrations compared to removable organic micropollutants. The efficacy of this novel risk reduction technology in a real wastewater effluent post-treatment was followed by analyzing microcomponents of raw and treated effluent waters both by gas chromatography–mass spectrometry and direct toxicity assessments. It was beyond our possibilities to optimize the technology. We aimed only to perform a proof-of-concept experiment under the most realistic conditions and to determine the necessary contact time between adsorbent and wastewater effluent for removing micropollutants with possible highest efficiency applying a feasible operation as fluidization technique. We also aimed at studying relationship between complex forming ability of selected micropollutants and their removal rate by BCDP sorbent in order to better understand the binding mechanism.

Increasing pollution of water by chemicals from industrial production, intensive agriculture, medical effluents, and household sewage presents an alarming hazard. Contaminated waters pollute not only water phases, but everything in direct or indirect contact with them, thus other parts of the environment such as soils, plants, animals, humans, etc. Several contaminants called emerging pollutants were not detected earlier chemically due to the lack of sophisticated analytical methods. Neither could their adverse impacts be identified due to their unknown and indirect effects manifesting in the long run. Many of these compounds belong to pharmaceutical and personal care products (PPCPs) including human and veterinary drugs, as well as cosmetics, detergents and nutraceuticals (Bolong et al., 2009; Snow et al., 2016; Richardson and Kimura, 2017). These chemical substances are xenobiotics and usually do not degrade in natural environment and accumulate in living organisms (Diaz-Cruz et al., 2019). Bioaccumulation may result in chronic toxicity, such as mutagenicity, carcinogenicity, reprotoxicity, sensitization, allergization, and endocrine disruption (Smital et al., 2004; Ding et al., 2017). Conventional wastewater treatment techniques such as sand filtration, sedimentation, flocculation, coagulation (primary treatments) and the biotechnologies (secondary treatments) turned out to be partly or totally insufficient for the removal of these micropollutants (Verlicchi et al., 2010) posing an increased risk to humans for instance in case of using living water as drinking water resource. Significant efforts have been concentrated on tertiary treatment of purified wastewater aiming at reducing these emerging pollutant concentrations still present after primary (physical) and secondary (biological) treatments. Reverse osmosis and nano/ultrafiltration as tertiary treatments demonstrated remarkable removal rates for drugs. However, the residual brine was more toxic than the influent water, so its disposal into environment was not allowable (Watkinson et al., 2007). Also membrane fouling and insufficient removal of some hazardous components inhibit widespread application of these technologies (Ha et al., 2004). Some micropollutants including drugs and pesticides are resistant to ozonation, chlorination, photolysis or other advanced oxidation technologies (AOTs) and the removal efficiency depends on the composition of water (dissolved organic and inorganic constituents) (Bouras and Lianos, 2008; Cruz-Alcalde et al., 2019; Czech and Oleszczuk, 2016; Ghosh et al., 2019; Lado Ribeiro et al., 2019; Russo et al., 2018). Application of AOTs is limited also by energy cost, catalyst management and potential residual toxicity in treated effluents (Lofrano et al., 2017). Several other technologies applying electrotreatments or membrane biofilm reactors are in phase of development (Brillas, 2014; Aydin et al., 2016; Zhao et al., 2018; Xiao et al., 2019; Silva et al., 2019). Toxicity of waters treated by these chemical and biochemical transformation processes might also be a concern because of eventual toxic byproducts (Richardson and Kimura, 2017; Plewa and Richardson, 2017). Comparing the various technologies being under development for xenobiotics removal from wastewater, those based on sorption seem promising due to small amount of waste production, low energy requirement and absence of harmful metabolites formation (Li et al., 2018a; Mohan et al., 2014). In addition to the most frequently used activated carbon a lot of other sorbent materials, such as organoclays, covalent organic frameworks, metal organic frameworks, carbon materials, such as biochar, graphene oxide, multiwall carbon nanotubes (MWCNT), and other nanomaterials as well as their combinations were developed and tried in small-scale laboratory experiments using mostly single-component model solutions (Huang et al., 2019; GonzálezHernández et al., 2019; Guégan, 2019; De Gisi et al., 2016; Li et al., 2018a,b; Mohan et al., 2014; Toński et al., 2018; Zaib et al., 2013). Numerous research groups started to develop sorbents containing cyclodextrins, as they form inclusion complexes with large variety of organic chemicals, including drugs, cosmetic ingredients, pesticides,

2. Materials and methods 2.1. Materials The organic micropollutants selected for the pilot-plant scale 2

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organic components and also nutrients (Kovacs et al., 2019). In this system plants were placed into suspended perforated baskets and their roots were grown into the reactor units’ wastewater, where artificial biomass carriers were also placed to increase mineralization. The reactors were designed to allow high variability in aeration and mixing making it possible to set aerobic, anaerobic, or anoxic conditions in any reactor of the cascade. The raw municipal wastewater was conducted through an 8-membered reactor cascade with 500 L/h flow rate ensuring 1.5 day hydraulic retention time. Each reactor unit having 2 m3 useful volume was equipped with aeration, water-level and temperature control. The following parameters were monitored in the PWWTP routinely using EN and ISO standards: chemical oxygen demand (COD), biochemical oxygen demand (BOD), total organic carbon (TOC), adsorbable organic halides (AOX), total nitrogen (TN), total phosphorus (TP), total suspended solids (TSS), turbidity, specific electric conductivity and pH. Also more than 80 organic micropollutants were frequently analyzed for 6 months by GC–MS method to assist selection and also showing probable concentration of non-removable ones, remained present in this cascade system effluent.

experiment (β−estradiol, ethinyl estradiol, estriol, ibuprofen, diclofenac, naproxen, ketoprofen, cholesterol and bisphenol A) were purchased from Sigma-Aldrich in analytical grade. The β-cyclodextrin polymer crosslinked with epichlorohydrin (BCDP) is a product of CycloLab Ltd. (Hungary). It consists of spherical beads of 0.06–0.32 mm diameter. This fraction was selected as the smaller beads caused clogging while the larger ones settled down when swollen in water in the fluidization process. BCDP was characterized by swelling capacity in water (∼5 mL/g at 25 °C) and cyclodextrin content (60–65%, 600–650 mg/g corresponding to 0.52–0.57 μM/g) measured by iodometry after acidic hydrolysis. BCDP was activated before application by washing with ethanol and water as described earlier (Jurecska et al., 2014) in order to remove the organic components sorbed from the air during long-term storage. The reagents used for analysis and ecotoxicological tests were also purchased from Sigma-Aldrich. 2.2. Preparation of spiking solution for pilot-plant scale micropollutantsremoving experiments Due to the varying composition of pilot-plant scale wastewater treatment plant’s (PWWTP) effluent, the sample used in the technological experiment was spiked with a solution containing 9 selected organic micropollutants in order to ensure an average micropollutants concentration determined in earlier tests in this PWWTP. A stock solution of each component was prepared taking into account its aqueous solubility, the calculated volumes were mixed, creating a spiking solution distributed homogeneously in 350 L pretreated effluent (Table 1). This spiked effluent was applied for testing post-treatment efficiency of BCDP in micropollutants removal.

2.3.1.2. Ultrafiltration. The purified wastewater was post treated by a prefiltration followed by an ultrafiltration (UF). Prefiltration membrane had 300 μm pore size, and the prefiltration capacity amounted to 3 m3/ h. At UF during our experiments 300 L/h hydraulic load was applied. The UF unit was equipped with INGE dizzer®XL membrane (pore size 20 nm) and its role was principally to remove the suspended solids. 2.3.1.3. Pilot experiment with BCDP sorbent. A fluidized bed type operation was selected for the pilot-plant scale application of BCDP on the basis of our preliminary observations at laboratory experiments (Nagy et al., 2014). The suspended-solids content of the effluent from wastewater treating reactor cascade was first removed by applying preand ultrafiltration. This effluent –free from suspended solids– was spiked by a solution containing 9 selected micropollutants (β−estradiol, ethinyl estradiol, estriol, ibuprofen, diclofenac, naproxen, ketoprofen, cholesterol, bisphenol A, as shown in Table 1) to obtain about 5 μg/L concentration for each, and this spiked effluent was subjected to BCDP sorption. The temperature of this spiked water was 17–19 °C. For the experiment 1 kg activated BCDP sorbent was applied. This sorbent was equally divided and filled into 3 parallel operating columns as adsorbers. A column had 15.6 cm diameter and 80 cm height. The parallel columns had together 46 L volume, and within that 40.8 L useful volume. The spiked effluent was conducted to the columns with a 3.5 cm/s (120 L/min) flow rate to ensure fluidization of BCDP beads. Fluidization provided more favorable conditions for adsorption on BCDP than in fix bed operation. A special filtering equipment with selfcleaning function was applied at columns head to keep back sorbent beads within columns. At this experiment not a usual continuous operation was maintained, but 300 L spiked effluent was treated in such a way that outflowing water from columns treated by BCDP was collected and recirculated. The goal of this recirculation type operation was only to define a necessary contact time of this adsorption process to result effective micropollutants removal in pilot-plant scale from a real wastewater effluent. Samples were taken from the recirculated, BCDPtreated effluent for micropollutant analysis (3 L) after 5 min, 1, 2, 6, 24 and 48 h operation time. Regarding the useful volume of the sorption system, the spiked effluent water flew through the columns two times, during the first 5 min, thus resulting an average 41 s contact that is retention time within the columns during this period. The flow chart of the technology is shown in Fig. 2.

2.3. Methods 2.3.1. Pilot-plant scale post treatment of a wastewater treatment plant effluent Our experiment was carried out with the effluent of a wastewater treatment plant operating with a special biotechnology (called as ecomachine technology) in pilot-plant scale. In this technological row BCDP sorption was mainly investigated as micropollutants removing post-treating step. 2.3.1.1. Pilot-plant scale wastewater treatment. The PWWTP at Telki (Hungary) was built in a greenhouse to treat the municipal wastewater containing the effluent of the local hospital (Fig. 1). This PWWTP technological system, consisting of wetland type reactors giving home to an artificial ecosystem combining close-to-nature phyto- and microbial operation, could efficiently degrade wastewater Table 1 Stock solutions for spiking 350 L wastewater effluent. Compound

β-Estradiol Ethinyl estradiol Estriol Ibuprofen Diclofenaca Naproxen Ketoprofena Cholesterol Bisphenol A a b c d e

Solubility in water

Stock solution applied

(mg/L)

conc. (mg/L)

volume (mL)

3.6b 11.3b 13.3b 21b 858c 16b 168d 1.8e 300b

1.43 ± 0.07 1.38 ± 0.07 1.47 ± 0.08 20.7 ± 0.6 382 ± 12 15.0 ± 0.5 112 ± 3 1.44 ± 0.05 280 ± 8

1300 1300 1300 87.5 5.0 118 17.5 1300 6.5

Na salt. PubChem (2019). Linas et al. (2007). Sheng et al. (2006). Haberland and Reynolds (1973).

2.3.2. GC–MS measurement of micropollutants in water Water samples were subjected to solid phase extraction (SPE), then the extracts were derivatized to trimethyl silyl oxime ethers/esters 3

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Fig. 1. Ecomachine technology in a greenhouse in PWWTP in Telki (2019).

2.3.4. Determination of apparent binding constants for inclusion complexes The apparent binding constants for the various micropollutants and hydroxypropyl-β-cyclodextrin (HPBCD) were determined as described by Rundlett and Armstrong (1996) and Puskás et al. (2015). The method is based on changed electrophoretic mobility of analytes in the presence of increasing concentrations of complex forming host molecules (0.1–10 mM concentration of HPBCD in this case) in phosphate buffer at pH 7.2. The method can be used only for water-soluble hosts, therefore the water-insoluble BCDP was modeled by HPBCD. Three parallel measurements were carried out in each concentration of HPBCD for at least 3 concentrations and for the system containing no cyclodextrin for all the micropollutants studied. The apparent binding constants and standard deviations were calculated using x-reciprocal method (Puskás et al., 2015).

before being injected into GC–MS according to the previously published method (Sebok et al., 2009; Varga et al., 2010). The method was applicable for detection and quantitative determination of more than 80 compounds with one single injection. Averages of measurements data got for three parallel samples were used. The LOQ values were calculated from the signal–noise ratio of the GC–MS measurements of water samples using at least ten different chromatograms.

2.3.3. Direct toxicity assessment The experiment aiming at post treatment by BCDP was also monitored by direct toxicity assessment. Two test organisms were selected for demonstrating decreased toxicity level on aquatic plants and animals. Duckweed (Lemna minor) is a highly sensitive test organism for characterizing phytotoxicity of aqueous pollutants, while the crustacean Heterocypris incongruens or seed shrimp, a fresh-water ostracod, is a representative of aquatic animals. Both tests are official for characterizing the effect of chemicals on aquatic organisms (OECD, 2006; ISO, 14371, 2012). Lemna minor (duckweed) growth inhibition test and Heterocypris incongruens mobility test were performed and evaluated as described by Nagy et al. (2014) and by Klebercz et al. (2012), respectively. The duckweed test is based on UV-photometric determination of chlorophyll content being proportional with plant biomass, while the freshwater ostracod method counts moving animals. Both tests were used to characterize chronic toxicity (duration of exposure was 7 days). The means of three parallel measurements and standard deviations were calculated for each sample and then inhibition percentages related to the data obtained for water having no micropollutant content were evaluated.

3. Results and discussion 3.1. Monitoring ecimachine technology The BCDP technology was implemented for further purification of effluent from the Telki ecomachine type pilot scale wastewater treatment plant. To learn more on ecomachine technology both the raw water and the treated water were monitored monthly for 6 months. Monitoring data related to macro-components in Table 2 demonstrate that biological treatment resulted in highly reduced organic content (chemical and biological oxygen demand, COD and BOD) in the effluent. Also total nitrogen (TN) and total suspended solids (TSS) values decreased in a high extent showing efficiency of the ecomachine technology. Further improvement of these parameter values was achieved Fig. 2. Flow chart of the technology consisting of 8-membered reactor cascade utilizing also plants for purification (R1–R8) (retention time approx. 1.5 days), sedimentation tank (S), microfiltration unit (MF), ultrafiltration unit (UF), a collecting tank (C) with mixer and spiking and sampling point and three fluidization units working parallel (A) with BCDP as adsorbent (retention time: 41 s/cycle).

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Table 2 Monitoring data of the ecomachine technology and subsequent ultrafiltration prior the experiment carried out for micropollutants removal.

COD (chemical oxygen demand) (mg/L) BOD (biochemical oxygen demand) (mg/L) TOC (total organic carbon) (mg/L) AOX (adsorbable organic halides) (μg/L) TN (total nitrogen) (mg/L) TP (total phosphorous) (mg/L) TSS (total suspended solids) (mg/L) Turbidity (NTU) pH Specific electric conductivity (μS/cm, 20°C)

Raw wastewater

Effluent from the reactor cascade

Ultrafiltrated water

760 ± 38 300 ± 15 n.m. n.m. 90 ± 5 n.m. 380 ± 19 n.m. 7.8 ± 0.1 n.m.

220 ± 11 < EQC (50) 99 ± 5 76 ± 4 50 ± 3 8.0 ± 0.4 170 ± 9 24.4 ± 1.2 7.5 ± 0.1 2150 ± 108

10 ± 2 <5 5.4 ± 0.2 25.6 ± 0.8 23 ± 1 5.4 ± 0.3 <2 0.9 ± 0.1 7.6 ± 0.1 1910 ± 95

EQC: environmental quality criteria (in this case < 50). n.m. not measured.

ecomachine technology were generally not sufficient, e.g. in effluents the concentration of ibuprofen changed between 3.0–8.5 μg/L (an average 82% removal rate), of bisphenol A 0.6–20 μg/L (77% removal rate), of ketoprofen around 1 μg/L (59% removal rate), of naproxen 0.1–1.8 μg/L (33% removal rate) of dibutyl phthalate 0.5–3.0 μg/L (9% removal rate), and diclofenac 2.0–4.5 (4% removal rate). Another viewpoint during organic micropollutants monitoring was to determine those ones found in effluents not only in higher concentration, but mainly in soluble form, that is not adsorbed by suspended solids. According to GCeMS measurements the following microcomponents were found to be present in effluents having an average higher dissolved concentration part within their total residual concentration: benzoic acid (99%), bisphenol A (89%), diclofenac (79%), ibuprofen (76%), caffeine (73%), triclosan (58%), benzophenone (54%), dibutyl phthalate (53%), and cholesterol (42%). Several other micropollutants were detected as bonded principally to suspended particles in effluent (less than 5–10% of their total concentration was determined only in water-phase). Those organic micropollutants, which are mainly sorbed by flocs containing suspended solids are effectively removable by ultrafiltration. For instance, 50–67% naproxen was removed by ultrafiltration from the ecomachine type cascade outflow.

by ultrafiltration. In this case especially high decrease of suspended solids concentration was observed as expected. The pilot wastewater treatment plant fulfilled the quality criteria regarding the demonstrated water quality-indicating values for macrocomponents. However, GC–MS analyses detected regularly 50–60 compounds belonging to the emerging organic pollutants in communal wastewater of the small village of Telki. Several of them including ketoprofen, diclofenac, dibutyl phthalate, naproxen, benzophenone, ferulic acid, palmitic acid, cholesterol, bisphenol A, caffeine, ibuprofen and triclosan were present also in the reactor cascade final effluent showing that the ecomachine technology was unable to eliminate them (similarly to other traditional wastewater treatment biotechnologies) (Sebok et al., 2009; Zuccato et al., 2006). As to micropollutants removal the efficacy of ecomachine technology fluctuated also in time. The volume of wastewater influent and concentration of micropollutants in it changed according to fluctuating use in hospital and in households, as well as to changing weather conditions, etc. Actual activity of biomass highly dependent on temperature was another factor influencing the efficiency. For example, the varying concentrations and removals of two typical organic micropollutants, bisphenol A and naproxen within 6 months are shown in Fig. 3. During monitoring both the raw and effluent wastewaters of the pilot-plant scale ecomachine type wastewater treating plant 30 organic micropollutants were found to show high degradation rate. In spite of the effective (more than 90%) removal in case of these biodegradable micropollutants, there were yet some present also in the plant effluent due to their altering (0.1–1000 μg/L) concentration in the initial raw water. As for instance the biodegradable cholesterol concentration reached sometimes 5–6 μg/L in PWWTP effluents, too. In case of other 26 organic microcomponents, removal rates by

3.2. BCDP treatment Due to the large variations in micropollutants concentrations in time we added 9 selected chemicals to the plant effluent to ensure an average concentration level (∼5 μg/L) during supplementary post treating experiments. Their selection was verified by their environmental impact and GC–MS data obtained during monitoring. The micropollutants selected for spiking the effluent regularly appeared in the village wastewater even after treatment, and were typically found also in surface waters, e.g. in river Danube (Sebok et al., 2009). The concentrations were selected based on the long-term monitoring of the purified wastewater in this village where the municipal wastewater is mixed with that of the local hospital. So these concentrations are realistic although highly fluctuating in time. The 9 compounds include typical hormone components of contraceptives (β-estradiol, ethinyl estradiol, estriol), non-steroid anti-inflammatory drugs (NSAIDs: ibuprofen, diclofenac, naproxen, ketoprofen), cholesterol, a typical food constituent and bisphenol A, an industrial additive. A similarly spiked biologically treated wastewater was successfully purified by sorption with BCDP in laboratory-scale fluidization experiments (Nagy et al., 2014). Based on these experiments BCDP was selected as sorbent in the pilot-plant scale test, too. BCDP was found to have optimal properties concerning the binding capacity: 55–65% cyclodextrin content accompanied by not too high swelling (5 mL/g) and optimal particle size (0.06–0.32 mm). In smallscale laboratory experiments the number of accessible cyclodextrin rings for sorption was determined mainly by these properties

Fig. 3. Inflow and outflow concentrations of bisphenol A (BPA) and naproxen of the ecomachine technology at various sampling times measured by GC–MS and their removal rates. 5

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Table 3 Concentrations of 9 selected micropollutants in the plant effluent before and after spiking and during BCDP treatment of wastewater effluent at 17–19 °C measured by GC–MS. Compound

Conc. in filtered effluent (μg/L)

Total conc. after spiking (μg/L)

Conc. at 5 min treatment (μg/ L)

Conc. at 48 h treatment (μg/ L)

β-Estradiol Et. estradiol Estriol Ibuprofen Diclofenac Naproxen Ketoprofen Cholesterol Bisphenol A

< 0.001 < 0.001 < 0.001 < 0.001 3.99 ± 0.51 < 0.001 < 0.001 0.83 ± 0.06 0.23 ± 0.02

5.22 5.15 5.38 5.18 9.09 4.98 5.10 6.09 5.38

0.17 ± 0.02 < 0.001 0.22 ± 0.02 0.75 ± 0.08 1.19 ± 0.16 4.08 ± 0.36 4.41 ± 0.41 0.85 ± 0.06 0.23 ± 0.05

< 0.001 < 0.001 0.21 ± 0.02 0.88 ± 0.09 1.31 ± 0.17 3.60 ± 0.32 4.35 ± 0.48 0.52 ± 0.04 0.03 ± 0.02

± ± ± ± ± ± ± ± ±

0.52 0.52 0.52 0.52 0.91 0.45 0.51 0.42 0.43

Fig. 5. Inhibition of Lemna minor growth and Heterocypris incongruens mobility in percentage (< 25% inhibition: non-toxic, 25–50%: slightly toxic, 50–75%: toxic, > 75%: very toxic) (Start*spiked with the micropollutants, before treatment with BCDP).

(Wiedenhof et al., 1969; Pratt et al., 2010; Fenyvesi and Szente, 2016; García-Padial et al., 2017; Morin-Crini et al., 2018). As it was detailed at methods’ description, BCDP was applied in fluidized bed for post treatment of ultrafiltrated and spiked ecomachine type PWWTP effluent, and samples taken from spiked effluent before and also after BCDP treatment at various time intervals were analyzed both by gas chromatography–mass spectrometry and by direct toxicity assessment. Table 3 shows the chemical analysis results of effluent samples before and after spiking and at various BCDP treatment periods. As it can be seen in Table 3 a prefiltered (micro- and ultrafiltrated) effluent was spiked by 9 selected organic microcomponents. In the prefiltered effluent three of these selected micropollutants (diclofenac, cholesterol and bisphenol A) were yet detected before spiking. According to the GC–MS measurements of the treated water more than 95% of hormones and bisphenol A, and more than 85% of ibuprofen, diclofenac and cholesterol were removed within the first 5 min during BCDP treatment (Table 3 and Fig. 4). Poor removal rates were observed only for two NSAIDs, for naproxen and ketoprofen (< 20%). The data (Fig. 4 and Table 3) show how fast the sorption process was: equilibrium or near-equilibrium removal rate for each investigated micropollutant was reached in 5 min that is after two cycles of recirculation of the effluent. A slight improvement in time was observed only for estradiol, naproxen, cholesterol and bisphenol A removal. It was noticed, that close to equilibrium data were also detected after 2 h for those micropollutants, whose concentration showed some change after 5 min. Data obtained after 2 h contact time turned out to be equal (within a 5% deviation range) to those determined after 48 h, and for most of the studied components the concentration values also did not show any decreasing trend in time after 2 h. No pH change was detected on the effect of BCDP treatment in fluidization experiment even after 48 h (both initial and final pH were 7.5–7.6). The temperature of water

was 17–19 °C. Similarly to our results using sand and charcoal or activated carbon as sorbents for treating effluents of conventional sewage treatment plants, high removal efficiency (> 90%) of estradiol and ethinyl estradiol was observed, while only 10–30% ibuprofen and diclofenac were removed (de Castro et al., 2018). These NSAIDs could not be removed effectively by various other sorption technologies as tertiary treatments. A special sorbent consisting of MWCNT modified with TiO2 and designed for eliminating pharmaceutical micropollutants from wastewater removed 32–45% ibuprofen from a model solution of NSAIDs (Zaib et al., 2013).

3.2.1. Monitoring ecotoxicity From the two ecotoxity tests applied as desribed in Section 2.3.3 the duckweed test showed high inhibition by the raw wastewater, which remained high even after biological treatment showing that some toxic compounds were not removed by this secondary treatment (Fig. 5). Tertiary treatment by sorption on BCDP, however, reduced the toxicity and resulted in no growth inhibition. On the other hand, Heterocypris incongruens mobility test was found to be less sensitive: the raw wastewater was only slightly toxic, and the purified water samples showed no toxicity for this test organism. With Lemna minor growth inhibition test, the lowest effect concentration (LOEC) values for Na-diclofenac and bisphenol A were 3.10 and 6.25 mg/L, respectively (Fekete-Kertész et al., 2015), both far above their concentration occurred in our experiment. On the other hand, ibuprofen inhibited the growth of Lemna minor with a LOEC of 1 μg/L concentration (Pomati et al., 2004), being lower than the concentration in our experiment. Cleuvers (2003) indicated that the duckweed Lemna minor test was more sensitive to various drugs including diclofenac and ibuprofen than the acute Daphnia or algal test. He also observed that tests with combinations of various drugs revealed stronger effects than expected from the effect measured singly. Our results clearly indicate that the toxicity of the combination of 9 selected micropollutants decreased on the effect of treatment.

3.3. Studies related to sorption mechanism To see the relationship between the sorption efficiency and the affinity of the cyclodextrin to encapsulate the given pollutant, apparent binding constants for the micropollutants/hydroxypropyl β-cyclodextrin (HPBCD) complexes were determined by capillary electrophoresis (CE) (Table 4). The complex association–dissociation equilibrium was characterized by binding constants (K):

Fig. 4. Removal of 9 selected micropollutants from spiked wastewater after 5 min, 2 and 48 h BCDP treatment. 6

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plays an important role in organic micropollutants sorption. Nevertheless also some other binding sites, for instance, the secondary cavities formed by the web of crosslinkages may be involved in sorption as it was proposed by several research groups and reviewed by Cova et al. (2018) and Morin-Crini et al. (2018). These most recent reviews on the application of cyclodextrin-epichlorohydrin polymers in water treatment not only demonstrated their efficiencies for various pollutants including emerging micropollutants but also discussed sorption mechanism. Based on more than 300 references it was concluded that the macromolecular network of crosslinked cyclodextrin polymer significantly contributed to the binding by cyclic cavities of cyclodextrins themselves via hydrogen bonding, hydrophobic, electrostatic and van der Waals interactions. These mixed mechanisms made possible the efficient sorption of various compounds such as dyes, phenols, monoand polycyclic aromatic hydrocarbons, chlorinated hydrocarbons, pesticides, drugs, endocrine disruptors and detergents (Morin-Crini and Crini, 2013; Morin-Crini et al., 2018). The sorption mechanism depends on the properties of the pollutants, too. Thus, hydrophobicity, ionic charge, size and molecular weight of the contaminants are crucial parameters as well as their actual concentrations in water (Cova et al., 2018). In multicomponent solutions competition between the components should be also taken into account (Cova et al., 2018; Morin-Crini et al., 2018). This competition is determined by the concentrations of the competing species and their binding affinities toward the sorbent. Among the studied micropollutants only diclofenac does not fit the correlation curve (red point in Fig. 6). It was removed by much higher rate (∼85%) than expected based on its relatively low apparent binding constant. The outstanding removal rate of diclofenac could be attributed to the fact that its concentration was higher than of the other model compounds. On the other hand, the binding constants were calculated for 1:1 molar ratio of host and guest molecules in inclusion complexes. This molar ratio was based on literature data (see the references under Table 4). Diclofenac, however, can form also higher order complexes (Mucci et al., 1999; Kurkov et al., 2010) partly explaining its unexpected behavior.

Table 4 Apparent binding constants (K) for HPBCD complexes. K measured in this work by CE at pH 7.2 (M−1)

Literature data for K (M−1)

Et. estradiol β-Estradiol Estriol Ibuprofen

29,180 ± 200 15,000 ± 1000 n.m. 3000 ± 200

Diclofenac Naproxen Ketoprofen

180 ± 20 380 ± 20 300 ± 10

Cholesterol Bisphenol A

n.m. 4520 ± 10

71,000 (DW)a 39,000 (DW)a 28200 (DW)b 37,000 (DW)a 3300 (pH 7)c 4700 ± 500 (pH 9)d 1580 ± 100e 237 (pH 6.5)f 300g 1400 ± 80 (pH 9)d 1670h 128 (pH 6)i 460 ± 50 (pH 9)d 480 ± 100e 19,000 (pH 6.4)j 1500k

n.m. not measured, DW distilled water, determined by fluorimetry in distilled water (Pérez and Escandar, 2013), b, h and k by phase solubility method (Másson et al., 2005; Okimoto et al., 1996; Araki et al., 2001), c and e by calorimetry (Perlovich et al., 2003), d and f by fluorimetry (Junquera and Aicart, 1999; Abdoh et al., 2007), g by NMR (Mucci et al., 1999), i by HPLC (Sridevi and Diwan, 2002), j by spectral displacements technique (Frijlink et al., 1991).

K=

[D − HPBCD] [D][HPBCD]

where [D], [HPBCD] and D-HPBCD] are the molar concentrations of the drug, HPBCD and their complex, respectively (Szejtli, 1988). The values depend on the method used for determination, therefore they characterize “apparent” binding constant. We calculated the K values from the change in electrophoretic mobility in the presence of HPBCD in phosphate buffer at pH 7.2. In addition to these values measured in our laboratory, the literature data determined by other methods were also listed in Table 4. The apparent binding constant values determined by CE – although varying – follow the order of values published in literature, determined by different methods and at different pH. The salt-forming NSAIDs are especially sensitive to pH (see K values for ibuprofen and ketoprofen). The extremely high binding constants for hormones justify the > 99% removal of these micropollutants by BCDP from wastewater effluent. The high removal rates for bisphenol A and cholesterol are also in correspondence with their high binding constants. Also the low removal rates for naproxen and ketoprofen (< 30% and < 20%, respectively) can be attributed to their relatively low affinity for complex formation. The removal rate of ibuprofen (∼85%) fits also the rough correlation curve shown in Fig. 6. R2 value of linear regression (0.84) proves the correlation. The correlation shown in Fig. 6 for molecules of so much different structure and lipophilicity suggests that inclusion complex formation

3.4. Economic considerations Binding capacity values were calculated from the reduced concentrations of the micropollutants in 300 L spiked effluent by using 1 kg BCDP in fluidization setup (Table 5). In this pilot-scale experiment the binding capacities for the 9 studied micropollutants were found lower than those obtained for single component systems in laboratory scale experiments using solutions of three orders of magnitude higher concentrations (3 μM/g diclofenac Table 5 Calculated binding capacities for the 9 selected micropollutants.

Fig. 6. Correlation between removal rates of micropollutants from PWWTP effluent and their apparent binding constants with HPBCD (the red point represents diclofenac) (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).

Organic micropollutant

Conc. after spiking μM//L

Removed concentration μg/L

Removed from 300 L μg

Removed from 300 L μM

β-Estradiol Et. estradiol Estriol Ibuprofena Diclofenaca Naproxena Ketoprofen Cholesterol Bisphenol A Total for the 9 micropollutants

0.019 0.017 0.019 0.025 0.029 0.022 0.020 0.016 0.024 0.191

5.06 5.15 5.16 4.43 7.90 0.90 0.71 5.24 5.14

1518 1545 1548 1329 2370 270 213 1572 1545 11,910

5.57 5.21 5.37 6.64 7.40 1.17 0.84 4.07 6.77 42.53

a

7

Used as Na salts.

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(Fenyvesi and Szente, 2016), 16 μM/g ibuprofen (Jurecska et al., 2014). The total amount of pollutants (0.043 μM/g) bound by BCDP was about one tenth of the sorbents’ cyclodextrin content (0.52–0.57 μM/g). This host-guest ratio is acceptable taking into account that inclusion complex formation is an equilibrium process where the component ratios are determined by the complex association constants. In addition, the 9 selected micropollutant compounds compete not only with each other for the sorbent binding sites but with hundreds of further components including those of natural organic matter (NOM) present in wastewater. In this study we aimed at justifying the selected sorbent and technology for the removal of typical organic micropollutants from wastewater and determining the necessary contact time but not the sorption capacity. As a next step in technology development, optimization of process parameters is planned to reach the possible highest sorption. In this experiment BCDP was not regenerated. It was proved earlier in laboratory-scale experiments that BCDP could be regenerated by washing with aqueous ethanol (1:1 vol ratio of water and ethanol) and neither the physicochemical properties (grain shape and size) were changed nor the binding capacity was decreased measurably after several sorption–desorption cycles (Orprecio and Evans, 2003; Jurecska et al., 2014; Li et al., 2009; Morin-Crini et al., 2018). Regeneration of the sorbent, e.g. with ethanol, always results in concentrated solution of the pollutants, which should be further treated. Recycling the regenerated solution should be also taken into account, otherwise incineration of the sorbent saturated with harmful components seems to be more economical. The efficiency of technology can be further enhanced by combining sorption with other tertiary treatments in order to improve pollutant removal. For example, using pretreatment with ozone or UV oxidation some reaction products which appeared to be sorbed more efficiently by BCDP were formed (Charles et al., 2014). Another possibility for further development is combination of cyclodextrin polymers with magnetic micro- or nanoparticles, which can be easily removed from the aqueous phase utilizing their magnetic character. These product types are, however, far from scaling up. One of the latest report on bisphenol A removal from model solution used β-CD-functionalized mesoporous magnetic clusters in a few mg scale (Lee and Kwak, 2019). More and more research groups have recognized the potential of cyclodextrin polymers in final polishing of purified wastewater, especially in the removal of residual pharmaceutical compounds and other emerging contaminants. Therefore scaling up of BCDP production is expected to decrease the cost, making this tertiary wastewater treatment technology economically acceptable.

mechanism although some other phenomena might also be involved. The reduced toxicity of water effluent after BCDP treatment was proved by ecotoxicity tests. The fast process and these extremely high removal rates for the selected micropollutants of public concern and hard to remove ones by traditional wastewater treatments make the BCDP technology highly important for reducing human health risk and decreasing potential impact on the environment. We were the first showing that BCDP can remove selected micropollutants from a wastewater effluent still containing several other organic contaminants –some of them at higher concentrations– even at pilot-plant scale. We demonstrated that BCDP treatment applying fluidization technology needs only a few minutes contact time, which makes this technology applicable as a tertiary treatment coupled to physical and biological treatment steps at full scale in wastewater treatment plants. The widespread pharmaceutical applications of cyclodextrins are based on their high affinity for binding drugs. This property can be utilized when cyclodextrin-based sorbent has been used for the sorption of drugs as micropollutants present in wastewater effluents deriving from medical facilities, as hospitals, pharmaceutical factories, etc. The BCDP sorbent tested in pilot-plant scale would be particularly suitable for application in local wastewater treatment facilities for effluents from hospitals and pharmaceutical factories. The increasing shortage of clean water will force the acceptance of such, today still relatively expensive technologies. Funding This work was supported by National Innovation Office [CDFILTER, TECH_08-A4/2-2008-0161]. Acknowledgement The GC–MS measurements are greatly acknowledged to Ibolya Perlné Molnár (Eötvös University, Budapest, Hungary). References Abdoh, A.A., Zughul, M.B., Davies, J.E.D., Badwan, A.A., 2007. Inclusion complexation of diclofenac with natural and modified cyclodextrins explored through phase solubility, 1H-NMR and molecular modeling studies. J. Incl. Phenom. Macrocycl. Chem. 57 (1–4), 503–510. https://doi.org/10.1007/s10847-006-9241-8. Alsbaiee, A., Smith, B.J., Xiao, L., Ling, Y., Helbling, D.E., Dichtel, W.R., 2016. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529, 190–194. https://doi.org/10.1038/nature16185. Araki, M., Kawasaki, N., Nakamura, T., Tanada, S., 2001. Removal of bisphenol A in soil by cyclodextrin derivatives. Toxicol. Environ. Chem. 79 (1–2), 23–29. https://doi. org/10.1080/02772240109358973. Aydin, E., Şahin, M., Taşkan, E., Hasar, H., Erdem, M., 2016. Chlortetracycline removal by using hydrogen based membrane biofilm reactor. J. Hazard. Mater. 320, 88–95. https://doi.org/10.1016/j.jhazmat.2016.08.014. Bolong, N., Ismail, A.F., Salim, M.R., Matsuura, T., 2009. A review of the effects of emerging contaminants in wastewaters and options for their removal. Desalination 239, 229–246. https://doi.org/10.1016/j.desal.2008.03.020. Bouras, P., Lianos, P., 2008. Synergy effect in the combined photodegradation of an azo dye by titanium dioxide photocatalysis and photo-fenton oxidation. Catal. Lett. 123 (3–4), 220–225. https://doi.org/10.1007/s10562-008-9466-9. Brillas, E., 2014. A review on the degradation of organic pollutants in waters by UV photoelectro-Fenton and solar photoelectro-Fenton. J. Braz. Chem. Soc. 25 (3), 393–417. https://doi.org/10.5935/0103-5053.20130257. Charles, J., Crini, G., Morin-Crini, N., Badot, P.-M., Trunfio, G., Sancey, B., de Carvalho, M., Bradu, C., Avramescu, S., Winterton, P., Gavoille, S., Torri, G., 2014. Advanced oxidation (UV-ozone) and cyclodextrin sorption: effects of individual and combined action on the chemical abatement of organic pollutants in industrial effluents. J. Taiwan Inst. Chem. Eng. 45, 603–608. https://doi.org/10.1016/j.jtice.2013.06.023. Cleuvers, M., 2003. Aquatic ecotoxicity of pharmaceuticals including the assessment of combination effects. Toxicol. Lett. 142 (3), 185–194. https://doi.org/10.1016/ S0378-4274(03)00068-7. Cova, T.F.G.G., Murtinho, D., Pais, A.A.C.C., Valente, A.J.M., 2018. Cyclodextrin-based materials for removing micropollutants from wastewater. Curr. Org. Chem. 22, 2150–2181. https://doi.org/10.2174/1385272822666181019125315. Crini, G., Fourmentin, S., Fenyvesi, É., Torri, G., Fourmentin, M., Morin‑Crini, N., 2018. Cyclodextrins, from molecules to applications. Environ. Chem. Lett. 16, 1361–1375. https://doi.org/10.1007/s10311-018-0763-2.

4. Conclusions After numerous laboratory-scale experiments using a few milligram or gram of cyclodextrin-containing sorbents we are the first to demonstrate the feasibility of BCDP for the removal of dissolved micropollutants as a tertiary treatment of wastewater in a pilot-plant scale experiment using real municipal wastewater effluent as raw water in the adsorptive post step of the investigated technology. A green technology (ecomachine technology combining phytoremediation with microbial degradation) was applied as secondary treatment for the removal of biodegradable hazardous materials. Suspended solid particles with the contaminants adsorbed on their surface were removed in post treatment by ultrafiltration. As a final step, xenobiotics non-biodegradable or biodegradable were removed by BCDP applied in a fluidized state at a pilot-plant scale experiment. The measured removal efficiencies determined by GC–MS were > 99% for the tested hormones and bisphenol A and ∼85% for two of the NSAIDs (ibuprofen and diclofenac). The rough correlation between the apparent binding constants determined by capillary electrophoresis and the removal rates in the pilotplant scale sorption experiment suggests that inclusion complex formation of micropollutants with cyclodextrin plays a role in the sorption 8

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