Nzvi-Catalyst Research Paper

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Page 1 of 40 Environmental Science: Water Research & Technology
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Water Impact Statement

Emerging pharmaceuticals and personal care products (PPCPs) including antibiotics,
antidepressants, or stimulants remain as a complex mixture in our wastewater or natural aquatic
Environmental Science: Water Research & Technology Accepted Manuscript

systems and have shown to pose adverse effects on fish and other aquatic organisms.
Understanding the competitive interactions of diverse PPCPs with the newly engineered
graphene-iron nanohybrids can provide with significant insight about their effective removal
from water through adsorption and/or advanced oxidation processes (AOP).
Published on 24 June 2020. Downloaded by University of Exeter on 6/25/2020 9:04:16 PM.
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1
2 Adsorption and Advanced Oxidation of Diverse Pharmaceuticals and

3 Personal Care Products (PPCPs) from Water Using Highly Efficient
4 rGO-nZVI Nanohybrids
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7 Arvid Masud,1 Nita G. Chavez Soria,2 Diana S. Aga,2 and Nirupam Aich1,*
8 1Department of Civil, Structural and Environmental Engineering, University at Buffalo, The State
9 University of New York, Buffalo, NY 14260
10 2Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260
11 Submitted to
12 Environmental Science: Water Research & Technology
13 06/22/2020
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26 * Corresponding Author: Nirupam Aich, Phone: 716-645-0977, Email: nirupama@buffalo.edu
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27 Abstract:
28 Engineered nanomaterials, like graphene with tunable adsorption sites and nanoscale zero-valent

29 iron (nZVI) with unique redox chemistry, offer great prospect for removing pharmaceutical and
30 personal care products (PPCPs) through adsorption and catalytic advanced oxidation process
31 (AOP) in comparison to bulk materials. Although PPCPs are found to be as a complex mixture in
32 wastewater and in the environment, most studies regarding nano-enabled PPCP removal reported
33 results with only one PPCP at a time and typically at high initial concentrations. In this study, we
34 utilized reduced graphene oxide (rGO) to support nZVI to synthesize rGO-nZVI nanohybrid (NH)
35 and used rGO-nZVI NH for the removal of a complex mixture of 12 diverse PPCPs that includes
36 antibiotic, anti-inflammatory, anti-seizure, and antidepressant pharmaceuticals, and are
37 recalcitrant in the environment. We also tested the removal of PPCPs at their individual
38 environmentally relevant concentrations at ppb level. The rGO-nZVI NH synergistically
39 performed as both an adsorbent and a heterogeneous Fenton catalyst (for AOP) in the presence of
40 H2O2, to remove ~95-99% of environmentally relevant concentrations (200 ppb) of the PPCPs
41 within 10 minutes. Even in the absence of H2O2, the hybridization resulted in better adsorptive
42 property (14-72% more removal) in the rGO-nZVI NH compared to the parent nanomaterials (rGO
43 or nZVI) for various PPCPs in the mixture, removing ~82-99% of the PPCPs, at the end of 30
44 minutes, with comparatively slower kinetics (~3-5.5 times) than in presence of H2O2.
45 Hydrophobic PPCPs were removed faster and more with both the adsorption and AOP. The
46 potential of utilizing rGO-nZVI NH in drinking/wastewater treatment system, or even in point-of-
47 use system where necessary, was substantiated by the enhanced and fast PPCP removal capacity
48 of the nanohybrid.
49
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50 1. Introduction
51 Pharmaceuticals and personal care products (PPCPs) are a diverse set of compounds including

52 antibiotics, analgesics, anti-seizure, nonsteroidal anti-inflammatory (NSAID), and antidepressants
53 used to treat diseases and improve quality of life, thus heavily used worldwide. Conventional
54 wastewater treatment plants (WWTPs) with primary (e.g., sedimentation) and secondary (e.g.,
55 activated sludge) treatment processes exhibit limited PPCP removal efficiencies.1-4 This causes
56 inevitable release of mixtures of PPCPs in natural aquatic environment,5 resulting in their presence
57 at ppb to ppt (µg/L to ng/L) levels in water bodies.6-8 Recently, trace level concentrations of
58 selective serotonin reuptake inhibitors (SSRIs), some of the most prescribed antidepressants, have
59 been detected in fish from the Great Lakes.9 Many of the PPCPs10-12 including SSRIs,4, 13-16 have
60 been reported to induce adverse physiological effects in aquatic organisms, e.g., mortality,
61 developmental and reproductive disorder, endocrine disruption.17, 18 Moreover, drinking water
62 quality may also be affected from the use of PPCP contaminated surface water that are used as
63 intake source for drinking water treatment plants (DWTPs).19-21 This warrants incorporation of
64 advanced treatment technologies i.e., adsorption and advanced oxidation process (AOP) into
65 WWTPs and DWTPs for the effective removal of these recalcitrant PPCPs including SSRIs.22-25
66 Engineered nanomaterials, having high surface area with tunable adsorption sites and
67 enhanced catalytic property, possess high potential for removing PPCPs through adsorption and
68 AOP, respectively, in comparison to conventional bulk materials.26-28 Graphene and its derivatives
69 namely graphene oxide (GO) and reduced graphene oxides (rGO) are two dimensional (2D)
70 carbonaceous nanomaterials that can favorably adsorb various PPCPs, mainly through
71 hydrophobic and electrostatic interaction.29-31 However, the adsorbed PPCP requires further
72 treatment for their degradation. On the other hand, nanoscale zero-valent iron (nZVI) particles has
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73 been explored as heterogeneous Fenton catalysts for AOP based PPCP degradation.32, 33 nZVI can
74 generate Fe2+ ions through slow dissolution at surface, which promotes formation of reactive

75 oxygen species (ROS) in the presence of hydrogen peroxide (H2O2). These nascent ROS react
76 with PPCPs to degrade them. But, nZVI suffers from low surface reactivity due to aggregation
77 because of its high magnetic and van der Waals attraction forces.34, 35 To mediate these challenges,
78 a nanohybrid approach can be followed36 that will utilize planar rGO to support nZVI particles
79 resulting in rGO-nZVI nanohybrids (NHs). rGO-nZVI NHs can offer a synergistic approach for
80 enhanced PPCP removal where rGO can adsorb PPCPs on its surface, that can simultaneously be
81 degraded using AOP catalyzed by nZVI.29, 37 Moreover, rGO can improve nZVI’s catalytic
82 property by providing fast electron transfer38, 39 and resisting nZVI aggregation.36
83 Recently, a few studies have reported graphene supported iron nanoparticles (mostly iron
84 oxides and hydroxides, but not nZVI) for heterogeneous Fenton catalysis and exploited combined
85 adsorption and AOP for enhanced PPCP removal.40-43 For example, goethite (α-FeOOH)
86 nanoparticle deposited rGO hydrogel utilized the advantage of strong Fe-O-C bond in generation
87 of reactive oxygen species which enhanced antibiotic tetracycline degradation.43 However, in the
88 case of rGO-nZVI, the zero valent state of iron in nZVI does not rely on the Fe2+/Fe3+ conversion
89 cycle facilitated by Fe-O-C bonds and can keep donating electron to generate Fe2+ at the surface
90 to directly interact with H2O2, thereby, making rGO-nZVI more catalytic than other graphene-iron
91 materials44 and our choice of material for this study. Moreover, all the above-mentioned studies
92 only focused on removal/degradation of only one antibiotic, and not a mixture of PPCPs. Also,
93 all these studies (except one) used PPCPs at significantly higher concentrations (>1 mg/L)
94 compared to the environmentally relevant PPCP concentrations (i.e., sub-ppm and ppb level).28, 32,
95 45-51 Although Peng et al. tested graphene for adsorption of a mixture of 7 antibiotics at sub-ppm
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96 level,52 realistically, actual wastewater contains a mixture of diverse PPCPs that include SSRIs,
97 SNRIs (Serotonin-Norepinephrine Reuptake Inhibitors), antibiotics, anti-seizure, and NSAID

98 pharmaceuticals. These various PPCPs including SSRIs may interact with each other affecting
99 their overall removal by these nanomaterials.53, 54 Therefore, evaluating the performance of rGO-
100 nZVI NHs in removing a mixture of PPCPs rather than individual ones is more relevant and
101 potentially benefit the water treatment processes by delineating the competition between PPCPs
102 during adsorption and AOP.
103 The objectives of this study were, for the first time, to determine and compare the extent
104 of adsorptive and AOP-based removal of (i) a complex mixture of diverse PPCPs, including SSRIs,
105 antibiotics, anti-seizure, NSAIDs, and stimulants, (ii) at environmentally relevant ppb level
106 concentration using (iii) catalytic rGO-nZVI NHs. We also aimed to compare the PPCP removal
107 performance of rGO-nZVI NHs with that of its parent materials, i.e., rGO and nZVI, to delineate
108 the effect of hybridization on PPCP removal. To achieve these aims, rGO-nZVI NHs were
109 synthesized through chemical reduction process and comprehensively characterized with
110 transmission electron microscopy (TEM), X-ray diffraction spectrometry (XRD), Raman
111 spectroscopy, thermogravimetric analysis (TGA), and Fourier-transform infrared (FTIR)
112 spectroscopy. The performance of rGO-nZVI NHs for the removal of a mixture of 12 PPCPs at
113 environmentally relevant ppb level concentration was investigated using liquid chromatography
114 tandem mass spectrometry (LC-MS/MS). A series of PPCP removal tests using the nanohybrids
115 and their parent nanomaterials (i.e., rGO and nZVI) and their mixtures were conducted to
116 determine the synergistic effect of hybridization and the effect of PPCP mixture along with
117 determining the underlying PPCP removal mechanisms (i.e., adsorption and/or AOP).
118 2. Materials and methods
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119 2.1 Chemical and Reagents
120 Single layer graphene oxide (GO, >99.3 wt%, thickness 0.43-1.23 nm), sodium borohydride

121 (NaBH4, >98%), and ferric chloride hexahydrate (FeCl3.6H2O, 98%) were purchased from US
122 Research Nanomaterials, Inc. (Houston, TX), Fisher Scientific (Fair Lawn, NJ), and Acros
123 Organics (Geel, Belgium), respectively. Standards for the selected 12 pharmaceuticals including
124 acetaminophen (ACT), caffeine (CAF), carbamazepine (CBZ), carbamazepine-d10, citalopram
125 (CIT), diclofenac (DIC), fluoxetine (FLX), ibuprofen (IBU), lamotrigine (LAM), naproxen (NPX),
126 paroxetine maleate (PRX), sulfamethoxazole (SMX), and venlafaxine (VEN) were purchased from
127 Cerilliant (Round Rock, Texas), Sigma Aldrich (St Louis, MO) and Cambridge Isotopes
128 (Tewsbury, MA). All the PPCPs had chromatographic purity over 98%. N,N′-diethyl-p-
129 phenylenediamine (DPD), ammonium molybdate, and potassium iodide were obtained from Hach
130 (Loveland, CO). Deionized (DI) water with conductivity of 18.2 Ω from Barnstead
131 NANOpureTM water system (Waltham, MA) was used for all the experiments. LC-MS grade
132 acetonitrile (>99.9%) was purchased from EMD Millipore Corporation (Billerica, MA). Formic
133 acid (88%) and n-butanol (>99.9%) was obtained from Fisher Chemical (Pittsburgh, PA) and
134 Sigma Aldrich (St Louis, MO) respectively.
135 2.2 Synthesis and characterization of nanohybrids
136 rGO-nZVI NHs were synthesized following a well-established wet chemistry method.55 Briefly,
137 100 mg GO was dispersed in 200 mL DI water (i.e., providing 0.5 mg/mL concentration) by
138 sonication for 2 hours (amplitude 50, pulse on 8 sec, pulse off 2 sec) with a microtip (1/4”) based
139 ultrasonic dismembrator (Q700, Qsonica Sonicators, Newtown, CT). Subsequently, 1 g
140 FeCl3.6H2O was added to make iron concentration 18.5 mM in the dispersion. A peristaltic pump
141 was used to add 20 mL of NaBH4 solution (1.59 M) with a flow rate of 0.5 mL/minute into the
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142 mixture to co-reduce GO and iron salt. The reaction was carried out in an inert atmosphere with
143 constant N2 gas flow (0.3 L/minute) under continuous magnetic stirring (300 rpm) at room

144 temperature. After adding the NaBH4, the suspension was kept stirring for another half an hour
145 under N2 gas. The suspension was filtered and was washed with ethanol and DI water for couple
146 of times through vacuum filtration (0.45 µm high volume low pressure (HVLP) filter) for removing
147 excess ions. The solid residues were dried overnight in vacuum oven at 60 oC before further
148 experiments. In case of parent nanomaterial synthesis, rGO and nZVI, similar synthesis protocol
149 was followed using their respective precursors individually. For rGO synthesis, no iron salt was
150 added and 20 mL 0.2 M NaBH4 was used dropwise to reduce GO. For nZVI synthesis, 1 g
151 FeCl3.6H2O was dissolved in 200 mL DI water without addition of any GO. For reduction of iron
152 salt, 20 mL 1.32 M NaBH4 was used under N2 gas flow.
153 Transmission electron microscopy (TEM, JEOL JEM 2010, JEOL USA, Inc.) was
154 performed at an accelerating voltage of 200 KV to image the physical morphology of the rGO,
155 nZVI, and rGO-nZVI NHs. 1 mg of sample was dispersed in 10 mL ethanol with ultrasonic
156 dismembrator for TEM sample preparation. One drop of the dispersion was placed on a carbon-
157 coated copper grid (100 mesh, Ted Pella, Inc., Redding, CA) using micro-pipette and was air-dried
158 for 20 minutes before analysis. The X-ray diffraction (XRD) analysis of the samples were
159 performed at room temperature by Rigaku Ultima IV (Rigaku Corporation) using the Kα emission
160 of a Cu X-ray source (λ = 1.5418 Å). The incident angle range was kept in the range from 5° to
161 90° with a scan rate of 2º/min and step size of 0.02º. The vibrational modes and lattice order of
162 the molecular structures were studied using Raman Microscope (Renishaw InVia, Renishaw plc.)
163 with incident laser wavelength of 514 nm. 1 mg of dried samples was placed as a thin layer on a
164 glass slide to carry out the Raman spectroscopy. Thermogravimetric analysis (TGA,
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165 Micromeritics Instrument Corp.) with the samples were carried out in air with a ramp rate of
166 10 °C/min to 1000 °C to analyze the thermal stability of the samples. A Fourier-transform infrared

167 (FTIR) spectroscopy instrument (1760 FTIR, Perkin-Elmer) was used to obtain infrared adsorption
168 spectrum of the samples within the range of 500–4000 cm−1 with 4 cm−1 resolution to characterize
169 the functional groups present in the sample. Elemental carbon content in the dry samples were
170 measured with a carbon, hydrogen, and nitrogen (CHN) bulk elemental analyzer (2400 Series II,
171 Perkin-Elmer).
172 2.3 PPCP removal experiments
173 Figure S2 presents a schematic showing the experimental steps for evaluating the efficacy of rGO-
174 nZVI NHs for PPCP removal through both adsorption and AOP based adsorption. In general,
175 PPCP mixtures were dosed with nanomaterials (either rGO, nZVI, or rGO-nZVI) in individual
176 vials and subjected to either only adsorption (no H2O2) or AOP augmented adsorption (with H2O2)
177 while shaking. This was followed by sample collection at different time intervals, reaction
178 quenching, centrifugation (to remove nanomaterials), and LC-MS/MS analysis to obtain and
179 compare PPCP removal efficiency to evaluate the performance of catalyst/oxidant system.
180 Detailed description of the experiments with specific quantities and time is given below. Two
181 different aqueous stock solutions were prepared for PPCP batch removal tests. One of the stock
182 solutions consisted of all 12 PPCPs that are listed in Table 1 with their chemical structures shown
183 in Figure S3, each having a concentration of 200 µg/L (ppb). The other stock solution, used for
184 kinetic removal tests, consisted of 6 PPCPs (serial no. 4, 5, 6, 10, 11, and 12 from Table 1) also
185 having concentration of 200 µg/L. PPCP removal tests were conducted under three different
186 experimental arrangements: (i) only H2O2 (control), (ii) nanomaterials (i.e., rGO-nZVI NHs;
187 parent nanomaterials rGO or nZVI; mixture of parent nanomaterials rGO and nZVI), and (iii)
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188 combination of nanomaterials and H2O2. For all of the removal tests, 15 mL PPCP solution was
189 placed in a glass vial covered with aluminum foil and kept under constant shaking at 150 rpm for

190 30 minutes. The nanomaterial dosage were set at 8 mg in the 15 mL PPCP solution (i.e., 533 mg/L
191 nanomaterials) for all the removal tests. In the case of removal test with mixture of parent
192 nanomaterials, 1.9 mg of rGO (i.e., 127 mg/L rGO) and 6.1 mg (i.e., 407 mg/L nZVI) of nZVI
193 were used. The amounts of individual nanomaterials (i.e., rGO and nZVI) for the mixture was
194 same as their amounts in the synthesized rGO-nZVI NH. For removal tests with H2O2, 15.60 µL
195 of 30 wt.% H2O2 was added to the 15 mL PPCP solution to achieve the final H2O2 concentration
196 of 10 mM. The initial pH was adjusted to 3 with 1M HCl and 1 M NaOH in all cases, which has
197 been reported in literature as the most favorable operating pH condition for heterogeneous Fenton
198 catalysts.32, 56 For kinetic removal tests, 300 µL aliquots were collected at 0, 5, 10, 15, 20, 25, and
199 30 minutes. 10 mM n-Butanol was added to the aliquots instantly to scavenge all the ROS and
200 centrifuged at15000 rpm for 1 minute. The amount of n-Butanol used in this study was chosen
201 based on the range presented in previous literature for n-Butanol amount for complete quenching
202 of ROS produced during heterogeneous Fenton reactions.57, 58 200 µL of supernatant was collected
203 and consequently spiked with an internal standard (Carbamazepine-d10, final concentration 50
204 µg/L) prior to LC-MS/MS analysis.
205 Hach (method 10290) procedures were followed to quantify residual H2O2 concentration
206 in batch reactions through DPD colorimetric method.59
207 2.4 LC-MS/MS analysis of PPCPs
208 A previously established LC/MS/MS method was adapted to monitor the 12 PPCPs in this study
209 (Table 1).60 In summary, analysis of PPCPs was perfo1rmed using an Agilent 1100 LC system
210 coupled to a 6410 triple quadrupole mass spectrometer (Palo Alto, CA). Chromatographic
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211 separation was achieved with a Waters Cortecs™ C18+ column (Milford, MA) with an inner
212 diameter and length of 2.1 mm and 150 mm respectively, and a 2.7 µm particle size. The column

213 was fitted with a 5.0 mm x 2.1 mm, 2.7 µm Cortecs™ guard cartridge (Milford, MA). A 39-
214 minute run time method was used with mobile phase A (0.3% formic acid in DI water obtained
215 from NANOpure™ water system, Waltham, MA) and B (100% acetonitrile). The gradient used
216 was as followed: 90% A for 2 minutes, ramp to 95% B over 23 minutes, followed by a four minute
217 hold time and brought back to starting conditions over 3 minutes. The column was equilibrated
218 for 7 minutes at the end of the gradient. The flow rate was set to 0.2 mL/min and a volume of 20
219 µL was injected. The mass spectrometer was set to positive electrospray ionization with 4 kV
220 spray voltage, 300 ◦C drying gas temperature, 15 psi nebulizer pressure (N2) and 6 L/min drying
221 gas flow (N2). Data collection and analysis were performed using Agilent Technologies Mass
222 Hunter Software Version B (Palo Alto, CA). Details of the multiple reaction monitoring (MRM)
223 transitions are listed in Table 1.
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224 Table 1. Target Analytes and LC/MS/MS parameters.

Serial Analyte Type Log Kow(§) Fragmentor MRM Collision
No. Voltage (eV) transitions Energy
(Q and q) (eV)
1 Acetaminophen Analgesic 0.5 100 152→65 29
(ACT) 152→110 14
2 Caffeine (CAF) Stimulant -0.1 126 195→42 33
195→138 18
3 Carbamazepine Anti-seizure 2.5 119 237→179 37
(CBZ) 237→194 18
4 Citalopram (CIT) Antidepressant 3.2 150 325→109 25
(SSRI) 325→262 15
5 Diclofenac (DIC) Nonsteroidal anti- 4.4 100 296→214 34
inflammatory 296→250 10
6 Fluoxetine Antidepressant 4.0 40 310→148 4
(SSRI)
7 Ibuprofen (IBU) Nonsteroidal anti- 3.5 60 207→119 20
8 Lamotrigine Anticonvulsant 1.4 140 256→109 60
256→211 20
9 Naproxen (NPX) Nonsteroidal anti- 3.3 100 231→115 60
(NSAID)
10 Paroxetine (PRX) Antidepressant 3.5 100 330→123 25
(SSRI) 330→192 20
11 Sulfamethoxazole Antibiotic 0.9 120 254→156 10
(SMX) 254→108 22
12 Venlfaxine (VEN) Antidepressant 2.9 114 278→121 30
(SNRI) 278→215 10
225 (§) https://pubchem.ncbi.nlm.nih.gov
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226 3. Results and Discussion
227 3.1 Physicochemical properties of rGO-nZVI NHs and parent nanomaterials

228 The physical morphology of the rGO-nZVI NHs along with parent nanomaterials rGO and nZVI
229 were analyzed using TEM images (Figure 1). The GO nanosheets are quasi-transparent with
230 lateral dimensions between 1-5 µm on average (Figure 1a). In the case of bare nZVI (Figure 1b),
231 the nanoparticles aggregated to form a chainlike connected structure through iron oxide formation
232 in the outer shell. In the case of rGO-nZVI NH (Figure 1c), much smaller nZVI particles
233 (compared to bare nZVI) were segregated and distributed throughout the rGO sheets. Further
234 analysis of the TEM images helped to determine the particle size distribution of nZVI particles for
235 bare nZVI and rGO-nZVI NHs (Figure S1). The nZVI particle size was mostly in the range of
236 100-200 nm for bare nZVI, whereas it was in the range of 10-40 nm for the rGO-nZVI NH. Similar
237 decrease in size of the nZVI particles due to hybridization with rGO nanosheets has been well
238 documented in previous literatures.35, 61 This confirms that the hybridization led to the successful
239 prevention of nZVI aggregation by the rGO nanosheets.
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240
241 Figure 1. TEM images of (a) rGO, (b) nZVI, (c) and (d) rGO-nZVI NH.
242 Figures 2(a, b, c, and d) present respectively the XRD, Raman, TGA, and FTIR spectra of
243 synthesized rGO-nZVI NHs and parent rGO and nZVI. The XRD spectrum of rGO shows the
244 characteristic carbon sharp peak for GO at ~10o and broadened peak for graphene at ~26o.35 The
245 XRD spectrum of bare nZVI has both Fe0 characteristic peaks at 45 and 65 along with Fe3O4
246 characteristics peaks at 30°, 35°, and 57°.35 The XRD spectrum of rGO-nZVI shows predominant
247 Fe0 peak at ~45° indicating that the iron nanoparticles on the graphene sheet were mostly present
248 in zero valence state. This suggests that graphene could resist oxidation of nZVI nanoparticle in
249 the rGO-nZVI NH.62 The Raman spectra shown in Figure 2(b) provide information regarding
250 surface defects for different nanomaterials studied here. The ratio of the defect D-band at (ID ∼
251 1350 cm–1) and graphitic G-band (IG ∼ 1590 cm–1) in the Raman spectrum, ID/IG is a measure of
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252 lattice defects in graphene lattice structure.61 The higher defect in graphitic structure for the NH
253 (ID/IG = 1.05) compared to rGO (ID/IG = 0.79) confirms the impregnation of nZVI particle on

254 graphene surface.55 Additionally, the signal for iron nanoparticles in lower Raman shift range (100
255 – 500 cm-1) also suggests the hybridization of nZVI with graphene. Figure 2c shows the TGA
256 results for rGO, nZVI, and rGO-nZVI NH, and shows that rGO gradually undergoes combustion
257 in the presence of air between 250 oC and 600 oC and decreases to 10% of its original mass which
258 finally decreases to 7% of its original mass at 1000 oC.63 However, for nZVI and rGO-nZVI, we
259 observe an increase in the mass after 400-500 oC during TGA. In case of nZVI the mass remains
260 same until 400 oC and then increases sharply to 139% at 550 oC. For rGO-nZVI, the mass steadily
261 decreases (due to rGO combustion) to 82% of its original mass until 500 oC and then sharply
262 increases to 96%. For both nZVI and rGO-nZVI, the reason of mass increase after 400-500 oC
263 can be attributed to the iron oxidation in the presence of air.64, 65 This suggests that the iron present
264 in nZVI, both in the rGO-nZVI NH and parent nanomaterial, are mostly in reduced form, and gets
265 oxidized during TGA. The FTIR spectrum of rGO suggests most of the functional groups were
266 removed during reduction from GO, as the peak for stretching vibration of C=O (at 1720 cm-1) and
267 C-O (at 1040 cm-1) bonds were significantly weakened in case of rGO compared to GO.66 In case
268 of FTIR spectrum of nZVI, the peaks at 547, 840, and 1630 cm-1 correspond to the Fe-O stretch.36
269 The weakened peak of the Fe-O band for rGO-nZVI NH spectrum can be attributed to lesser
270 oxidation and smaller size of nZVI in the nanohybrid which results in more amorphous
271 structures.67 The stretching vibration band for the functional groups are also absent in case of
272 rGO-nZVI NH. The shift of the C=C band to 1560 cm-1 (compared to 1605 cm-1) can be attributed
273 to chemical bond between nZVI and the graphitic skeleton of rGO.68 The CHN analysis suggests
274 the elemental carbon content in rGO and rGO-nZVI NH is 62.35% and 14.91% respectively. This
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14.91
275 indicates the rGO content in the NH to be 23.93% (= 0.623 %). If the rest of the rGO-nZVI
NH is considered to be nZVI, the ratio of rGO and nZVI turns out to be ~1:3.2, which conforms

276
277 to our previous study.61

278
279 Figure 2. (a) XRD, (b) Raman, (c) TGA, and (d) FTIR spectra of rGO-nZVI NH and parent
280 nanomaterials rGO and nZVI.
281 3.2 PPCP removal efficiencies for rGO-nZVI NHs and parent nanomaterials
282 3.2.1. Adsorptive removal of PPCPs
283 Aqueous solution combining a diverse matrix of 12 PPCPs including 4 antidepressants (1 SNRI +
284 3 SSRIs), 3 NSAIDs, 1 analgestic, 2 anti-seizure, 1 antibiotic, and 1 stimulant drug, each at an
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285 environmentally relevant concentration (200 ppb), was used to evaluate and compare the PPCP
286 removal performance of the rGO-nZVI NH along with the parent nanomaterials under the same

287 experimental conditions. Figure 3a and Table S1 present the results for PPCP removal efficiency
288 by nanomaterial based adsorption using rGO-nZVI NH or rGO or nZVI for 30 min. One of the
289 parent nanomaterials, nZVI, had minor adsorptive removal capacity, removing less than 15% of
290 the initial concentaration of all the PPCPs after 30 minutes. The other parent nanomaterial rGO,
291 removed significantly higher amount of PPCPs than nZVI; however, still had removal efficiency
292 within the range of 15-51% except for paroxetine (SSRI) with a removal efficiency of 71%. In the
293 case of rGO-nZVI NH, the PPCP removal efficiencies ranged from 74-100% after 30 minutes. The
294 NH showed more than 95% removal performance for six of the PPCPs including all 3 SSRIs
295 (citalopram, paroxetine, and fluoxetine), 2 NSAIDs (diclofenac and naproxen), and 1 anti-seizure
296 (lamotrigine). The lowest removal performance (74%) by the NH was observed for
297 sulfamethoxazole (antibiotic), but this removal performance by NH was still higher than removal
298 performance by the parent nanomaterials for any of the PPCPs including sulfamethoxazole.
299 Therefore, a significant increase (28% - 70%) in the adsorptive PPCP removal percentage was
300 observed for rGO-nZVI NHs compared to the parent nanomaterials rGO and nZVI. A Previous
301 study, which worked with bare graphene to remove a mixture of antibiotics at environmentally
302 relevant concentrations, showed similar removal efficiency (>89%) but with much higher dose of
303 the nano-adsorbent (1 mg/mL) i.e., double the dose used in our study and only afer a long
304 equilibrium time of upto 24 hours.52
305 The significantly better PPCP adsorptive removal performance by the rGO-nZVI NH,
306 compared to parent nanomaterials, can be attributed to increased adsorption sites resulting from
307 nZVI acting as a spacer resisting restacking of rGO nanosheets, whereas rGO simultaneously
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308 resiting nZVI aggregation by grafting nZVI on its surface.69-71 In addition, the heterojunction at
309 metal-graphene interface can act as specific adsorption sites and contribute to the overall increase

310 of adsorption capactity in the NH.72, 73 The rGO-nZVI NH, along with the parent nanomaterials,
311 exhibited different removal performance for different PPCPs in the matrix. This can be attributed
312 to the physicochemical properties of both the adsorbent and also the PPCPs. Mostly, the
313 hydrophobicity of the studied PPCPs appears to govern the adsorption process. In the case of
314 PPCPs with high log Kow value (>3, SSRIs: citalopram, paroxetine, fluoxetine; NSAIDs:
315 diclofenac and naproxen; Table 1), except ibuprofen, the rGO-nZVI NH was able to remove more
316 than 98% of the initial concentration, suggesting hydrophobic interaction a dictating adsorption
317 mechanism. The relatively lower removal of ibuprofen (89%) can be attributed to the presence of
318 a single aromatic ring and a hydrophilic carboxylic group, which may cause reduced π-π
319 interaction (compared to others), ultimately resulting in less competitive adsorption within the
320 PPCP matrix.74 The two least removed PPCPs, sulfamethoxazole (antibiotic, 74%) and
321 acetaminophen (analgesic, 83%), as expected, have significantly low log Kow value (0.9 and 0.5
322 respectively). In addition to low hydrophobicity, both of these PPCPs also remains predominantly
323 as neutral species in the experimental pH range (~3), further negating any possibility for
324 electrostatic intercation with charged adsorent surface.75-77
325 However, despite having the lowest log Kow value, caffeine showed significantly high
326 removal percentage (93%) when adsorbed by the rGO-nZVI NH. Electronegative nitrogen and
327 oxygen atoms present in caffeine induce polarity even in its neutral form (pKa ~ 10.4) causing
328 electrosataic interaction with rGO-nZVI NH.78, 79 Additionally, the presence of nitrogen atom in
329 aromatic ring also facilitates π- π electron donor-acceptor interaction with NH resulting in
330 significantly high removal of caffeine.31, 80 This suggests that other adsorption mechanisms (e.g.,
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331 electrostatic and π-π electron donor acceptor interaction, hydrogen bond), in addition to the
332 hydrophobic interaction, can contribute to PPCP removal by the rGO-nZVI NH. In the case of

333 SSRIs i.e., for citalopram, paroxetine, and fluoxetine, along with their relatively high logKow value,
334 the presence of 3, 4, and 5 hydrogen bond acceptors, respectively, (identified with black dots in
335 respective chemical structures in Figure S3) can contribute to adsorptive removal due to the
336 formation of hydrogen bond with functional groups of rGO-nZVI NH.81-83 Additionally, these
337 three SSRIs – citalopram, paroxetine, and fluoxetine, unlike other PPCPs in the matrix, have 1, 1,
338 and 3 highly electronegative fluorine atoms, respectively (as shown in Figure S3), which facilitate
339 higher electrostatic interaction with NH compared to other PPCPs not containing fluorine,
340 ultimately resulting in high removal efficiency ( > 98%).84
341 3.2.2. AOP augmented adsorptive removal of PPCPs
342 To evaluate the synergistic adsorptive and AOP based removal of the PPCPs by the rGO-nZVI
343 NH and parent nanomaterials, similar removal tests were carried out in the presence of H2O2 (15.6
344 µL, 28-30%). Figure 3b and Table S2 presents the results for PPCP removal using this AOP
345 augmented adsorption. nZVI (present in the NH or bare) works as a heterogeneous Fenton catalyst
346 for activating H2O2 to generate reactive oxygen species (e.g., hydroxyl radical (•OH)), which can
347 further augment PPCP removal by oxidative degradation in addition to adsorption.32, 51 We found
348 that rGO with H2O2 performed PPCP removal in the range of 3-73%, with similar removal for
349 individual PPCPs compared to only rGO, confirming the absence of any Fenton catalytic activity.
350 Bare nZVI, as a heterogeneous Fenton catalyst in the presence of H2O2, showed significant
351 increase ( ≥ 10% removal) in removal only for ibuprofen and acetaminophen compared to without
352 addition of H2O2. The highest removal of ~22% with bare nZVI with H2O2 for acetaminophen can
353 be accounted only for oxidative degradation, as bare nZVI did not show any adsorptive removal
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354 for acetaminophen. The rGO-nZVI NH showed the best PPCP removal performance for AOP
355 augmented adsorption process, with more than 93% removal for all the PPCPs, which ranged upto

356 20% higher than only adsorptive removal of PPCPs by the rGO-nZVI NH (Figure S5). In the case
357 of sulfamethoxazole, which was least removed in case of only adsorption by rGO-nZVI NH, the
358 removal percentage increased by 20% in AOP augmented condition. This can be attributed to the
359 isoxazole ring of sulfamethoxazole structure, which is susceptible to degradation under •OH
360 attack.85 However, bare nZVI, as Fenton catalyst in presence of H2O2, could not improve
361 sulfamethoxazole removal compared to only adsorptive removal performed in absence of H2O2.
362 This indicates better Fenton catalytic activity of nZVI when hybridized on graphene support. The
363 other PPCPs in the mixture are also susceptible to •OH, which initiates degradation through
364 subsequent hydroxylation and decarboxylation reaction pathways.86-89 This resulted in enhanced
365 removal of PPCPs in AOP augmented condition by the rGO-nZVI NH. However, for bare nZVI,
366 the overall removal efficiency across all PPCPs was still less than 25% in AOP augmented
367 condition. The limited catalytic performance of bare nZVI compared to rGO-nZVI NH can be
368 attributed to aggregation, passive oxide layer formation and, moreover, absence of synergistic
369 adsorption by a support medium.90, 91
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370
371 Figure 3. (a) Adsorptive and (b) AOP augmented adsorptive removal of PPCPs by rGO-nZVI NH
372 and parent nanomaterials rGO and nZVI after 30 minutes.
373 3.3 PPCP removal kinetics for rGO-nZVI NHs and their parent nanomaterials
374 To determine the PPCP removal kinetics for parent nanomaterials and rGO-nZVI NH, a second
375 set of PPCP removal tests were carried out using a mixture of six PPCPs which included 3 SSRIs:
376 citalopram, paroxetine, and fluoxetine; 1 NSAID: diclofenac; 1 anti-seizure: carbamazepine; 1
377 antibiotic: sulfamethoxazole. This subset of PPCPs were selected from the first set, keeping
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378 PPCPs from different classes and including the three SSRIs. To evaluate and compare the kinetic
379 performance, the removal of PPCPs after first 10 minutes by the nanomaterials are reported in

380 Figure 4 (also in Table S2). These confirm the faster removal kinetics for NH compared to the
381 parent nanomaterials for both adsorptive (Figure 4a) and AOP augmented adsorptive (Figure 4b)
382 removal. Furthermore, a significant increase in removal efficiency (27-58 %) across all the 6
383 PPCPs at 10 minutes can be observed for rGO- nZVI NH with H2O2 compared to only rGO-nZVI
384 NH. For the adsorptive removal of 6 PPCPs without H2O2, 52-77% of the total removal occurred
385 in the first 10 minutes, whereas the removal percentage was 94-100% in case of AOP augmented
386 adsorption condition after 10 minutes. This confirms, in AOP augmented condition, synergistic
387 adsorption and advanced oxidation is taking place simultaneously, which is enabling faster
388 removal kinetics for the rGO-nZVI NH compared to only adsorptive removal. As far as the
389 removal efficiency is concerned after 30 minutes, for both adsorptive and AOP augmented
390 adsorptive removal, rGO-nZVI NH performed significantly better than the parent nanomaterials
391 (Figure S6 (a) and (b)) which is similar to the results for the first set of PPCPs (12 PPCPs).
392 However, for this smaller set of 6 PPCPs, the parent nanomaterials seem to perform better
393 compared to their performance for the larger set of 12 PPCPs due to less competition for removal.
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394
395 Figure 4. (a) Adsorptive and (b) AOP augmented adsorptive removal of PPCPs by rGO-nZVI NH
396 and parent nanomaterials rGO and nZVI after 10 minutes.
397 To further evaluate the time dependent performance of the nanomaterials, the PPCP
398 removal was reported through kinetic plots at 5 minute time intervals over 30 minutes (Figures 5
399 and S7). The kinetic plots for two PPCPs, fluoxetine (a representative of SSRI group) and
400 sulfamethoxazole (antibiotic, which had the least removal in the first set of experiments) are
401 reported in Figure 5 and the rest are in the electronic supplementary information (Figure S7). Each
402 row in these figures presents removal kinetics results for one specific PPCP. In each row of Figures
403 5 and S7, the left and middle figures present the results of PPCP removal kinetics, respecitively,
404 by adsorptive (only) and AOP augmented adsorption for all three nanomaterials i.e., rGO, nZVI,
405 and rGO-nZVI NH. The right figure in each row presents the comparison between PPCP removal
406 kinetics by adsorption (only) and AOP augmented adsorption for the rGO-nZVI NH. For all the
407 6 PPCPs, parent nanomaterials showed slower kinetics compared to the rGO-nZVI NH for both,
408 adsorptive and AOP augmented adsorptive condition, over the entire period of 30 minutes. For
409 example, under adsorptive (only) condition, parent nanomaterial rGO could remove ~85% of
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410 paroxetine at the end of 30 minutes which was relatively close to the removal performance by NH
411 (~100%). However, the kinetics was much faster for the rGO-nZVI NH, as the removal by NH

412 was 75% in the first 5 minutes, whereas that by rGO was only 38%. In case of AOP augmented
413 condition, paroxetine and diclofenac seem to be more prone to oxidative degradation, as
414 significantly high removal of these two PPCPs was possible by bare nZVI (74% and 99%
415 respectively), although less compared to the rGO-nZVI NH (~100%). However, NH with H2O2
416 still exhibited faster removal kinetics for these two PPCPs compared to bare nZVI, with all the
417 100% removal in the first 5 minutes compared to 27% and 21% removal respectively by nZVI.
418
419 Figure 5. Kinetics of (a, d) adsorptive (only) and (b, e) AOP augmented adsorptive removal of
420 PPCPs by parent nanomaterials and rGO-nZVI NH; (c, f) Comparison of PPCP removal by rGO-
421 nZVI NH via adsorption (only) and AOP augmented adsorption for fluoxetine and
422 sulfamethoxazole.
423 To further quantify the removal kinetics, the rate constants for individual PPCP removal
424 by both the adsorption (k1) and AOP augmented adsorption (k2) by rGO-nZVI NH were estimated
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425 considering both processes as pseudo-first order reaction since the R2 values suggested better
426 conformity to pseudo-first order reaction than any other reaction order. However, deviation from

427 exact conformity to pseudo-first order reaction rate constant (i.e., low R2 values) in case of few
428 PPCPs can be attributed to various reasons including the presence of multiple PPCPs in the
429 mixture.52, 92-94 Moreover, the adsorbate sample collection, processing, and analyses within an
430 interval shorter than 5 minutes was significantly challenging (for multiple NH-PPCP
431 combinations) which may have contributed to the low R2 values as well. The rate constants along
432 with the R2 values are shown in Table 2 and Figure S8. The reaction rate constants for AOP
433 augmented adsorption by rGO-nZVI NH was ~3-5.5 times higher than that for only adsorption for
434 individual PPCPs (Table 2). This can be attributed to the effect of heterogeneous Fenton catalysis,
435 which further illustrates the merit of synergistic AOP augmented adsorptive removal of PPCPs.
436
437 Table 2. Rate constants for individual PPCP removal by adsorption (red) and AOP augmented
438 adsorption for rGO-nZVI NH.
Citalopram Paroxetine Fluoxetine Diclofenac Carbamazepine Sulfamethoxazole

Pseudo First Order
Rate Constant, 0.16 0.21 0.16 0.17 0.09 0.06
kNH (min-1)
R2 0.93 0.96 0.98 0.98 0.97 0.99
Pseudo First Order
Rate Constant, 0.88 0.87 0.61 0.51 0.35 0.27
kNH + H2O2 (min-1)
R2 0.79 0.88 0.27 0.98 0.85 0.98
kNH + H2O2 / KNH 5.50 4.14 3.81 3.00 3.89 4.50
439
440
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441 3.4 Mechanism of AOP augmented adsorption: H2O2 activation
442 To better comprehend the enhanced performance of rGO-nZVI NH in AOP augmented condition,

443 we quantified residual H2O2 concentration with time in similar batch test in presence of all these
444 nanomaterials individually to analyze their catalytic property (Figure 6). AOP based contaminant
445 degradation (including PPCPs) are known to be caused by reactive oxygen species (ROS)
446 generated through activation of H2O2 in the presence of homo- or heterogeneous catalysts.32, 95, 96
447 These ROS may include super oxide radical anion (O2·-), hydroperoxyl radical (HO2·), and ·OH
448 radical.97, 98 We found that in the case of control (without any nanomaterial) and rGO, there was
449 no H2O2 decay, suggesting no catalytic activation of H2O2 to form various ROS. However, both
450 nZVI and rGO-nZVI NH showed H2O2 decay over time confirming the presence of catalytic
451 activation of H2O2. While the rGO-nZVI NH showed a high H2O2 decay (82%) over 30 minutes
452 with the fastest kinetics, nZVI showed a steady decay of H2O2 reaching 49% decay at the end of
453 30 minutes. This suggests that the rGO-nZVI NH could perform catalytic oxidation much faster
454 and better than the parent nanomaterials which may have resulted in better and faster PPCP
455 removal by the rGO-nZVI NH mediated AOP augmented adsorption, as shown above.
456
457 Figure 6. H2O2 decay over time by rGO-nZVI NH and parent nanomaterials rGO and nZVI.
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458 It is also important to note that both the adsorption and AOP processes in this study was
459 performed at pH 3. We did this because pH 3 has been described as the most favorable operating

460 conditions for both homo- and heterogeneous Fenton reactions in the literature.32, 56, 99 Most
461 previous studies involving nZVI as heterogeneous Fenton catalyst have shown better catalytic
462 performance at pH 3 than at neutral and alkaline pH.32, 56, 99 There are several reasons for such
463 behavior of nZVI catalyst. Firstly, at low pH, Fe0 at the nZVI surface reacts with H2O2 or O2
464 present in water via a two-electron transfer process to continuously generate surface bound Fe2+
465 ions, which further reacts with H2O2 to generate ROS and Fe3+.99-102 Moreover, the nZVI core
466 (Fe0) can transfer electron to the oxidized Fe3+ ions at the nZVI surface to repeat the cycle of Fe2+
467 generation on the surface and can continuously generate ROS.51, 103 Overall, this leads to relatively
468 higher H2O2 activation and more ROS formation by nZVI based catalysts at acidic pH (as shown
469 in the following equations) than at alkaline pH.
470 Fe0 + H2O2 + 2H+ → Fe2+ + 2H2O
471 Fe0 + O2 + 2H+ → Fe2+ + 2H2O2
472 Fe2+ + H2O2 → Fe3+ + •OH + OH−
473 2 Fe3+ + Fe0 → 3Fe2+
474 Moreover, at alkaline pH, the Fe2+/Fe3+ ions generated from nZVI convert into passive iron
475 oxides (e.g., Fe(OH)3, FeOOH) either at nZVI surface or as precipitates.100, 104 Acidic pH inhibits
476 such nZVI passivation which in turn resulting in better performance of nZVI catalyst. This
477 phenomenon can also be observed in case of homogenous Fenton processes (that involves Fe2+
478 ions), making acidic pH (̴ 2.8-3.2) favorable operating condition.105-107
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479 3.5 Hybridization induced enhancement in PPCP removal performance of rGO-nZVI
480 NH

481 To further elucidate the synergistic effect of hybridization, similar removal tests with mixture of
482 parent nanomaterials were carried out. The mixture contained 1.9 mg of rGO and 6.1 mg of nZVI
483 to match the ratio (~1:3.2) of these nanomaterials in the synthesized rGO-nZVI NH. This mixture
484 of rGO and nZVI were also tested for removal of the same 6 PPCPs in the presence and absence
485 of H2O2 and compared with the performance of equivalent dose of rGO-nZVI NH (Figure 7).
486 Overall, the nanomaterial mixture showed limited PPCP removal when compared to the removal
487 performance by the rGO-nZVI NH. In case of solely adsorptive removal of these PPCPs, removal
488 percentage by rGO-nZVI NH was 66- 88% higher than the removal by the nanomaterial mixture.
489 Similarly, for AOP augmented adsorptive removal, the difference in removal performance was
490 56%, 57%, 60%, and 54% in favor of the rGO-nZVI NH for citalopram, fluoxetine,
491 carbamazepine, and sulfamethoxazole, respectively. However, for paroxetine and diclofenac, the
492 mixture with H2O2 itself can remove 87% and 98% respectively comparable to the ~100% removal
493 by the rGO-nZVI NH. These two PPCPs are highly susceptible to oxidative degradation as already
494 observed in the removal test with bare nZVI with H2O2 (Figure S7), removing 75% and 99% of
495 the initial concentration respectively. This indicates the nZVI alone can be attributed to the high
496 removal of paroxetine and diclofenac by the parent nanomaterial mixture.
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497
498 Figure 7. Comparative PPCP removal by rGO-nZVI NH and mixture of parent nanomaterials rGO
499 and nZVI.
500 Kinetic tests were also carried out with the mixture of parent nanomaterials. The kinetic
501 test further showed that the hybridization triggered faster PPCP removal kinetics than the mixture
502 of parent nanomaterials. The kinetic plots for fluoxetine and sulfamethoxazole are reported in
503 Figure 8, the rest are shown in Figure S9.
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504
505 Figure 8. Comparative kinetics of (a, c) adsorptive, (b, d) AOP augmented adsorptive removal by
506 rGO-nZVI NH and mixture of rGO and nZVI for fluoxetine and sulfamethoxazole.
507 4. Conclusion
508 In this study, we used rGO-nZVI NH to remove a complex matrix of PPCPs including novel
509 antidepressants that are found in trace (ppb level) concentrations within wastewater treatment
510 plants. We compared the ability of rGO-nZVI NH to enhance PPCP removal efficiencies and
511 kinetics via two water treatment methods, i.e., adsorption and AOP. We found that rGO-nZVI NH
512 can significantly enhance the PPCP removal via these processes when compared to its parent
513 materials rGO and nZVI. Moreover, synergistic AOP augmented adsorption process showed much
514 better (more than 93% removal efficiency) and faster PPCP removal for almost all of the PPCPs
515 than only adsorption process when rGO-nZVI NH was used. We also found that the differences
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516 in removal efficiencies between individual PPCPs within the mixture was caused by their
517 competitive adsorption that depended upon their individual chemical nature and differences

518 between hydrophobic and electrostatic interactions with the rGO-nZVI NHs. The results of this
519 study are very encouraging and have important implications for de facto potable water reuse,
520 majorly within an urban/industrial water infrastructure. The high efficiency and fast kinetics for
521 PPCP removal reveals the potential of utilizing rGO-nZVI NH at point of high concentration
522 emission (e.g., hospital, pharmaceutical industry effluent) and even at point of use/entry at the user
523 end to mitigate the huge risk associated with PPCP contaminated water. Moreover, rGO-nZVI
524 NH mediated AOP can be included within the already existing municipal wastewater treatment
525 train possibly right before the biological wastewater treatment processes, since rGO-nZVI NH has
526 the potential to breakdown the recalcitrant PPCPs, through heterogeneous Fenton catalysis, to non-
527 aromatic small-chain organic acids108 which can be further mineralized by microbes. However,
528 for achieving this, identifying the PPCP degradation products for rGO-nZVI NH based AOP and
529 understanding associated by-product toxicity to aquatic organisms and microbes will be important.
530 These product identification and toxicity studies can only be performed using individual PPCPs
531 instead of using PPCP mixture due to technical challenges associated with correlating and
532 connecting degradation products with their respective source PPCPs within a mixture.
533 Conflict of Interests
534 The authors declare no conflict of interest.
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or omissions in this Accepted Manuscript or any consequences arising

Water Impact Statement

Environmental Science: Water Research & Technology Accepted Manuscript

Environmental Science: Water Research & Technology Accepted Manuscript

9 University of New York, Buffalo, NY 14260

12 Environmental Science: Water Research & Technology

26 * Corresponding Author: Nirupam Aich, Phone: 716-645-0977, Email: nirupama@buffalo.edu

Environmental Science: Water Research & Technology Accepted Manuscript

36 antibiotic, anti-inflammatory, anti-seizure, and antidepressant pharmaceuticals, and are

38 environmentally relevant concentrations at ppb level. The rGO-nZVI NH synergistically

46 potential of utilizing rGO-nZVI NH in drinking/wastewater treatment system, or even in point-of-

Environmental Science: Water Research & Technology Accepted Manuscript

61 developmental and reproductive disorder, endocrine disruption.17, 18 Moreover, drinking water

Environmental Science: Water Research & Technology Accepted Manuscript

82 property by providing fast electron transfer38, 39 and resisting nZVI aggregation.36

97 SNRIs (Serotonin-Norepinephrine Reuptake Inhibitors), antibiotics, anti-seizure, and NSAID

Environmental Science: Water Research & Technology Accepted Manuscript

102 during adsorption and AOP.

111 spectroscopy, thermogravimetric analysis (TGA), and Fourier-transform infrared (FTIR)

118 2. Materials and methods

119 2.1 Chemical and Reagents

Environmental Science: Water Research & Technology Accepted Manuscript

124 acetaminophen (ACT), caffeine (CAF), carbamazepine (CBZ), carbamazepine-d10, citalopram

134 Sigma Aldrich (St Louis, MO) respectively.

135 2.2 Synthesis and characterization of nanohybrids

139 ultrasonic dismembrator (Q700, Qsonica Sonicators, Newtown, CT). Subsequently, 1 g

Environmental Science: Water Research & Technology Accepted Manuscript

152 salt, 20 mL 1.32 M NaBH4 was used under N2 gas flow.

Environmental Science: Water Research & Technology Accepted Manuscript

172 2.3 PPCP removal experiments

Environmental Science: Water Research & Technology Accepted Manuscript

204 µg/L) prior to LC-MS/MS analysis.

206 in batch reactions through DPD colorimetric method.59

207 2.4 LC-MS/MS analysis of PPCPs

Environmental Science: Water Research & Technology Accepted Manuscript

223 transitions are listed in Table 1.

224 Table 1. Target Analytes and LC/MS/MS parameters.

Environmental Science: Water Research & Technology Accepted Manuscript

226 3. Results and Discussion

227 3.1 Physicochemical properties of rGO-nZVI NHs and parent nanomaterials

Environmental Science: Water Research & Technology Accepted Manuscript

239 prevention of nZVI aggregation by the rGO nanosheets.

Environmental Science: Water Research & Technology Accepted Manuscript

Environmental Science: Water Research & Technology Accepted Manuscript

Environmental Science: Water Research & Technology Accepted Manuscript

277 to our previous study.61

280 nanomaterials rGO and nZVI.

282 3.2.1. Adsorptive removal of PPCPs

Environmental Science: Water Research & Technology Accepted Manuscript

304 equilibrium time of upto 24 hours.52

Environmental Science: Water Research & Technology Accepted Manuscript

324 electrostatic intercation with charged adsorent surface.75-77

Environmental Science: Water Research & Technology Accepted Manuscript

340 ultimately resulting in high removal efficiency ( > 98%).84

341 3.2.2. AOP augmented adsorptive removal of PPCPs

Environmental Science: Water Research & Technology Accepted Manuscript