Environmental Research 183 (2020) 109205

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Environmental Research
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Short communication

Iron foam combined ozonation for enhanced treatment of pharmaceutical T

wastewater
Yuanxing Huanga, Jiewen Jianga, Luming Mab, Yaowei Wanga, Manli Lianga, Zhiguo Zhanga,
Liang Lia,∗
a
School of Environment and Architecture, University of Shanghai for Science and Technology, No. 516 Jungong Rd., Shanghai, 200093, PR China
b
Department of Environmental Science and Engineering, Tongji University, Shanghai, 200092, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, iron foam combined ozonation was employed as an advanced oxidation process to treat the organic
Iron foam contaminants in real pharmaceutical wastewater. It was found that this procedure worked well in a wide range
Ozonation of pH, the existence of iron foam in ozonation system markedly elevated the mineralization level of organic
Pharmaceutical wastewater contaminants. Within the reaction time of 120 min, iron foam combined ozonation achieved 53% of DOC re-
moval percentage, which was 21% higher than that of ozone alone. Meanwhile, the biodegradability of the
pharmaceutical wastewater was improved, a large part of the organic pollutants containing benzene rings and
amino groups were effectively degraded, and a certain amount of phosphate and nitrogen also get removed. In
iron foam combined ozonation, zero valent iron played the role as an activator. It was oxidized into iron oxides
and oxyhydroxides, the electrons transferring among different valences of iron stimulated the decomposition of
ozone and the generation of hydroxyl radicals, which accounted for most of the organic contaminants de-
gradation.

1. Introduction wastewaters, the traditionally employed treatment methods were bio-

logical processes that including anaerobic and aerobic systems. How-
During the manufacture of pharmaceutical products, for instance, ever, many recalcitrant and refractory compounds present in pharma-
antibiotics, betablockers, blood lipid-lowering agents, antihistamines ceutical wastewaters could hardly be efficiently eliminated, for these
and hormones, multifarious organic and inorganic constituents in- compounds often impede the ordinary metabolic function of micro-
cluding ingredients, solvents, additives and reactants were involved in organisms (Ng et al., 2016). As a consequence, researchers began to cast
the process water, feed water, or cooling water, and finally mixed and eyes over some non-biological treatments, such as adsorption, ozona-
discharged as pharmaceutical wastewaters (Gadipelly et al., 2014; Kaya tion, Fe3+/CaO2 system, Fenton-like reaction and other advanced oxi-
et al., 2017). These generated wastewaters were featured with en- dation processes (AOPs), which presented great potential for treating a
ormous volume, complex and hazardous nature, and had very high wide range of emerging contaminants (Kanakaraju et al., 2018; Lester
chemical oxygen demand (COD), biological oxygen demand (BOD), and et al., 2013; Lu et al., 2020; Wang et al., 2019; Zhou et al., 2019).
solid contents (Changotra et al., 2019). Markedly high concentrations Ozonation and combinations of ozone with hydrogen peroxide, ul-
of diverse pharmaceutical residues were found in these wastewaters. traviolet radiation, or solid catalysts have been extensively applied to
The rapid development of pharmaceutical industry has made pharma- the removal of pharmaceuticals from water as a chemical oxidation
ceutical wastewater a serious source of water pollution, and the process, and they were proved to be fairly effective (Dai et al., 2014;
awareness regarding the detrimental impact of pharmaceutical waste- Gomes et al., 2017; Huang et al., 2019a). The use of heterogeneous
water has grown copiously. solid materials was an especially interesting approach to enhance the
The national regulations required that these pharmaceutical was- ozone action over organic pollutants by improving mineralization and
tewaters be treated at the manufacturing plant prior to discharge to easy separation from the aquatic phase (Gomes et al., 2017; Kasprzyk-
reduce the environmental load of pollutants (China, 2008). For these Hordern et al., 2003). Among the solid materials, the transition metals

∗
Corresponding author. School of Environment and Architecture, University of Shanghai for Science and Technology, No. 516 Jungong Rd., Shanghai, 200093, PR
China.
E-mail addresses: [email protected] (Y. Huang), [email protected] (J. Jiang), [email protected] (L. Ma), [email protected] (Y. Wang),
[email protected] (M. Liang), [email protected] (Z. Zhang), [email protected] (L. Li).

https://doi.org/10.1016/j.envres.2020.109205
Received 25 October 2019; Received in revised form 27 December 2019; Accepted 30 January 2020
Available online 31 January 2020
0013-9351/ © 2020 Elsevier Inc. All rights reserved.
Y. Huang, et al. Environmental Research 183 (2020) 109205

as well as their oxides or alloys have attracted many attentions, and into the reactor, with stirring the ozone gas was bubbled from the
iron was one of the most frequently used metals (Huang et al., 2015; bottom into the reactor continuously during the whole ozonation pro-
Wang and Bai, 2017; Wu et al., 2016; Zhao et al., 2013). Nevertheless, cedure, and the escaped ozone gas was trapped by KI solution. The
the majority of these works were confined to laboratories, only a small sampling frequency was 20 min and the residual ozone was quenched
part of these studies have evaluated their potential to treat real was- by helium gas.
tewater directly from chemical industries.
Core-shell zero-valent iron, micro-sized iron powder and iron cov- 2.3. Analytical and characterization methods
ered with iron oxides were the frequently used forms as heterogeneous
catalyst (Sun et al., 2016; Xiong et al., 2016, 2018), but the application The soluble chemical oxygen demand (sCOD), dissolved total or-
of its porous form as three-dimensional iron foam was sparsely re- ganic carbon (DOC) and 5-day biochemical oxygen demand (BOD5) of
ported, despite its excellent properties in terms of permeability, con- the water samples were measured to monitor the organic matters. Other
trolled pore size, shape stability, thermal shock resistance and ma- parameters of total nitrogen (TN), NH4+-N, NO3− −
- N, NO2- N, and total
chinability (Deng et al., 2018). In one of our previous researches, phosphate (TP) were detected to characterize the water quality. The
ozonation process with iron-nickel foam was employed on the treat- measurement methods were referring to the Monitoring and Analysis
ment of real petrochemical wastewater, which have successfully Methods for Water and Wastewater (China, 2002). UV254 of the water
speeded up the mineralization of target organic pollutants (Huang sample was detected by spectrophotometer (UV2600, Shimadzu,
et al., 2019a). Besides the catalytic effect, iron-nickel foam could en- Japan). The ozone concentrations in the water samples were quantified
hance the ozone utilization efficiency by prolonging the residence time immediately after sampling via indigo colorimetric method (APHA,
of ozone in water. In this context, meanwhile considering the activity, 2005). The dissolved iron in the water were measured by an Inductively
mechanical strength, recovery mode and the cost of the solid material, Coupled Plasma Mass Spectrometry (ICP-MS, NexION 300, Perki-
we chose iron foam to combine with ozonation to treat real pharma- nElmer, USA).
ceutical wastewater. Hence the main objectives of the present study are: The pH of water samples was adjusted to 2, 7 and 11, respectively,
and the compositions of organic matters were extracted out through
(1) Demonstrate the feasibility of iron foam combined ozonation in liquid–liquid extraction with dichloromethane as solvent (China, 2002).
removing the main recalcitrant organic contaminants in real was- Then the organic species in the solvent were detected by Gas Chro-
tewater from a pharmaceutical manufacturing factory; matograph (GC, 7890 A, Agilent, USA) coupled Mass Spectrometer (MS,
(2) Investigate the impact of operation parameters, explore the 5975C, Agilent, USA) with capillary column (HP-5MS,
working mechanism of the iron foam/ozonation combination pro- 30 m × 250 μm × 0.25 μm). The GC/MS program was run as fol-
cess in removing the target contaminants. lowing: 1 μL sample was injected in splitless mode with an inlet tem-
perature of 260 °C, carrying gas ultrapure helium flowed with rate
2. Materials and methods 1 mL min−1, the initial oven temperature was 100 °C, then increased to
260 °C at 10 °C/min and kept for 2 min, subsequently increased to
2.1. Chemicals 290 °C at 3 °C/min and kept for 2 min. The mass spectra were run in
scan mode from 20 to 550 m/z.
The bulk iron foam (porosity 98%, density 0.2 g cm−3) was from The iron foam corrosion products participated during ozonation
Jiayisheng Electronics Co., Ltd (Kunshan, China). The average pore were filtrated, then rinsed with deionized water and finally dried by
numbers were 40 PPI (number of pores per inch) with a diameter of vacuum freeze drying. The following techniques were used to char-
0.25–1.0 mm. Each cylinder-shape iron foam has a height of 10 mm and acterize the corrosion product: The infrared spectra of the corrosion
a basal diameter of 70 mm. Before use it was soaked in NaOH product were obtained by Fourier transform infrared spectroscopy (FT-
(1.0 mol L−1) for 24 h, and using deionized water to rinse it till the IR, Tensor27, BRUKER, Germany). An X-ray Photoelectron
eluent was neutral, then it was soaked in the solvent of di- Spectroscopy (XPS, Amicus, Shimadzu, Japan) was used to determine
chloromethane for 10 min to clean the possible organic impurities, and its surface elements chemical states; The scanning electron microscopy
soaked in HCl (0.1 mol L−1) for 10 min, rinsed by deionized water (SEM) (S-4800, Hitachi, Japan) was used to visualize its surface mor-
again and finally dried under 50 °C in oven. phology.
The actual pharmaceutical wastewater was taken from a pharma- To determine the generation of hydroxyl radicals (%OH) in iron
ceutical manufacturing factory located in Jiangsu Province after bio- foam combined ozonation system, the trapper of dimethyl sulfoxide
logical treatment processes. To alleviate the biodegradation of organics (DMSO) was induced to react with %OH to generate formaldehyde,
by bacteria, it was filtered and then stored in a 4 °C refrigerator. Before which further reacted with 2,4-dinitrophenylhydrazine (DNPH) to form
ozonation experiments, the stored wastewater was taken out and kept DNPH-HCHO (Fukui et al., 1993). Using high performance liquid
in the lab till it reached room temperature (15–20 °C). Deionized water chromatography (HPLC) (Waters, e2695, USA) and UV–Visible detector
was used to prepare all the other water solutions. The reagent po- (Waters, 2489, USA), DNPH-HCHO could be quantitatively analyzed.
tassium indigo trisulfonate (> 99%) were purchased from Supelco Co., The set program was as following: column: (Atlantis, T3, Waters, USA);
Ltd. (PA, USA). Other chemicals were from Sinopharm Chemical mobile phase: methanol-water (80: 20, v/v); wavelength: 355 nm
Reagent Co., Ltd. (Shanghai, China), all was of analytical grade and (Huang et al., 2019b; Tai et al., 2004). Electron paramagnetic re-
used as received without further purification. sonance (EPR, EMX-8, Bruker, Germany) experiments were conducted
with 50 mM 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) as spin-trap-
2.2. Ozonation treatment of pharmaceutical wastewater ping agent.

The ozonation was performed in a 2.5 L glass reactor with an inner 3. Results and discussion
diameter of 70 mm under the temperature of 15–20 °C. The ozone gas
(1%, V/V) was produced from an ozone generator (KX-S10, Kangxiao 3.1. Improvement of organic contaminants removal in pharmaceutical
Environment Protection Equipment Co., Ltd., Shanghai, China) with wastewater by iron foam combined ozonation and the influence of radical
oxygen as the feeding gas, and then introduced into the reactor through inhibitors
a sintered-glass diffuser. The initial bubble size was within the range of
1.0–3.0 mm and could grow larger in the reactor. To begin with, 2.0 L Heretofore limited research has been carried out on the removal of
pharmaceutical wastewater and certain dosages of iron foam were put organic contaminants from real pharmaceutical wastewater through the

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Y. Huang, et al. Environmental Research 183 (2020) 109205

observe their impact.

HPO42− was able to occupy the active sites on solid catalyst surface
through strong bonding with the Lewis acid sites, it could also scavenge
%OH due to the following reactions (1) (k < 107 M−1s-1) and (2)
(k < 105 M−1s−1) (Kasprzyk-Hordern et al., 2003; Lv et al., 2010).
HCO3− reacted with %OH in the bulk solution very rapidly as in
equation (3) (k = 1.5 × 107 M−1s−1) and (4)
(k = 4.2 × 108 M−1s−1), so as to quench their action effectively
(Kasprzyk-Hordern et al., 2003).

%OH + HPO42− → OH− + H2PO4− (1)

%OH + H2PO4− → OH −
+ H2PO4% (2)
− −
%OH + HCO3 → OH + HCO3% (3)
−
%OH + CO32− → OH + CO3% -
(4)

The results of Fig. 1 indicated that the decomposition of ozone was

obviously depressed by both HPO42− and HCO3−. With the HPO42−
and HCO3− concentration increasing, the decomposition rate of ozone
decreased, and the organic contaminants removal dropped nearly to
that one in ozone alone. It is evident that considerable amount of %OH
were formed in the ozone/Fe foam system. To further elucidate the
action of active species, molecular probe dimethyl sulfoxide (DMSO)
was used to detect the formation of %OH quantatively. Fig. 2(a) pre-
sented the accumulative %OH quantity in both ozone alone and ozone/

Fig. 1. Influence of radical inhibitors on the reduction of organics in pharma-

ceutical wastewater: (a) DOC; (b) sCOD. Aqueous ozone concentration: 9.0 mg
L−1; Fe foam dosage: 80 g L−1; initial DOC: 40–50 mg L−1; initial sCOD:
120–150 mg L−1; initial pH: 8.4.

combination of ozone and iron foam. To assess the performance of iron

foam in ozonation process and understand the working mechanism, a
series of comparative tests were designed and conducted, in which the
degradation and mineralization of organic contaminants in real phar-
maceutical wastewater were examined.
The obtained results in Fig. 1 showed that inspite of its high por-
osity, the adsorption of organic matters by iron foam in absence of
ozone was very weak. When iron foam worked together with ozone, the
removal of organic matters reached the highest point of 53% in the case
of DOC removal at the reaction time of 120 min, while ozone alone
removed just 32% of the DOC, as in Fig. 1 (a). For sCOD removal,
ozone/Fe foam process reached 73% organic removal and ozone alone
treatment obtained almost the same level of contaminant removal, as
shown in Fig. 1 (b).
These results certified the higher mineralization performance of
ozone/Fe foam process, and exhibited a synergetic effect between iron
foam and ozone. According to many literatures, the enhanced ozone
oxidation was attributed to catalytic ozonation, and the elevated or-
ganic contaminant removal was due to the generation of stronger oxi-
dative species via decomposition of ozone during the process
(Kasprzyk-Hordern et al., 2003; Kolosov and Yargeau, 2019; Wang and
Fig. 2. The determination of hydroxyl radicals by: (a) HPLC quantification
Bai, 2017; Wu et al., 2016). To verify the role of active radicals, two
(DMSO: 250 mM; aqueous ozone concentration: 9.0 mg L−1; Fe foam dosage:
inhibitors - HPO42− and HCO3− were added into the reaction system to
80 g L−1); (b) EPR test (DMPO: 50 mM; Fe foam dosage: 2.0 g L−1).

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Y. Huang, et al. Environmental Research 183 (2020) 109205

Fe foam systems, it indicated that in ozone alone system, the accumu- corrosion products. In Fig. 3 (c) and (d), XPS results of the original iron
lative %OH amount was 31 μmol at the reaction time of 60 min, while in foam surface showed that there was some iron oxides covered on the
ozone/Fe foam system, the accumulative %OH amount reached 98 μmol surface, which might be formed through slow oxidation in the air
under the same condition. So from the above results, the existence of % (Yamashita and Hayes, 2008).
OH in the ozonation systems could be definitely confirmed. EPR test From FT-IR spectra in Fig. 4 (a), the features of functional groups on
was also performed to monitor the generation of %OH during ozonation. iron foam surface after ozonation could be derived. The absorption
As shown in Fig. 2(b), clear DMPO-OH signals were observed in the peak at a broad wave number near 3400 cm−1 was generally attributed
ozone/Fe foam system, which was consistent with the results reported to the stretching vibration of O–H stretching bands arising from metal-
in a previous study (Li et al., 2018). hydroxyl groups, the peak at around 1600 cm−1 was corresponding to a
H2O deformation from the water molecules attached on the surface of
3.2. The characterization of ozonized iron foam corrosion products and the iron corrosion products, the peak observed at 630 cm−1 could be as-
working mechanism of iron foam in ozonation signed to cation-oxygen vibrations (Li et al., 2004). On the other side,
no obvious FT-IR signal was observed for raw iron foam as shown in
Iron foam can be easily oxidized by ozone, thus the formed products Fig. 4 (c).
need to be tested to investigate its influence on ozonation. By using ICP- The surface morphologies of iron foam after ozonation obtained by
MS, 93 μg/L of additional dissolved irons were detected out after ozo- SEM was displayed in Fig. 4 (b), revealing a rough surface dispersed
nation for 120 min, which might mostly exist in the form of Fe3+ since with schistose crystals, which was attributed to the formation of a
ozone is a strong oxidizing reagent with a standard oxidation potential complex mixture of amorphous and crystalline iron oxides and oxy-
of +2.07 V. Moreover, solid iron corrosion products were continually hydroxides such as iron oxides, hydroxides and hydroxyoxides on iron
formed and covered on the iron foam surface. Interpreting the com- foam surface. As shown in Fig. 4 (d) (SEM) and Fig. S1 (photo), the
position of these corrosion products would help to interpretate the role surface of raw iron foam was observed to be relatively smooth.
of iron foam in ozonation. XPS spectra of the iron foam corrosion Given the mechanisms of organic contaminants removal by iron
products in Fig. 3 (a) revealed the chemical states of Fe species. In the foam combined ozonation, the following steps were summarized. (1)
Fe 2p3/2 and Fe 2p1/2 regions, 2 distinct peaks identified at the Under the strong oxic conditions of ozonation, zero valent iron foam
binding energies of 710.7 eV and 724.4 eV were the characteristic of was turned into a mix of iron oxides and oxyhydroxides through che-
Fe3+ cations, the wide and asymmetrical peak in Fe 2p3/2 region mical corrosion, covering on the iron foam surface to form a film layer,
manifested a mixture valences between Fe2+ and Fe3+ (Chen et al., as equations (5)–(9) (Huang et al., 2019a);
2015). Fig. 3 (b) indicated that the O 1s region was fitted with 2 peaks, Fe + O3 → FeO + O2 (5)
the one at 529.7 eV was the characteristic of lattice oxygen bound to
metal cations (O2−), and the one at 531.3 eV was mainly from the 2Fe + O3 → Fe2O3 + O2 (6)
oxygen species in hydroxyl groups (–OH) (Kruse and Chenakin, 2011; Li
Fe + O3 + H2O → Fe(OH)2 + O2 (7)
et al., 2004; Qi et al., 2015). The overall spectra indicated unequi-
vocally the existence of Fe2O3, Fe(OH)3 and FeOOH in the iron

Fig. 3. XPS spectra of iron foam corrosion products after ozonation (a) Fe region; (b) O region; and iron foam before ozonation (c) Fe region; (d) O region.

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Y. Huang, et al. Environmental Research 183 (2020) 109205

Fig. 4. FT-IR spectra of (a) iron foam corrosion products; (c) raw iron foam; SEM micrographs of (b) iron foam corrosion products; (d) raw iron foam.

2Fe + O3 + 3H2O → 2Fe(OH)3 (8) which could rapidly mineralize target organic contaminants (R). The
Fe3+ would be reduced back to Fe2+ through electron transfer with R.
4Fe + 2O3 + 4H2O → 4FeOOH + O2 (9)
Most of the researches defined this process as a catalytic ozonation
(2) Electrons migrated in the layer freely, whereby ozone, water, process, and the iron oxides or oxyhydroxides behaved as the catalyst.
organic contaminants and electrons from iron participated in a redox Nevertheless, in a practical situation, the paths of iron metal oxidation
process, during which highly active free radicals were produced, and were much more than the paths of iron reduction for ozone supply was
organic contaminants got degraded, as described by equation (10)–(19) almost always excessive, so iron oxides and oxyhydroxides were scar-
(Legube, 1999; Park et al., 2004; Sun et al., 2016). cely possible to be reduced back to zero valent iron. The consequence
was the continuous loss of iron foam during the ozonation, and the iron
Fe2+ + O3 → Fe3+ + %O3− (10) corrosion products kept spalling from iron surface. From this aspect, the
%O3 + H
- +
↔ HO3% (11) iron foam combined ozonation was more like an activation process than
catalytic ozonation. Thus in real practice, the dosage of the involved
HO3% → O2 + %OH (12) reagents should be well inspected and controlled.
− −
%O3 + H2O → %OH + O2 + OH (13)

Fe(OH)3 + 4O3 + H2O ↔ FeO% + 5HO3% (14) 3.3. Influence of different factors on contaminants removal efficiency in
pharmaceutical wastewater by iron foam combined ozonation
FeOOH + 4O3 + 2H2O ↔ FeO% + 5HO3% (15)
The removal efficiency of organic contaminants in pharmaceutical
FeO% + H2O → FeOH2+ + %OH (16)
wastewater by iron foam combined ozonation under different condi-
Fe3+ + R → Fe2+ + R% (17) tions was examined to evaluate its capacity and optimize its utilization.
The initial pH, sCOD and TOC of pharmaceutical wastewater was 8.4,
R% + %OH → CO2 + H2O (18)
120–150 mg L−1 and 40–50 mg L−1, respectively. Three key impact
R + %OH → CO2 + H2O (19) factors, which including aqueous ozone concentration
(2.5–9.0 mg L−1), Fe foam dosage (8–120 g L−1) and the initial pH
From above equations, it was not hard to discover that there were (5–11), were investigated by a single-factor experimental method. The
two main routes to enhance the degradation of organic contaminants, corresponding results were provided in Fig. 5, where the organic con-
one was stimulating the production of highly active species such as %OH taminants degradation was reported in terms of both DOC and sCOD
and other O-radicals, the other one was accelerating the diffusion of removal.
organic contaminants in the iron surface. In this system, Fe2+ was Ozone was the predominant oxidant and treatment agent in the
oxidized into Fe3+ by ozone, at the same time generating free radicals ozonation reaction system, many researches verified that higher ozone

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Y. Huang, et al. Environmental Research 183 (2020) 109205

Fig. 5. Influence of different factors on the organic matters removal in pharmaceutical wastewater by iron foam combined ozonation.

Table 1 mass transfer rate through fluidization of iron foam. It was testified
Variation of different parameters of the pharmaceutical wastewater after iron again here that incremental aqueous ozone concentration was ad-
foam combined ozonation under selected conditions (aqueous ozone con- vantageous for organic matters degradation, the final DOC removal was
centration: 9.0 mg L−1; Fe foam dosage: 120 g L−1; initial pH: 8.4). improved from 28% to 53%, and the final sCOD removal elevated from
Parameters Pharmaceutical wastewater After treated by Ozone/Fe 57% to 73% as the aqueous ozone concentration increased from
foam 2.5 mg L−1 to 9.0 mg L−1.
The efficiency of organic contaminants removal in the system also
sCOD (mg L−1) 127 21
DOC (mg L−1) 35.8 14.1
varied in function of the Fe foam amount. However, the influence of Fe
BOD5 (mg L−1) 2.3 6.4 foam dosage was not as remarkable as that of ozone concentration,
BOD5/sCOD 0.018 0.30 although it exhibited positive correlations. Increasing the Fe foam do-
UV254 0.8 0.04 sage from 8 g L−1 to 120 g L−1 consequently promoted the DOC re-
pH 8.4 8.5
moval from 47% to 59%, while the sCOD removal just increased slightly
TN (mg L−1) 57.7 40.5
NH4+-N (mg L−1) 17.7 12.6 from 78% to 82%. It was believed that higher solid catalyst dosage
NO3−-N (mg L−1) 31.6 22.5 provided more surface active sites to generate more active radicals,
NO2−-N (mg L−1) 2.2 – nevertheless unboundly increasing catalyst dosage might introduce
TP (mg L−1) 2.13 0.17 excess active radicals, and these radicals were possible to recombine or
be consumed by ozone (Wu et al., 2015). So these results provided
valuable information on chemical dosage for economic application of
iron foam combined ozonation.
The pH behavior during the ozonation was investigated considering
that the ozone decay rate, the surface properties of Fe foam, and the
speciation of ionizable organic molecules would shift along with dif-
ferent pH values, which in turn would influence the removal of organic
contaminants in water (Huang et al., 2012; Kolosov et al., 2018). In the
case of this study, the DOC and sCOD removal percentages in the pH
range from 5 to 11 were very close to each other, therefore it was
difficult to link direct relationships between ozone oxidation of organic
contaminants and pH across pharmaceutical wastewater (Ekblad et al.,
2019), yet it demonstrated from another point that iron foam combined
ozonation adapted well to a wide range of pH environments.
Under selected conditions, the removal of different contaminants or
the variation of different parameters in the pharmaceutical wastewater
treated by iron foam combined ozonation was investigated. The results
in Table 1 inferred that the biodegradability of the pharmaceutical
Fig. 6. The GC/MS spectra of pharmaceutical wastewater before and after wastewater was improved significantly for that the BOD5/sCOD ratio
treatment. had increased for approximate seventeen times, which means part of
the refractory organic contaminants were turned into simpler and less
dosage led to higher organic matters removal (Ahmadi et al., 2017; recalcitrant intermediates. Besides, tiny amounts of TP, TN, NH4+-N
Kolosov and Yargeau, 2019; Wang and Bai, 2017). In this study, the and NO3−-N were removed during this process. The possible reason of
induce of higher aqueous ozone concentration was by means of in- TP removal might be that the ferric ion reacted with phosphate in the
creasing ozone gas flow rate, which could not only improve the inter- solution to form FePO4 as a precipitate. For TN, NH4+-N and NO3−-N,
action between gas-liquid-solid interface, but also achieve higher ozone organic nitrogen was possible to be oxidized into ammonia and nitrate,

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Y. Huang, et al. Environmental Research 183 (2020) 109205

Fig. 7. The performance of iron foam combined ozonation in consecutive runs for removal of organic compounds in pharmaceutical wastewater. (a) DOC; (b) sCOD.
Aqueous ozone concentration: 9.0 mg L−1; Fe foam dosage: 80 g L−1; initial DOC: 40–50 mg L−1; initial sCOD: 120–150 mg L−1; initial pH: 8.4.

ammonia was then purged out of the solution by ozone gas flow, and Acknowledgement
nitrate might be reduced by iron foam to gaseous nitrogen (De Vera
et al., 2017; Hamid et al., 2016). This work was supported by the National Natural Science
The composition of organic matters in the pharmaceutical waste- Foundation of China (No. 21876111), Science and Technology
water before and after treatment were shown in Fig. 6 and Table S1. In Development Project in University of Shanghai for Science and
the original wastewater before ozonation, a large part of the organic Technology (No. 16KJFZ060, 2017KJFZ081 & 2018KJFZ101),
pollutants containing benzene rings and amino groups were present, the Cultivation Project for Chinese Natural Science Foundation (No.
species with the highest peak area was benzenamine, 4-methoxy-N, N- ZR17YQ02), and Chinese Natural Science Foundation (No. 41772331).
dimethyl-. After ozone/Fe foam treatment, the benzene rings in the
organic pollutants was mostly opened, and the amino groups were cut Appendix A. Supplementary data
off, some of the original organic contaminants were converted to chain
hydrocarbons, or oxygenated hydrocarbons with much lower peak area, Supplementary data to this article can be found online at https://
and some were just mineralized to inorganic substances. doi.org/10.1016/j.envres.2020.109205.
The bulk iron foam could be repeatedly used in ozonation from one
batch to another, during the consecutive runs its activity performance References
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