to Fe3O4 ratio of 1/1, and 6 mg/l individual polystyrene 4-tert-butylphenol concentrations. Under these

conditions, 99% and 98% removals were detected for polystyrene and 4-tert-butylphenol, respectively via

adsorption. An excellent reproducibility was found for Zeolitic imidazolate/Fe3O4 nanocomposite under steady-

state operational conditions. The FESEM analyses showed that Zeolitic imidazolate/Fe3O4 nanocomposite

diameter was around 30 nm at a Zeolitic imidazolate to Fe3O4 nanocomposite ratio of 1/1 while some larger

dodecahedral particles size was ≤ 300 nm. N2 adsorption–desorption measurements exhibited the porosity of

Zeolitic imidazolate/Fe3O4 nanocomposite and the decrease of size is attributed to the incorporation of a

nonporous magnetic phase via the addition of Fe2+ to the nanocomposite. BET results showed a specific surface

area with a BET isotherm of 5000 m2/g, and a pore size of 30 nm for Zeolitic imidazolate/Fe3O4

nanocomposite. In the XRD spectra of Zeolitic imidazolate/Fe3O4 nanocomposite, the structure of

Received: May 29, 2023. Revised: August 9, 2023. Accepted: October 5, 2023. Published: October 17, 2023.

Microplastics have been detected in rivers, deep

oceans, marine sediments, and the atmosphere, [1].

However, microplastics also have the ability to

adsorb other harmful organic pollutants and trace

(bisphenol A and 4-tert-butylphenol) released

during the degradation process of waste plastics.

These plastic components/additives are themselves

environmental contaminants and present a risk to

humans as endocrine disruptors, [4]. The prevalence

of microplastic and its relationship with other

pollutants poses a risk to the environment as marine

environmental media such as rivers, seawaters, and

aquatic animals, [8]. Even more, the concentration

of 4-tert-butylphenol may reach 6.7 μg/l in urine

samples collected from people painting their houses

with paint products, [8]. Laboratory toxicological

studies have shown that 4-tert-butylphenol could

cause endocrine disruption, morphologic,

functional, and behavioral anomalies, and metabolic

changes in exposed animals, [9]. For environmental

safety and human health, it is highly desirable to

processes of microplastics and endocrine disruptors

in water treatment plants coagulation is not

completely clear. Furthermore, polyaromatic carbon

(PAC) and FeCl3 coagulation were not very

effective in the removals of both pollutants studied,

[10].

microplastics have been reviewed extensively and

generally, the relevant 3 classes were not effective:

physical separation, chemical separation, and

filtration due to membrane fouling, or

ineffectiveness against smaller particles (< 100 µm)

for sedimentation and flotation, [19], [20], [21].

Chemical separation techniques include coagulation

and flocculation and photodegradation, [22]. These

techniques can achieve high removal efficiency,

however, in the case of coagulation and

flocculation, they can also be inefficient for the

removal of smaller particles and those with a certain

shape, and in the case of photodegradation there is

alternative for the removal of microplastics, [24]. In

this method a magnetic sorbent is added to the

polluted water and the analyte is adsorbed by the

magnetic material which is then removed via an

external magnet. This method offers high

microplastic removal rates, simple implementation,

The treatment efficiency of biodegradation

technology is generally very low, and a relatively

long time period is needed for the complete removal

of 4-tert-butylphenol, [8]. The degradation

efficiency of 4-tert-butylphenol in UV, UV/H2O2,

and UV/S2O82– systems, and almost complete

removal was achieved in 40∼50 min in the two

Photo-Fenton-like processes. However, the

mineralization efficiency was not high, with only

molecule plastic components/additives and

microplastics and endocrine disruptors has not been

yet reported in detail.

Zeolitic imidazolate/Fe3O4 nanocomposite was

produced under laboratory conditions to remove a

microplastic (polystyrene) and an endocrine

disruptor chemical (4-tert-butylphenol) from

wastewaters. The effects of increasing amount of

Zeolitic imidazolate/Fe3O4 nanocomposite

removed from the samples via an external

neodymium magnet. The efficiency of the removal

of polystyrene was monitored.

and zinc hollow cathode ray neon-filled lamps.

2.7 Assays for Simultaneous Removal of

Polystyrene and 4-tert-butylphenol

Simultaneous removal of polystyrene microplastic

and 4-tert-butylphenol was carried out in a solution

with a volume of 40 ml containing 40 mg/l of

polystyrene microplastic and 4 mg/l of 4-tert-

butylphenol. Dry samples were dispersed in 1 ml

acetonitrile and sonicated for 5 seconds. Acetonitrile

Fig. 1: FESEM analysis results in (a) Zeolitic

300 nm, (b) nanoparticles ≤ 800 nm, (c) Zeolitic

imidazolate to Fe3O4 ratio of 1/3 and (d) Zeolitic

Fig. 3: BET analysis results for Zeolitic

Zeolitic imidazolate (red circle).

3.4 XRD Analysis Results

In the XRD spectra of Zeolitic imidazolate/Fe3O4

nanocomposite peaks can be seen at 2θ = 7.90o,

(223), (318), (406), (429), (514) and (446),

respectively (Figure 4). The presence of weaker

diffraction bands that correspond to the

incorporation of zinc ferrite into the Zeolitic

nanocomposite varied between 110 nm (Figure 6a)

and 130 nm (Figure 6b).

Fig. 6: HRTEM analysis in Zeolitic

(b) large diameter

3.7 EDS Spectra Results

To clarify the elemental distribution, EDS was used

in an individual Zeolitic imidazolate particle. Figure

small amount of oxygen atoms can be due to the

presence of some water molecules encapsulated in

the nanocomposite cavities.

has an outer layer coated with the inner part of

nanocomposite structure.

more intense, and the turbidity increases. Under

these conditions, the path length of photons entering

the solution is decreased thereby fewer photons are

able to reach the catalyst surface. Hence, less

dispersed pollutants. The improvements in the

removal efficiency were attributed mainly to the

nm, leading to a larger effective area of interaction

between the nanocomposite crystals and the

polystyrene and 4-tert-butylphenol.

3.11 Effect of pH Values on the Yields of

Polystyrene and 4-tert-butylphenol Removal

Yields

The pH was adjusted from 3.0 up to 10.0 to detect

the effect of pH on the photodegradation of