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Abstract

In this study, a dinitrodiphenyldiquinoline derivative is synthesized, purified, and characterized, and its adsorptive ability is examined for the first time. Twelve common polycyclic aromatic hydrocarbons are chosen as potential adsorbates for removal by using dinitrodiphenyldiquinoline as an adsorbent surface. The adsorptive capacity and the efficiency of removal depend on several variables such as adsorbent dose, polycyclic aromatic hydrocarbon initial concentration, pH, and contact time. This paper summarizes the adsorbent parameters and the kinetic models that can optimize and describe the adsorption process used to treat aqueous solutions of polycyclic aromatic hydrocarbons. Experimentally, the optimum adsorbent dose, the initial concentration, and contact time are found to be 0.1 g, 1 ppm, and 60 min, respectively. Mathematical treatment of the adsorption data reveals that the adsorption of all the polycyclic aromatic hydrocarbons by dinitrodiphenyldiquinoline adopted a pseudo second-order adsorption model. As a result, the dinitrodiphenyldiquinoline derivative is found to be a very good adsorbent surface for several hazardous organic pollutants such as polycyclic aromatic hydrocarbons.

Keywords

adsorption kinetic models adsorption dinitrodiphenyldiquinoline host–guest technology organic adsorbent organic pollutants polycyclic aromatic hydrocarbons

Introduction

Organic and inorganic pollutants are considered to be a critical issue, especially if they exist in drinking and clean water resources. Many previous studies have reported high levels of various contaminants in different water types.^1–3 Over the last two decades, researchers have devoted significant efforts to finding efficient methods to eliminate or at least minimize the concentrations of pollutants in different water resources. Generally, organic and inorganic pollutants are very complicated to remove or reduce efficiently when conventional physicochemical methods are used, such as filtration, coagulation, sedimentation, flocculation, phytodegradation, photolysis, or ozonation, despite these methods being considered the most common and effective treatment processes.^4–10 Therefore, easier techniques are found to be more effective, such as adsorption; the adsorption technique involves using cheap, safe, and large surface area and recyclable adsorbent materials. Recent publications have investigated and reported different chemical, physical, and biological techniques for contaminated water treatment.^1–3 In particular, adsorbent surfaces can be used to reduce or remove organic pollutants and are classified as natural adsorbents (such as charcoal, clays, clay minerals, zeolites, and ores)¹¹ and synthetic adsorbents (such as diphenyldiquinoline (DPDQ)).¹² In a previous study, our group investigated the adsorptive ability of a DPDQ derivative against phenol as an organic pollutant.¹²

In this context, polycyclic aromatic hydrocarbons (PAHs) are considered to be one of the most common organic pollutants that exists at high levels in the environment, especially in water resources.¹³ PAHs are chemically stable in the environment, not easily biodegradable, and can accumulate over time to very dangerous doses in the environment,^14–17 and can cause carcinogenic, mutagenic, and toxic effects.^18–25 The prime source of PAH emissions is the combustion of fuels, forest fires, volcanic eruptions, some biological activities, and anthropogenic sources.^26–28 Furthermore, creosote and coal tar usage are categorized as the main sources of PAH compounds in environmental elements such as air,^29,30 soil and sediments,^31,32 water resources, and animal and plant tissues.^33,34 Recent studies have demonstrated that long-term exposure to PAH environmental pollutants may adversely affect human health.^35,36 Therefore, adsorbents with large surface areas and high numbers of adsorption sites are needed to remove PAHs from the environment effectively.

This study aims to investigate the efficacy of dinitrodiphenyldiquinoline (DNDPDQ) 3 on the adsorption of 12 different PAH pollutants. Three types of hazardous PAHs ( PAF , PBCB ^b B ^k, and B ^k _pDB ^ghi I ) were used as potential adsorbates since they are found in high quantities in the environment and have different disturbing properties. The selected PAHs are grouped into classes consisting of two, three, or four aromatic rings, which are known to have different physiochemical properties. In addition, the study also identifies the optimal adsorption parameters for the DNDPDQ adsorbent, including contact time and kinetic adsorption models. This work may have important implications for environmental remediation efforts and for the protection of human health from hazardous pollutants.

Results and discussion

Preparation of adsorbent 3

The adsorbent candidate 3 (dinitrodiphenyldiquinoline (DNDPDQ)) was synthesized, purified, and characterized according to the literature procedure (scheme 1).³⁷

Scheme 1.

Synthesis of the dinitrodiphenyldiquinoline (DNDPDQ) 3 adsorbent.

Adsorption of Phenanthrene, Anthracene and Fluoranthene (PAF)

Contact time effect

The removal efficiency vs the contact time of phenanthrene, anthracene and fluoranthene (PAF) (Figure 1) during adsorption process on DNDPDQ is shown in Figure 2(a). The maximum adsorption was reached within 60 min, indicating quick removal efficiency by the DNDPDQ adsorbent. Therefore, the optimum contact time was 60 min.

Figure 1.

Structures of phenanthrene, anthracene, and fluoranthene.

Figure 2.

(a) The effect of contact time on the adsorption of PAF, and kinetic models: (b) first order, (c) pseudo first order, and (d) pseudo second order. (Optimum conditions: 0.1 g of DNDPDQ (3) adsorbent, 1 ppm of the PAH solution, 60 min contact time, pH = 7).

Adsorption kinetics

Kinetic modeling of the adsorption process was achieved by mathematical treatment of the adsorption data presented in Figure 2. The adsorption kinetics of PAF in the presence of the DNDPDQ adsorbent were analyzed using three kinetic models: the first order of Santos, the pseudo-first order of Lagergren, and the pseudo-second order of Ho and McKay. As illustrated in Figure 2(d), the pseudo second-order model exhibited the highest linearity level compared to the first-order adsorption (Figure 2(b)) and pseudo first-order adsorption (Figure 2(c)). In this context, the results indicate that the removal process of PAHs by the DNDPDQ adsorbent was mainly controlled by the chemisorption interaction mechanism. Table 1 shows the results of the kinetics study.

Table 1.

The rate constant values for adsorption of PAH on the DNDPDQ adsorbent.

Kinetic model	PAH	K	K₁	K₂ g.mg ⁻¹.min⁻¹	q_e mg.g⁻¹	r²
First order of Santos	phenanthrene	27.4	min⁻¹	–	0.979	0.599
	phenanthrene	27.4	0.021	–	0.979	0.599
	anthracene	54.8	0.028	–	0.993	0.813
	fluoranthene	65.0	0.029	–	0.995	0.837
Pseudo-first order of Lagergren	phenanthrene	–	mg.g⁻¹ .min⁻¹	–	0.979	0.711
	phenanthrene	–	0.041	–	0.979	0.711
	anthracene	–	0.045	–	0.993	0.982
	fluoranthene	–	0.039	–	0.995	0.953
Pseudo-second order of Ho and Mc Kay	phenanthrene	–	–	0.485	0.979	0.999
	anthracene	–	–	0.607	0.993	0.999
	fluoranthene	–	–	1.390	0.995	1.000

PAH: polycyclic aromatic hydrocarbon; DNDPDQ: dinitrodiphenyldiquinoline.

Adsorption of Chrysene, Benzo(a)anthracene, Pyrene, Benzo(b)fluoranthene, and Benzo(k)fluoranthene (CBPB^bB^k )

Contact time effect

The removal efficiency (%) vs contact time (min) for the adsorption of chrysene, benzo(a)anthracene, pyrene, benzo(b)fluoranthene, and benzo(k)fluoranthene (CBPB^b B ^k) (Figure 3) on DNDPDQ adsorbent 3 is illustrated in Figure 4(a). It is remarkable that the ability of the adsorbent reached a plateau within 60 min. Therefore, the optimum contact time was 60 min.

Figure 3.

Structures of pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, and benzo(k)fluoranthene.

Figure 4.

(a) Effect of the contact time on the adsorption of CBPB^b B ^k, and the kinetic models: (b) first order, (c) pseudo first order, and (d) pseudo second order. (Optimum conditions: 0.1 g of DNDPDQ (3) adsorbent, 1 ppm of the PAH solution, 60 min contact time, pH = 7).

Adsorption kinetics

The kinetic model adopted for each PAH was achieved by applying the first order of Santos, the pseudo first order of Lagergren, and the pseudo second order of Ho and McKay for the adsorption of CBPB^b B ^k onto DNDPDQ adsorbent 3.

The pseudo-second-order adsorption kinetic model was found to have the highest level of linearity as shown in Figure 4(d) compared to the first-order adsorption kinetic model shown in Figure 4(b) and the pseudo-first-order adsorption kinetic model shown in Figure 4(c). The results of the kinetic studies are presented in Table 2.

Table 2.

The rate constant values for adsorption of CBPB^b B ^k on the DNDPDQ adsorbent.

Kinetic model	PAH	K	K₁	K₂ g.mg ⁻¹.min⁻¹	q_e mg.g⁻¹	r²
First order of Santos	pyrene	38.6	min⁻¹	–	0.994	0.923
	pyrene	38.6	0.027	–	0.994	0.923
	benzo(a)anthracene	93.3	0.027	–	0.995	0.933
	chrysene	164.7	0.030	–	0.996	0.844
	benzo(b)fluoranthene	244.4	0.031	–	0.997	0.829
	benzo(k)fluoranthene	287.0	0.032	–	0.998	0.802
Pseudo first order of Lagergren	pyrene	–	mg.g⁻¹ .min⁻¹	–	0.994	0.907
	pyrene	–	0.030	–	0.994	0.907
	benzo(a)anthracene	–	0.020	–	0.995	0.367
	chrysene	–	0.031	–	0.996	0.683
	benzo(b)fluoranthene	–	0.031	–	0.997	0.603
	benzo(k)fluoranthene	–	0.035	–	0.998	0.660
Pseudo second order of Ho and McKay	pyrene	–	–	1.89	0.994	1.000
	benzo(a)anthracene	–	–	5.40	0.995	1.000
	chrysene	–	–	10.47	0.996	1.000
	benzo(b)fluoranthene	–	–	16.19	0.997	1.000
	benzo(k)fluoranthene	–	–	17.93	0.998	1.000

CBPB^b B ^k: chrysene, benzo(a)anthracene, pyrene, benzo(b)fluoranthene, and benzo(k)fluoranthene; DNDPDQ: dinitrodiphenyldiquinoline; PAH: polycyclic aromatic hydrocarbon.

Adsorption of Dibenzo(a, h)anthracene, Benzo(a)pyrene, Benzo(g,h,i)perylene and Indo(1,2,3,4-c,d)pyrene (DB^a_pB^ghiI)

Contact time effect

The removal efficiency (%) vs contact time (min) for the adsorption of dibenzo(a,h)anthracene, benzo(a)pyrene, benzo(g,h,i)perylene, and indo(1,2,3,4-c,d)pyrene ( DB ^a _pB ^ghi I ) (Figure 5) on DNDPDQ adsorbent 3 is illustrated in Figure 6(a). It can be seen that the maximum removal was again achieved within 60 min. Thus, the optimum contact time was 60 min.

Figure 5.

Structures of dibenzo(a,h)anthracene, benzo(a)pyrene, benzo(g,h,i)perylene, and indo(1,2,3,4-c,d)pyrene.

Figure 6.

(a) The effect of the contact time on the adsorption of DB ^a _pB ^ghi I , and the kinetic models: (b) first order, (c) pseudo first order, and (d) pseudo second order. (Optimum conditions: 0.1 g of DNDPDQ (3) adsorbent, 1 ppm of the PAH solution, 60 min contact time, pH = 7).

Adsorption kinetics

As in the previous sections, the first-order adsorption of Santos, the pseudo-first order of Lagergren, and the pseudo-second order of Ho and McKay kinetic models were applied. The adsorption kinetics of DB ^a _pB ^ghi I onto the DNDPDQ adsorbent 3 were examined. The pseudo second-order adsorption kinetic model has the highest level of linearity, as shown in Figure 6(d) in comparison to the first-order adsorption kinetic model shown in Figure 6(b) and the pseudo first-order adsorption kinetic model shown in Figure 6(c). A summary of the kinetics is presented in Table 3.

Table 3.

The rate constant values for the adsorption of DB ^a _pB ^ghi I on the DNDPDQ adsorbent.

Kinetic model	PAH	K	K₁	K₂ g.mg ⁻¹.min⁻¹	q_e mg.g⁻¹	r²
First order of Santos	benzo(a)pyrene	15.5	min⁻¹	–	0.949	0.692
	benzo(a)pyrene	15.5	0.014	–	0.949	0.692
	dibenzo(a,h)anthracene	220.9	0.098	–	1.000	0.961
	benzo(g,h,i)perylene	868.2	0.046	–	0.999	0.997
	indo(1,2,3,4-c,d)pyrene	1098.0	0. 116	–	1.000	0.915
Pseudo first order of Lagergren	benzo(a)pyrene	–	mg.g⁻¹ .min⁻¹	–	0.949	0.686
	benzo(a)pyrene	–	0.024	–	0.949	0.686
	dibenzo(a,h)anthracene	–	0.027	–	1.000	0.489
	benzo(g,h,i)perylene	–	0.027	–	0.999	0.366
	indo(1,2,3,4-c,d)pyrene	–	0.031	–	1.000	0.432
Pseudo second order of Ho and McKay	benzo(a)pyrene	–	–	3.76	0.949	1.000
	dibenzo(a,h)anthracene	–	–	18.48	1.000	1.000
	benzo(g,h,i)perylene	–	–	24.39	0.999	1.000
	indo(1,2,3,4-c,d)pyrene	–	–	55.50	1.000	1.000

DB ^a _pB ^ghi I : dibenzo(a,h)anthracene, benzo(a)pyrene, benzo(g,h,i)perylene and indo(1,2,3,4-c,d) pyrene; DNDPDQ: dinitrodiphenyldiquinoline; PAH: polycyclic aromatic hydrocarbon.

The efficiency removal was enhanced by the presence of a polyaromatic moiety, which is responsible for different motifs of interactions that possibly explain the adsorption process between the adsorbent and adsorbate molecules. The most common interaction is π–π stacking, which can exist in the form of face–face, face–edge, or edge–edge interactions. Table 4 compares the data for the DNDPDQ adsorbent with some reported adsorbents in the literature. It is obvious that the removal efficiency of DNDPDQ is much higher than those of other studies. Therefore, DNDPDQ proves to be an excellent adsorbent compared to those listed in Table 4.

Table 4.

Comparison of the removal of PAHs by DNDPDQ (3) and other adsorbents.

Adsorbent	Adsorbent dosage (g/L)	Removal		Ref.
Adsorbent	Adsorbent dosage (g/L)	Time	Efficiency (%)	Ref.
Periodic mesoporous organosilica (removal of pyrene and fluoranthene, respectively).	0.10	24 h	50 and 40	Carla et al.³⁸
Chemical treatment methods	Mixture of: 0.35 mg L^−L KMNO₄ 2 mg L^−L NaClO 18 mg L^−L FeCl₃	8 h	45–100	Isabel et al.³⁹
Granular activated carbon	0.05 to 0.8 g/L	5 h	5%–55%	Dinushika et al.⁴⁰
DNDPDQ (3)	0.10	60 min	>95	This study

PAH: polycyclic aromatic hydrocarbon; DNDPDQ: dinitrodiphenyldiquinoline.

Conclusion

The presence of different hazardous organic pollutants in water resources is considered a serious problem for the environment and humankind. In this study, the DNDPDQ derivative 3 proved to be a good adsorbent surface for removing hazardous organic pollutants such as PAHs from aqueous solutions. Experimentally, the optimum adsorbent dose, initial concentration, and contact time were found to be 0.1 g, 1 ppm, and 60 min, respectively. The kinetics of the adsorption process showed a very good removal efficiency at the optimum adsorption parameters. Further studies and investigations of the parameters are being undertaken in order to fully understand the adsorption process. Based on our findings and the concept of the adsorption process, a normally slight change in the molecular structure of the adsorbent will lead to a great change in its adsorptive behavior. Therefore, studies on the modification of the structure of DNDPDQ are ongoing with similar adsorbates.

Experimental

Chemicals and reagents

All chemicals used in this study, including 2-amino-5-nitrobenzophenone, bicyclo[3.3.1]nonane-3,7-dione, ethanol and HCl, and PAHs, were commercially available and purchased from Aldrich Chemical Company (analytical grade). They were used without further purification.

Instruments and analysis

The concentrations of the PAHs (NAP, ANT, FLA, BaA, CHR, BbF, BkF, DahA, PYR BaP, IcdP, and BghiP) were determined using a high-performance liquid chromatography (HPLC) instrument (Shimadzu SCL10Avp fitted with a photo diode array (PDA) detector (SPD M10Avp) at 254 nm). The AHYPERSIL Green PAH 100 X 4.6 mm column was used.

The instrument parameters were as follows: eluents: (A: H₂O and B: CH₃CN); the gradient was 40% of B up to 5 min and then increased gradually at a flow rate of 1.6 mL/min. After 30 min, the gradient was kept constant at 100% of B.

Contact time effect

The optimum contact time in which the adsorption has reached the equilibrium is used later to determine the adsorption rate constant. In the process of determining the rate of the adsorption process, the adsorption experiments were carried out using 100 mL (1 ppm) of standard PAH solutions at pH = 7, and the supernatant was analyzed for residual pollutants at different contact time intervals.

Batch adsorption experiments

Batch adsorption experiments were performed to investigate the optimum adsorption conditions of three aqueous solutions containing 1 ppm of each of the four PAH compounds onto the prepared DNDPDQ (3) adsorbent. Standard solutions of the three PAHs (X, Y, and Z) with an initial concentration of 1 ppm were used in the kinetic studies and in obtaining the calibration curves. The use of acetone proved efficient as a co-solvent for enhancing the solubility of the selected PAHs in aqueous systems.³³ For the adsorption kinetic experiment, 0.1 g of the DNDPDQ (3) adsorbent and 100 mL of the 1 ppm of the PAH solution were mixed in a 250 mL dark flask. The obtained mixtures were shaken for the required time using an electric thermostatic shaker at 110–125 St/min at room temperature. DNDPDQ (3)-PAH adsorption experiments were performed until the PAHs concentration became constant in the aqueous solution. Control samples containing no DNDPDQ and containing only the same PAHs were prepared as described above. Upon completion, DNDPDQ was removed from the solution by filtration, and the PAH concentration in the supernatant was determined. Three replicates were used for each PAH adsorption experiment. The adsorption capacity (mg of adsorbate per g of adsorbent) was calculated using equation (1)

A = \frac{V (C_{1} - C_{t})}{m}

(1)

where A is the amount of PAH (mg/g) adsorbed at equilibrium,

C₁: initial concentration of PAH in mg/L, C_t: equilibrium concentration of PAH in mg/L

V: solution volume of the flask in L, and m: the dosage of the adsorbent in g.

Footnotes

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding

The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: The author would like to thank the Scientific Research Support Fund (SRSF, Jordan) for financial support through the research grant EWE\2\03\2011, and Mutah University for providing the necessary technical support needed to complete this research.

ORCID iD

Salah A Al-Trawneh

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Kinetic study on the adsorption of some polycyclic aromatic hydrocarbons using dinitrodiphenyldiquinoline adsorbent

Abstract

Keywords

Introduction

Results and discussion

Preparation of adsorbent 3

Adsorption of Phenanthrene, Anthracene and Fluoranthene (PAF)

Contact time effect

Adsorption kinetics

Adsorption of Chrysene, Benzo(a)anthracene, Pyrene, Benzo(b)fluoranthene, and Benzo(k)fluoranthene (CBPBbBk )

Contact time effect

Adsorption kinetics

Adsorption of Dibenzo(a, h)anthracene, Benzo(a)pyrene, Benzo(g,h,i)perylene and Indo(1,2,3,4-c,d)pyrene (DBapBghiI)

Contact time effect

Adsorption kinetics

Conclusion

Experimental

Chemicals and reagents

Instruments and analysis

Contact time effect

Batch adsorption experiments

Footnotes

Declaration of conflicting interests

Funding

ORCID iD

References

Adsorption of Chrysene, Benzo(a)anthracene, Pyrene, Benzo(b)fluoranthene, and Benzo(k)fluoranthene (CBPB^bB^k )

Adsorption of Dibenzo(a, h)anthracene, Benzo(a)pyrene, Benzo(g,h,i)perylene and Indo(1,2,3,4-c,d)pyrene (DB^a_pB^ghiI)