Elsevier

Journal of Hazardous Materials

Volume 307, 15 April 2016, Pages 350-358
Journal of Hazardous Materials

Simultaneous removal and degradation characteristics of sulfonamide, tetracycline, and quinolone antibiotics by laccase-mediated oxidation coupled with soil adsorption

https://doi.org/10.1016/j.jhazmat.2015.12.062Get rights and content

Highlights

  • Fourteen kinds of antibiotics were simultaneously removed.

  • Soil adsorption was introduced into the laccase system to assist the simultaneous removal.

  • Antibiotics were removed above 70% in 15 min and close to 100% in 180 min.

  • Sulfonamides were removed mainly by laccase oxidation and quinolones by soil adsorption.

Abstract

The uses of laccase in the degradation and removal of antibiotics have recently been reported because of the high efficiency and environmental friendliness of laccase. However, these removal studies mostly refer to a limited number of antibiotics. In this study, soil adsorption was introduced into the laccase-oxidation system to assist the simultaneous removal of 14 kinds of sulfonamide, tetracycline, and quinolone antibiotics, which differed in structures and chemical properties. The complementary effects of laccase-mediated oxidation and soil adsorption enabled the simultaneous removal. Removal characteristics were determined by a comprehensive consideration of the separate optimum conditions for laccase oxidation and soil adsorption removal experiments. With concentrations of laccase, syringaldehyde (SA), and soil of 0.5 mg/mL, 0.5 mmol/L, and 50 g/L, respectively, and at pH 6 and 25 °C, the removal rates of each antibiotic exceeded 70% in 15 min and were close to 100% in 180 min. Sulfonamide antibiotics (SAs) were removed mainly by laccase oxidation and quinolone antibiotics (QUs) mainly by soil adsorption. Tetracycline antibiotics (TCs) were removed by both treatments in the coupled system, but laccase oxidation dominated. Electrostatic adsorption was speculated to be one of the adsorption mechanisms in soil adsorption with QUs and TCs.

Introduction

The presence of antibiotic pharmaceutical compounds in the ecosystem has become an emerging concern since the mid-1990s when the use of these compounds was widespread and new analytical technologies were developed [1]. Their environmental impacts lie mainly in affecting the ecological system and the generation of microbial strains resistant to antibiotics [2]. Residues of human and veterinary antibiotics have been detected in different matrices [3], [4], [5], [6], [7], [8], [9], indicating their ineffective removal from water and wastewater using conventional treatment methods [10].

To prevent environmental matrices contamination, several processes to degrade/remove antibiotics have been studied, including conventional techniques (biological processes, filtration, coagulation, flocculation, and sedimentation), advanced oxidation processes (AOPs), adsorption, membrane processes, and combined methods [1]. AOPs like ozonation, Fenton oxidation, or photocatalytic oxidation are efficient procedures for the transformation of emerging organic contaminants [11], [12]. However, AOPs necessitate the addition of catalysts and oxidants that are costly and may lead to secondary pollution [13].

In the endeavor to find less resource-intensive technologies, enzyme-catalyzed transformation methods for the removal of emerging organic contaminants have been explored in recent years. One group of enzymes receiving special attention is that of laccases [14]. Laccase, an oxidoreductase enzyme, catalyzes the oxidation of certain aromatic compounds, particularly phenolic compounds, using molecular oxygen as the terminal electron acceptor. Studies have indicated that laccases have enormous potential in the remediation and treatment of contaminated water or soil, such as the decolorization of dyes [15] and the degradation of pesticides [16] and several Pharmaceutical andPersonal Care Products (PPCPs) [17], [18]. The presence of low-molecular-weight mediators has also been reported to enhance the oxidative ability of laccase [19]. Laccase can oxidize these mediators to free radicals, thereby enabling a highly effective removal of a wide spectrum of compounds.

The uses of laccase in the degradation and removal of antibiotics have been recently reported, and removal efficiencies are quite high in some of reports on laccase-oxidation systems [20]. However, these removal studies mostly refer to a limited number of antibiotics, such as two or three kinds of sulfonamides or tetracyclines. Research on the simultaneous removal of several categories of antibiotics is limited. Various antibiotics are known to exist in environmental matrices, and the simultaneous removal of as many antibiotics as possible is necessary.

From literatures and our preliminary experiments, sulfonamide antibiotics (SAs) and tetracycline antibiotics (TCs) tend to be oxidized by laccase-oxidation systems, whereas quinolone antibiotics (QUs) are relatively recalcitrant to laccase-oxidation systems. On the contrary, QUs and TCs are easily adsorbed by sediments because of their high Kd values, whereas the Kd of SAs are relatively low [21], [22]. Accordingly, we assumed that the complementary action of laccase oxidation and soil adsorption can simultaneously remove SAs, TCs, and QUs. Therefore, in our study, an adsorption method was introduced into the laccase-oxidation system to assist the simultaneous removal of 14 kinds of SAs, TCs, and QUs. Scientists have investigated the adsorption removal of antibiotics by several materials, including montmorillonite [23], chitosan particles [24], aluminum oxide [25], activated carbon [26], and graphene oxide [27]. However, using natural soils as adsorbents for the removal of antibiotics is relatively rare, and studies on the soil adsorption of antibiotics have mainly focused on the environmental transformation behaviors of antibiotics so far [28], [29], [30], [31], [32], [33].

In this study, we focused on the soil adsorption removal of antibiotics because of the significant advantages of low cost and easy access of natural soils as adsorbents. We chose a kind of typical red soil located in south China, which showed good application in pollutant removal in our preliminary studies [34]. To our knowledge, this report is the first one on antibiotic removal by laccase oxidation coupled with soil adsorption, as well as on the simultaneous removal of three categories, i.e., 14 kinds of antibiotics. Our method is promising for the repair of the soil antibiotic pollution and the antibiotic polluted water as well.

Section snippets

Chemicals and reagents

SAs including sulfadiazine (SD, ≥99.0%), sulfamethazine (SMZ, ≥99%), sulfapyridine (SPD, ≥99.0%), sulfamethoxazole (SMX, ≥98.0%), and sulfathiazole (STZ, ≥98.0%) were purchased from Sigma–Aldrich (China). TCs including tetracycline hydrochloride (TC, 98%), chlortetracycline hydrochloride (CTC, 97%), oxytetracycline hydrochloride (OTC, 97%), doxycycline hydrochloride (DC, 95%), and demeclocycline hydrochloride (DTC, 99%) were purchased from J&K (China). QUs including ofloxacin (OFX, 98%),

Effects of mediators, mediator concentration, pH, temperature, and laccase concentration on antibiotic removal by laccase-oxidation systems

As shown in Fig. 2(a), the removals of TCs (OTC, TC, CTC, and DC) were efficient both in laccase-HBT and laccase-SA treatments. However, TCs were highly unstable according to the control treatment. The average removal rate of the control treatment was 50% in 3 h. The removals of QUs (ENX, NFX, OFX, CFX, and EFX) were not significant in each treatment, showing that the laccase-oxidation systems in the experiments were useless for QUs removal. For SAs (SD, STZ, SPD, SMZ, and SMX), the removal

Conclusions

A novel method of laccase-mediated oxidation coupled with soil adsorption for the simultaneous removal of SAs, TCs, and QUs was proposed. Removal characteristics were determined by a comprehensive consideration of the separate optimum conditions for laccase oxidation and soil adsorption removal experiments. Laccase-mediated oxidation coupled with soil adsorption was verified in this study as an efficient method for the simultaneous removal of SAs, TCs, and QUs. Removals of each antibiotic

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 41331174, 31400405), Water Science and Technology Fund of Jiangxi Province in China (Grant No. KT201412), Water Resources and Water Environment Research Center Fund of Water Resources Ministry in China (Grant No. kfjj201403), Science and technology promotion project of Ministry of Water Resources (Grant No. TG1520), Environmental Protection Projects of Hubei Province (Grant No. 2014HB08).We thank Mr. Zong

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