Removal of p-nonylphenol isomers using nitrifying sludge in a membrane sequencing batch reactor

doi:10.1016/j.cej.2015.07.018

Chemical Engineering Journal

Volume 281, 1 December 2015, Pages 860-868

https://doi.org/10.1016/j.cej.2015.07.018 Get rights and content

Highlights

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Enriched nitrifying biomass was used to remove p-nonylphenol isomers (p-NP).
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Sorption and biodegradation were evaluated in a membrane SBR.
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Biodegradation is the main mechanism for p-NP removal.
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The biodegradation of p-NP is related to the ammonium-oxidizing activity.
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Mono(2-ethylhexyl) phthalate is an intermediary of p-NP biodegradation.

Abstract

The aim of this study was to assess p-nonylphenol removal mechanisms under nitrifying conditions in a bioreactor system. The removal of a technical mixture of p-nonylphenol isomers was evaluated in a membrane sequencing batch reactor without the addition of an organic carbon source in enriched nitrifying sludge. The p-nonylphenol concentration was quantified in the liquid and solid phases to accurately differentiate between biodegradation and sorption mechanisms. The predominant removal mechanism was p-nonylphenol biodegradation (62%), followed by sorption, which resulted in a total removal of 96%. In addition, ammonium-oxidizing microorganisms controlled the biodegradation of p-nonylphenol, and 1,2-benzenedicarboxylic acid, mono(2-ethylhexyl)ester was identified as the main intermediary metabolite. These results suggested that co-metabolic biodegradation by heterotrophic microorganisms is necessary to completely mineralize p-NP isomers under nitrifying conditions. This study provides an important contribution to existing knowledge of nonylphenol biodegradation.

Introduction

Nonylphenol (NP) is a degradation product of nonylphenol polyethoxylates (NPEs), which are compounds that belong to the alkylphenol family and are used in the formulation of a large variety of lubricants, paints, detergents, pesticides and resins [1]. Due to the extensive use of NPEs, the amounts of NPs in sewage treatment systems are large enough to result in their incomplete degradation. The presence of NP has been widely reported in groundwater and surface waters, the atmosphere, sewage sludge-amended soils and food [2]. In addition, NP can have toxic and endocrine disrupting effect on wildlife and humans and its bioaccumulation in aquatic species is widely known [3]. Overall, NP is a hydrophobic compound (log K_ow = 4.48) that consists of a phenol ring with a hydroxyl group and a linear nonyl chain in the para-position. This chemical structure gives NP amphiphilic properties that allow NP to favor physicochemical interactions and sorption to different matrixes. Because of its persistence in the environment and its high endocrine disrupting effect, the removal of NPs is a priority concern.

The removal of NP in sewage treatment occurs through two main mechanisms, sorption and biodegradation. However, several studies of bioreactors show the removal rates of NP by simply considering the differences between the influent and effluent concentrations. Thus, the amounts of NP removed by the sorption and biodegradation processes remain unknown. Torres-Bojorges and Buitrón [4] found that the adsorption of NP onto biomass was significant, representing between 33 and 44% of the initial NPs. Other studies have reported that the removal of NP under aerobic, anoxic and anaerobic conditions [2]. However, oxygen appears to be particularly important for the complete mineralization of NPs [2]. Although the aerobic biodegradation of NPs has been largely discussed in pure cultures and activated sludge [2], [5], [6], [7], information regarding NP biodegradation under nitrifying conditions is scarce. Kim et al. [8] and Lee et al. [9] reported the degradation of NPs by nitrifying activated sludge. However, unclear information was provided regarding the amount of NPs adsorbed to the sludge. Nitrifying sludge resulted in the highest observed NP removal and degradation rate with a lower adaptation time compared with the acclimated 4-chlorophenol and activated sludge [4]. Several authors have shown that autotrophic nitrifying sludge can degrade natural and synthetic estrogens (ethinyl estradiol) and emerging micropollutants without an adaptation period [10]. The ability of autotrophic nitrifying sludge to cometabolize many low weight molecular organic compounds with heterotrophic microorganisms is catalyzed by the ammonium monooxygenase (AMO) enzyme [10], [11]. Moreover, the solids retention time (SRT) is an important parameter for improving the micropollutant removal efficiency from wastewater. High SRT contents can enrich slow growing specific degraders and allow microorganisms to adapt to micropollutants [12], [13]. For SRT values of less than 8 days, the removal of micropollutants is governed by sorption mechanisms [13]. Sequencing batch reactor (SBR) processes have demonstrated their efficiency and flexibility in the treatment of wastewaters with high concentrations of nutrients, nitrogen, phosphorous, and recalcitrant compounds from domestic and industrial sources [14]. That is possible because of the selection pressure applied to the biomass, due to the fill and draw regime, allowing the adaptation of microorganisms capable of degrading persistent and inhibitory compounds [15]. The SBR is a discontinuous process; nevertheless, by using two or more tanks, the process can be applied to continuous flow discharges [14]. It has been observed that high SRT can enrich slow growing specific degraders and allow microorganisms to adapt to micropollutants [12], [13]. An alternative to operate at high SRT is the use of a membrane reactor. The advantages of membrane and batch reactors can be obtained in a membrane sequence batch reactor (MSBR). This technology consists of using a submerged membrane in combination with a sequencing batch reactor (SBR) to achieve a solid–liquid separation [16]. The SBR is more versatile than a continuous reactor because it has wider flow capacities and can be used to help mitigate membrane fouling [17]. The combination of this type of reactor with a submerged membrane promotes a high sludge concentration relative to conventional activated sludge systems, which results in a greater microbiological concentration in the reactor [12]. Several authors have studied the biodegradation of p-NP isomers under aerobic conditions. However, not enough information exists regarding the intermediary metabolites of p-NP biodegradation under nitrifying conditions.

To assess NP removal mechanisms under nitrifying conditions at high SRT, a technical mixture of p-NP isomers was evaluated in a MSBR containing an enriched nitrifying sludge and without the addition of an organic carbon source. The p-NP concentrations were determined in the liquid phase and sludge to quantify the removal of NP by the biodegradation and sorption mechanisms. Additionally, the roles of ammonium-oxidizing and nitrite-oxidizing microorganisms on the biodegradation of p-NP were studied relative to the initial ammonium concentration and using allylthiourea as an AMO enzyme specific inhibitory agent. Finally, the presence of intermediary metabolites was studied using GC–MS analysis to enhance our knowledge regarding the biodegradation of p-NP under nitrifying conditions.

Section snippets

Nitrifying inoculum

The nitrifying biomass from an activated sludge collected from a municipal wastewater treatment plant was enriched in a SBR over 150 days in batch mode feeding the reactor once a day. The exchange volume was 75% of the total volume of the reactor. The acclimation cycles lasted one day and each of the phases lasting: 15 min (feeding); 23 h (reaction); 30 min (settling) and 15 min (decanting). The ammonia concentration was 300 mg N–NH₄⁺/L using a C/N ratio of 5 [18]. The mineral salt medium was prepared

Membrane filtration

According to the filtration tests described in Section 2.3, a critical flux of 66 L h⁻¹ m⁻² and an operation limit value of TMP of 44 ± 1.8 kPa were determined. When the TMP reached the operation limit value, the membrane underwent chemical cleaning. The membrane operation is shown in Fig. 2. During the 281 days of operation, the flux showed low variability with an average value of 23.6 ± 0.8 L h⁻¹ m⁻². Similarly, the membrane showed good performance throughout the experiment and only required six chemical

Conclusions

In this study, a nitrifying membrane sequence batch reactor was evaluated for the removal of p-NP isomers. Overall, the feasibility of efficiently removing p-NP under nitrifying conditions was demonstrated in an enhanced bioreactor. In addition, the biodegradation and sorption mechanisms were correctly differentiated, which indicated that biodegradation was the predominant mechanism of p-NP removal (62%). Furthermore, the results indicated that biodegradation is related to the

Acknowledgment

The authors gratefully acknowledge Jaime Perez Trevilla for providing technical assistance and DGAPA-UNAM for providing a postdoctoral fellowship to G. Cea.

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Removal of p-nonylphenol isomers using nitrifying sludge in a membrane sequencing batch reactor

Highlights

Abstract

Introduction

Section snippets

Nitrifying inoculum

Membrane filtration

Conclusions

Acknowledgment

Chemosphere

Chemosphere

Water Res.

Process Biochem.

Chemosphere

Water Res.

Chemosphere

Water Res.

Water Res.

J. Membr. Sci.

J. Membr. Sci.

Water Res.

J. Chromatogr. A

J. Chromatogr. A

Talanta

Water Res.

Water Res.

Water Sci. Technol.

Water Res.