Elsevier

Science of The Total Environment

Volume 673, 10 July 2019, Pages 719-725
Science of The Total Environment

Characteristics and mechanism of dimethyl trisulfide formation during sulfide control in sewer by adding various oxidants

https://doi.org/10.1016/j.scitotenv.2019.04.131Get rights and content

Highlights

  • Intermittent oxidants dosing for H2S control can lead to DMTS formation in sewer.

  • Enzymatic methylation of polysulfide was the pathway of DMTS formation.

  • Reduction of DMSO was another pathway of DMTS formation in the subsequent oxidant addition.

  • Alternative control methods for controlling both H2S and VSC should be considered.

Abstract

The addition of chemical agents to control the production of hydrogen sulfide (H2S) is currently the principal technology used to control odor emissions from sewers. In this study, laboratory reactors were used to investigate the change in dimethyl trisulfide (DMTS) concentrations when dosing with oxidant to control sulfide in sewers. Our results show that the intermittent addition of oxidant leads to sulfide regeneration and increased DMTS formation. Additional experiments were conducted to investigate the processes that result in the formation of DMTS. The results indicate that the polysulfide produced after oxidant addition was a key intermediate in DMTS production. Enzymatic methylation of polysulfide was an important process in DMTS formation. Dimethylsulfoxide (DMSO) was observed in the reactor when oxidant was again added but it was reduced to DMTS when the oxidant was depleted. There are side-effects of adding oxidant, and alternative control measures for volatile sulfur compounds (VSCs) need to be investigated further.

Introduction

Urban wastewater sewer systems collect and transport domestic sewage generated in residential neighborhoods and industrial wastewater. They are an important part of the urban infrastructure and fundamental to the recycling of urban water resources (Pikaar et al., 2014). However, microorganisms, which generate malodorous gases, such as sulfate-reducing bacteria (SRB), can colonize sewer sediment and conduit walls (Guisasola et al., 2008; Chen and Szostak, 2013; Eijo-Río et al., 2015; Liu et al., 2015a, Liu et al., 2015b, Liu et al., 2015c; Liu et al., 2016). Sewer odor is a notorious global problem in sewer management (Pikaar et al., 2014).

Hydrogen sulfide (H2S) is a well-known pollutant that corrodes sewers and creates undesirable odors (Æsøy et al., 2002; Vollertsen et al., 2008; Liu et al., 2016; Song et al., 2019). Several techniques have been used to mitigate the problems caused by H2S. The leading method adopted for H2S control has been dosage with chemical agents. The addition of nitrate has been proven to be effective and is widely used for sulfide control in sewers (Mathioudakis and Vaiopoulou, 2006; Mohanakrishnan et al., 2008; Ganigue et al., 2011; Jiang et al., 2013; Auguet et al., 2016). Other strong electron acceptors, such as H2O2, have been used as chemical sulfide oxidants to control H2S (Tomar and Abdullah, 1994). Ferric iron is frequently used as an electron acceptor to oxidize sulfide to elemental sulfur, and the Fe2+ generated in the oxidizing reaction can remove dissolved sulfide by forming FeS (Firer et al., 2008; Rebosura et al., 2018).

Volatile sulfur compounds (VSCs), such as methyl mercaptan, dimethyl sulfide, dimethyl disulfide (DMDS) and dimethyl trisulfide (DMTS), are also major odorants in sewers (Pandey et al., 2016; Sivret et al., 2016; Talaiekhozani et al., 2016; Jiang et al., 2017; Son, 2017). These VSCs have much lower odor threshold concentrations (OTC) than H2S (the OTC of some odorants in liquid phases are shown in Table S1), among which DMTS is a typical malodorous compound with an OTC of 10 ng/L (Wajon and Heitz, 1995; Heitz et al., 2000; Jiang et al., 2016). DMTS is produced during the degradation of organosulfur compounds, such as methionine, cysteine, and their derivatives methyl methionine and cysteine methyl ester, during anaerobic biodegradation (Smet et al., 1998; He et al., 2018). DMTS can also be formed by methylation of sulfides and oligosulfides (Franzmann et al., 2001; Zhou et al., 2017). However, the characteristics and mechanisms of DMTS formation in sewers after the addition of oxidants have not received much attention, and the effect of controlling H2S in sewers by the addition of oxidants on DMTS formation is not clear. We investigated the changes in DMTS concentration using three different oxidants when oxidant dosage was used for sulfide control. This paper is the first published report on DMTS formation when controlling H2S by intermittently adding an oxidant. Our main objectives were: a) to investigate the changes in DMTS concentration resulting from intermittently adding one of various oxidants to control H2S; b) to understand the mechanism of DMTS formation using simulated sewer reactors.

Section snippets

Experimental setup

Three cylindrical airtight containers each with a volume of 1.1 L (10 cm in diameter and 15 cm in height), named Reactor 1, Reactor 2 and Reactor 3, were used as reactors in the experiments (Fig. 1). The depth of the sediment in each reactor was about 3 cm, which is consistent with the ratio of sediment thickness to reactor height found in the literature (Liang et al., 2016). This ratio is also close to the value found in most sewers. The sediments used in this study were collected from a main

Effect of oxidants on sulfide and DMTS concentrations

Fig. 2 shows the changes in the concentrations of sulfide and DMTS before and after the addition of nitrate, H2O2 and FeCl3 oxidants in Reactors 1, 2 and 3. As shown in Fig. 2, the concentrations of sulfide in all three reactors first increased and then stabilized at 50–60 mg/L in Phase I. The sulfide concentrations in Phase I were much higher than those found in field studies reported in the literature (Chen and Szostak, 2013; Liu et al., 2015a, Liu et al., 2015b, Liu et al., 2015c; Liu et

Conclusions

The formation of DMTS during the control of H2S in a sewer system was simulated in a laboratory-scale reactor using intermittent oxidant dosing, with a variety of oxidants, as the method of control. Experiments were also conducted to investigate the activity of polysulfide and SRB in the formation of DMTS. The main findings are:

  • The intermittent addition of an oxidant to the sewer reactor leads to increased sulfide regeneration and DMTS formation.

  • Polysulfide, which is produced during the oxidant

Acknowledgments

The authors gratefully acknowledge support from the China Major Science and Technology Program for Water Pollution Control and Treatment (2017ZX07201) and the Key Special Program on the S&T of Zhejiang Province (2015C03015). We sincerely thank Professor Feng Jiang from the School of Chemistry & Environment, South China Normal University, Guangzhou, China for his support in this study.

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