Accepted Manuscript

Role of dissolved Mn(III) in transformation of organic contaminants: Non-oxidative

versus oxidative mechanisms

Erdan Hu, Ya Zhang, Shuyan Wu, Jun Wu, Liyuan Liang, Feng He

PII: S0043-1354(17)30013-1
DOI: 10.1016/j.watres.2017.01.013
Reference: WR 12614

To appear in: Water Research

Received Date: 23 October 2016

Revised Date: 14 December 2016
Accepted Date: 5 January 2017

Please cite this article as: Hu, E., Zhang, Y., Wu, S., Wu, J., Liang, L., He, F., Role of dissolved Mn(III)
in transformation of organic contaminants: Non-oxidative versus oxidative mechanisms, Water Research
(2017), doi: 10.1016/j.watres.2017.01.013.

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 ACCEPTED MANUSCRIPT

Graphic Abstract

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1 Role of dissolved Mn(III) in transformation of organic

2 contaminants: non-oxidative versus oxidative
3 mechanisms

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4 Erdan Hu1, Ya Zhang1, Shuyan Wu1, Jun Wu1, Liyuan Liang2, Feng He1,*

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5 College of Environment, Zhejiang University of Technology, Hangzhou 310014,

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6 China

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7 Environmental Molecular Sciences Laboratory, Pacific Northwest National
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8 Laboratory, Richland, WA 99352, USA

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12 Submission Date: 12/14/2016

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14 *Corresponding author: Phone: 86-571-88871509; Fax: 86-571-88871509; E-mail:

15 fenghe@zjut.edu.cn

16 (Emails: Erdan Hu, huerdan@zjut.edu.cn; Ya Zhang, yazhangsyf@163.com; Shuyan

17 Wu, wsy801006@163.com; Jun Wu, wujun@zjut.edu.cn; Liyuan Liang,
18 liyuan.liang@pnnl.gov; Feng He, fenghe@zjut.edu.cn)
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21 Abstract

22 Mn(III) is a strong oxidant for one electron transfer, which may be important in the

23 transformation of organic contaminants during water/wastewater treatment and

24 biogeochemical redox processes. This study explored the reaction mechanisms of

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25 dissolved Mn(III) with organics. The role of dissolved Mn(III) either as a catalyst or

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26 an oxidant in reactions with organics was recognized. Aquo and/or hydroxo (or free)

27 Mn(III), generated from the bisulfite activated permanganate process, facilitated

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28 efficient N-dealkylation of atrazine via a β-elimination mechanism, resulting no net

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29 redox reaction. In contrast, free Mn(III) degraded 4-chlorophenol via intramolecular
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30 redox processes, the same as hydroxyl radical (·OH), resulting in dechlorination, OH

31 substitution, ring-opening and mineralization. Mn(III)-pyrophosphate compounds did

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32 not react with atrazine because complexation by pyrophosphate rendered Mn(III)

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33 unable to bond with atrazine, thus the electron and proton transfers between the
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34 reactants couldn’t occur. However, it degraded 4-chlorophenol at a slower rate

35 compared to free Mn(III), due to its reduced oxidation potential. These results showed
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36 two distinct mechanisms on the degradation of organic contaminants and the insights
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37 may be applied in natural manganese-rich environments and water treatment

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38 processes with manganese compounds.

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40 Keywords: trivalent manganese organic∣contaminants non-oxidation oxidation

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44 1. Introduction

45 Manganese is an important element in environmental processes and in catalytic

46 materials due to its rich redox chemistry and ability to form species of high catalytic

47 activity (Duan et al., 2015; Hocking et al., 2011; Johnson et al., 2016; Palucki et

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48 al.,1998; Sun et al., 2015). The most stable and prevalent forms of manganese are

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49 Mn(IV) and Mn(II), which have received great attention in Mn biogeochemical

50 studies (Herszage and dos Santos Afonso, 2003; Huynh et al., 2015; Johnson et al.,

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51 2016; Luther et al., 2005; Marafatto et al., 2015). Since the electron acceptance and

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52 donation are spatially distinct in the dz2 and dx2–y2 orbitals of Mn(IV) and Mn(II),
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53 one-electron transfer can occur in the reduction of Mn(IV) or oxidation of Mn(II),

54 with intermediates as Mn(III) (Johnson et al., 2016; Luther et al., 2005; Morgan, 2005;
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55 Zhang et al., 2008).

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56
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57 Natural sources of soluble Mn(III) include phytoplankton decomposition in the

58 photosynthetic processes (Webb, 2005), biotic or abiotic oxidation of Mn(II) to

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59 Mn(IV) (Duckworth et al., 2005; Morgan, 2005; Parker et al., 2004; Webb, 2005),
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60 microbial (Lin et al., 2012; Myers and Nealson, 1988), photochemical (Marafatto et
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61 al., 2015) and chemical reduction of Mn oxides with sulfide (Johnson et al., 2016),

62 Cr3+ (Nico and Zasoski, 2000) and organics such as ethylenediaminetetraacetate

63 (Klewicki and Morgan, 1999), triclosan (Zhang and Huang, 2003) and oxalate (Xyla

64 et al., 1992), and nonreductive ligand-promoted dissolution of Mn(III) containing

65 minerals (Duckworth and Sposito, 2005; Klewicki and Morgan, 1999). Recently,

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66 aqueous Mn(III) species have been directly detected in suboxic regions of oceanic

67 environments (up to 5 µM and at 100% of the total dissolved Mn) and estuary

68 sediment pore waters (up to 90% of the dissolved Mn) (Dellwig et al. 2012; Madison

69 et al., 2013; Oldham et al., 2015; Trouwborst et al., 2006; Wang and Giammar, 2015;

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70 Yakushev et al., 2009). These findings demonstrate that Mn(III) is a major component

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71 of dissolved Mn at oxic/anoxic interfaces in the environments. Mn(III) also exists at

72 (sub)nanomolar concentration in oxic waters of lakes and oceans, as has been found

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73 for Fe(III) (Trouwborst et al., 2006). Given its ubiquitous and abundant presence in

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74 natural waters in comparison to 10 − 16 − 10 − 15 M of ·OH (He et al., 2014;
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75 Schwarzenbach et al., 2003), one of the most common oxidative species in surface

76 waters), the role of Mn(III) in organic cycling may have been overlooked.
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77
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78 Aqueous Mn(III) ion, Mn3+(aq), is a strong Bronsted acid. Two hydrolysis products
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79 of monomeric Mn3+ have been reported at very low pH solutions with ionic strength

80 of 3 M (Biedermann and Palombari, 1978):

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81 Mn3+ + H2O = Mn(OH)2+ + H+ log*β1 = 0.4 ± 0.1 (1)

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82 Mn3+ + 2H2O = Mn(OH)2+ + H+ log*β2 = 0.1 ± 0.1 (2)

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83 Due to its tetragonally distorted electron configuration, free Mn(III) is labile and

84 susceptible to disproportionation to Mn(II) and Mn(IV) according to the following

85 reaction (Davies, 1968):

86 2Mn3+(aq) + 2H2O = MnO2(s) + Mn2+(aq) + 4H+ log K ~ 7-9 (3)

87 Disproportionation of Mn3+ is spontaneous and rapid, so Mn3+ and its hydrolysis

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88 products have short life (seconds) in aqueous solution (Davies, 1968). However, free

89 Mn(III) can be stabilized through complexation with high affinity ligands, such as

90 pyrophosphate (PP), oxalate, citrate, and siderophores, which are widely present in

91 natural aquatic and soil systems (Duckworth and Sposito, 2005; Klewicki and Morgan,

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92 1998; Parker et al., 2004; Wang and Stone, 2008). With a smaller atomic radius and

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93 higher electrostatic charge, Mn(III) complexes are even more stable than Mn(II)

94 complexes (Duckworth et al., 2009).

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95

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96 Mn(III) is a strong and important oxidant for one electron transfer reactions
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97 (equations 4 and 5) (Kostka et al., 1995), it could play important roles in water

98 treatment and biogeochemical redox processes.

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99 Mn3+ + e- Mn2+ E0 = +1.51 V (4)

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100 MnOOH + 3H+ + e- Mn2+ + 2H2O E0 = +1.50 V (5)

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101 Mn(III) oxides or complexes are able to rapidly oxidize a variety of organics

102 including ethylenediaminetetraacetic acid (EDTA) (McArdell et al., 1998),

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103 nitrilotrismethylenephosphonic acid (NTMP) (Nowack and Stone, 2002), phenol

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104 (Nico and Zasoski, 2001), and citrate (Klewicki and Morgan, 1999). Mn(III) centers
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105 on the surface of Mn oxides are also involved in the redox processes of Mn minerals

106 (Li et al., 2015; Nico and Zasoski, 2001; Simanova and Peña, 2015). A recent study

107 demonstrated that addition of oxalate could dramatically accelerate the oxidative

108 degradation of carbadox (C11H10N4O4) by MnO2, as the reaction of MnO2 and oxalate

109 can produce dissolved Mn(III) (Chen et al., 2013). Additionally, during Mn(VII)

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110 oxidation of triclosan (TCS) and bisphenol A (BPA), dissolved Mn(III) was also

111 identified as an intermediate and considered to enhance the reaction rate (Jiang et al.,

112 2010; Jiang et al., 2012).

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114 As soluble, free Mn(III) are unstable under typical environmental conditions, up to

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115 now, most of the studies on transformation or interaction of organic contaminants with

116 Mn(III) have been performed with long-lived Mn(III) species, including Mn(III)-rich

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117 MnO2 (Li et al., 2015; Nico and Zasoski, 2000; Zhang and Huang, 2003), naturally

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118 occurring Mn(III/IV) oxides (Jun and Martin, 2003; McArdell et al., 1998; Stone,
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119 1987), and soluble Mn(III) complexes (Kostka et al., 1995; Wang et al., 2013).

120 Although dissolved Mn(III) species have been anticipated as a potential

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121 environmental oxidant, their reactivity and kinetic characteristics are not fully
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122 appreciated or understood. Recently, Sun et al. (2015) reported that soluble free
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123 Mn(III) (including aquo and hydroxo Mn3+, i.e., only complexed with H2O and OH−)

124 could be generated in permanganate reduction by bisulfite, serving as a strong oxidant

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125 for extremely rapid (40-80 ms) degradation of organic contaminants at micromolar
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126 concentration. However, the interaction mechanism of organic contaminants with free
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127 Mn(III) has not been studied. It remains unknown if the extraordinarily fast reaction

128 of Mn(III) with organics is caused by its strong oxidative capability. Even for

129 reactions of Mn(III) complexes with organics, only simple oxidation mechanism was

130 assumed. In addition, although numerous studies have shown that dissolved Mn(III)

131 intermediates can significantly accelerate the degradation of organic compounds by

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132 Mn oxides, the role of Mn(III) remains unclear.

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134 This study was conducted to explore the reaction mechanism of dissolved Mn(III)

135 with organics, with an aim to explain the differences in reaction rates and pathways

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136 between organics and various manganese species. Specifically, two typical organics,

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137 atrazine and 4-chlorophenol , which are common pollutants in soil, surface water, and

138 groundwater, were selected as the model reactants to probe effects of molecular

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139 structure of the organics in the interaction with dissolved Mn(III). Free Mn(III) was

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140 generated by permanganate/bisulfite (PM/BS) process (Sun et al., 2015). Degradation
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141 of atrazine and 4-chlorophenol by free Mn(III) and Mn(III)-pyrophosphate

142 (Mn(III)-PP) compound was investigated, and compared with the most common
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143 oxidant hydroxyl radical (·OH). The use of free Mn(III) and Mn(III)-PP allows us to
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144 study Mn(III) as a catalyst or oxidant or both. The results make a new breakthrough
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145 on the reaction mechanism of Mn(III) with organics and can provide a better

146 understanding on the degradation of organic contaminants in natural manganese-rich

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147 environments and in water treatment processes using manganese compounds.

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148
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149 2. Materials and Methods

150 2.1. Chemicals

151 Potassium permanganate (99.5%) and sodium thiosulfate pentahydrate (greater than

152 99.0% purity) were purchased from the Xiaoshan Chemical Reagent Co., Ltd.

153 (Zhejiang, China); sodium bisulfite (AR grade) was obtained from Shisihewei

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154 Chemical Reagent Co., Ltd. (Shanghai, China); ferrous sulfate (FeSO4·7H2O, AR

155 grade) and hydrogen peroxide (30.0%, AR grade) were supplied by the Sinopharm

156 Chemical Reagent Co., Ltd. (Shanghai, China); atrazine (greater than 99.0% purity)

157 was purchased from Yiji Chemical Reagent Co., Ltd. (Shanghai, China); sodium

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158 pyrophosphate (PP, AR grade) and 4-chlorophenol (AR grade) were obtained from

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159 Aladdin Reagent (Shanghai, China); 1,4-benzoquinone (99.0%), hydroquinone

160 (99.5%), 1,2,4-trihydroxybenzene (99.0%), maleic acid (99.0%), salicylic acid

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161 (99.0%), 2,3-dihydroxybenzoic acid (99.0%), 2,5-dihydroxybenzoic acid (99.0%), and

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162 catechol (99.0%) were obtained from J&K Scientific Ltd. (Beijing, China); ammeline
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163 (98.0%) was obtained from Dr. Ehrenstorfer (Augsburg, Germany);

164 deethydeisopropylatrazine (98.0%) was obtained from AccuStandard (New Haven,

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165 U.S.). HPLC grade methanol was supplied by CNW Technologies (Dusseldorf,
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166 Germany). All chemicals were used as received. The standard mixtures for instrument
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167 calibration were prepared from the single-compound solutions in methanol.

168 Laboratory distilled, deionized water (resistivity of 18.2 MΩ·cm) was used in
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169 preparation of all aqueous solutions. All samples were stored at 4 °C in the dark, and
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170 analyzed within 2 weeks (aqueous-based samples were analyzed within 2 days). The
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171 stock solution of NaHSO3 (50.0 mM), Na2S2O3 (50.0 mM), and FeSO4 (50.0 mM)

172 were freshly prepared for each set of experiments to avoid oxidation by oxygen. The

173 solutions were adjusted to the target pH levels by adding H2SO4 or NaOH.

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175 2.2. Experimental Procedures

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176 The kinetic experiments were conducted in a 250 mL glass beaker open to the air.

177 Free Mn(III) was generated by permanganate/bisulfite (PM/BS) process as previously

178 developed by Sun et al.(2015) Reactions were initiated by quickly adding NaHSO3

179 and KMnO4 into the solution containing the test organics (atrazine or 4-chlorophenol),

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180 with NaHSO3 at a 5-fold excess. ·OH was generated by Fenton process, with FeSO4

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181 and H2O2 at a mole ratio of 2:1. Permanganate alone as oxidant was also performed

182 for comparison. The constituents were mixed with a magnetic stirrer. At

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183 predetermined time intervals, 1.0 mL of sample was rapidly transferred into a 10 mL

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184 glass bottle and immediately quenched with 100 µL of 50 mM thiosulfate for Mn(III)
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185 and KMnO4 or 1 mL of methanol for ·OH. Previous study has shown that Mn(III)

186 couldn’t be produced in the reduction of permanganate by thiosulfate (Sun et al.,

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187 2016). The resulting solutions were filtered (0.22 µm) and then analyzed.
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188
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189 To determine the dechlorination and mineralization of atrazine and 4-chlorophenol

190 in the presence of Mn(III) or ·OH, a series of atrazine (139.5 µM) and 4-chlorophenol
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191 (390.6 µM) were reacted with Mn(III) or ·OH for five cycles. Specifically, 500 µM of
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192 NaHSO3 and 100 µM of KMnO4 were added to the test solutions every five minutes
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193 to investigate the mineralization ability of Mn(III), while for ·OH, 200 µM of FeSO4

194 and 100 µM of H2O2 were added every ten minutes. Samples were collected after each

195 reaction cycle, filtrated and analyzed for total organic carbon (TOC) and chloride

196 ions.

197

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198 2.3. Chemical Analysis

199 The identification and quantification of atrazine, 4-chlorophenol and their

200 degradation intermediates were accomplished using ultra-performance liquid

201 chromatography/tandem mass spectrometry (UPLC/MS/MS) on a Xevo-TQS triple

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202 quadruple mass spectrometer (Waters, U.S.). For atrazine, the positive electrospray

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203 ionization mode (ESI+) was used and for 4-chlorophenol we used negative

204 electrospray ionization mode (ESI-). Aliquots of 5 µL were injected into an Acquity

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205 BEH C18 analytical column (50 mm × 2.1 mm, 1.7 µm) maintained at 40 oC using

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206 isocratic methanol/water (70:30, v/v) at 0.2 mL/min and the total run time was 3.0
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207 min for both atrazine and 4-chlorophenol. Detection was carried out in multiple

208 reaction monitoring (MRM) mode for atrazine and selective ion reaction (SIR) mode
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209 for 4-chlorophenol. The MRM mode was not suitable for detection of 4-chlorophenol
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210 and its degradation products as their daughter ions are too small (MW< 80 Da.) and
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211 easy to be interfered by the background. The tune page parameters and conditions

212 (Table S1 and S2, Supporting Information) for each of the MRM and SIR transitions
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213 were optimized by infusing neat standard solutions of the individual analytes (1 mg
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214 L-1) into the mass spectrometer at 10 µL min-1. Quantification of all target analytes
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215 was based on external calibration using mixed standard solutions.

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217 The UV-Vis absorbance spectrum of the Mn(III)-PP compound was determined

218 with a TU-1810PC UV spectrophotometer (Purkinje, Beijing, China) by scanning

219 from 200 to 800 nm as compared to a blank of distilled, deionized water. Absorbance

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220 at 260 nm was used to monitor the Mn(III)-PP concentration unless otherwise

221 indicated.

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223 The concentration of hydroxyl radicals generated by Fenton’s reaction was

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224 determined by an HPLC method (Jen et al., 1998). The hydroxyl radicals were

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225 generated, and then trapped by salicylic acid. A UV detector was used to monitor the

226 hydroxylated derivatives and salicylic acid after they had been separated with HPLC.

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227 From the total concentration of hydroxylated derivatives, the hydroxyl radicals used

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228 for hydroxylation can be obtained, and the formation of hydroxyl radicals under the
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229 specified conditions can be estimated. Standard stock solutions (100 mg L-1) of

230 salicylic acid, 2,3-dihydroxybenzoic acid (2,3-dHBA), 2,5-dihydroxy benzoic acid

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231 (2,5-dHBA) and catechol were prepared by dissolving them in distilled, deionized
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232 water. All of the solutions were stored in brown glass bottles, and kept in a 4 oC
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233 refrigerator for a maximum of two weeks. Fresh working solutions were prepared

234 daily by appropriate dilution of the stock solutions. The generation and trapping
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235 of ·OH radicals was achieved by introducing 1 mL of a 5 mM H2O2 solution (pH 3.5)
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236 into 50 ml reaction vessels containing appropriate amounts of salicylic acid and 200
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237 µM of ferrous ion. Samples were then taken for HPLC analysis at various time

238 intervals throughout the reaction process. HPLC analyses were performed on an

239 Agilent 1260 equipment (Agilent Technologies, Palo Alto, California, U.S.). The

240 VWD detector was set at 296 nm. 20 µL of samples were injected and separated by an

241 Agilent Zorbax Eclipse Plus-C18 column (100 × 4.6 mm, particle size 3.5 µm). A

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242 mixture of methanol and 0.3 M acetic acid (60:40, v/v) was used as the mobile phase

243 and performed at the isocratic elution with a flow rate of 1.0 mL/min.

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245 Total organic carbon (TOC) was measured by a TOC analyzer (Shimadzu TOC-L

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246 CPH CN 200, Japan) equipped with an auto sampler. Chloride concentration was

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247 measured using an ICS-1000 ion chromatography system (Dionex, Sunnyvale, CA)

248 equipped with a IonPac AS11 analytical (4 mm × 250 mm) column. A 38 mM sodium

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249 hydroxide (NaOH) solution was used as the eluent with a flow rate of 1.0 mL/min.

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250
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251 3. Results and Discussion

252 3.1. Non-oxidative reaction of atrazine with free Mn(III)

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253 To investigate the degradation mechanism of atrazine with Mn(III) and ·OH (the
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254 most common oxidant in the environment for comparison), the generation of free
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255 Mn(III) and ·OH in corresponding NaHSO3-KMnO4 and Fenton processes was

256 quantified first. As free Mn(III) and its hydrolysis products have short lifetimes
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257 (seconds) in aqueous solution due to rapid disproportionation, PP was chosen to trap
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258 Mn(III) by forming stable Mn(III)-PP complex (logKa of 31.35 at pH = 8). The same
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259 method has been used to quantify the free Mn(III) generated in permanganate/bisulfite

260 process in the previous study (Sun et al., 2015). Mn(III)-PP can be easily quantified

261 by UV-vis spectrophotometry (λ1 = 480 nm, ε1 = 65 M-1; λ2 = 258 nm, ε2 = 6,750 M-1)

262 (Webb et al., 2005). The absorption spectrum of Mn(III)-PP exhibited a main peak at

263 260 nm, which is the characteristic of electron transition from the ligand to the central

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264 Mn(III) ion (Michalkiewicz and Malyszko, 2000). The generation of Mn(III) was very

265 rapid and the absorption intensity of Mn(III)-PP kept constant once the

266 KMnO4-NaHSO3 process initiated (Figure S1(a)). Previous stop-flow experiments

267 have suggested that generation of Mn(III) in KMnO4-NaHSO3 process completed

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268 within 0.2 s (Sun et al., 2015). The concentration of Mn(III)-PP calculated from the

peak intensity at 260 nm and its molar absorption coefficient (6,750 M-1) was about

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270 85.9 µM, when the initial concentrations of KMnO4 and NaHSO3 were 100 µM and

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271 500 µM, respectively.

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272 It is noteworthy that time-resolved spectroscopy of manganese species in the
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273 permanganate/bisulfite process has demonstrated that free Mn(III) increased sharply

274 and formed a peak at ~10 ms, while the absorbance of Mn(III)-PP complex peaked at
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275 0.2 s (Sun et al., 2015). Therefore, PP cannot change the reaction pathways in
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276 permanganate/bisulfite process. Our additional experiments showed that increasing PP

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277 concentration after it was sufficient to trap all the free Mn(III) did not result in the

278 change of Mn(III)-PP absorbance at 260 nm (Figure S2), further suggesting that the
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279 addition of PP did not affect the generation of free Mn(III) in permanganate/bisulfite
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280 process.
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281 The production of ·OH in the Fenton process followed a second-order kinetics (k =

282 0.15 µM· s-1) (Figure S1(b)), and reached equilibrium around 480 s with a maximum

283 concentration of 79.4 µM, when the initial concentrations of H2O2 and FeSO4 were

284 100 µM and 200 µM, respectively. Therefore, the molar concentration of free Mn(III)

285 produced in the process of NaHSO3 activated KMnO4 and that of ·OH generated from

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286 the Fenton process was comparable in this study.

287

288 The rates of atrazine degradation with free Mn(III) and ·OH are compared in Figure

289 1a. To avoid the generation of Mn(IV) species, the pH was adjusted to 3.5, which had

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290 no obvious change during the degradation processes. Atrazine degradation with

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291 Mn(III) was extremely fast. About 80% of atrazine disappeared within 5 s, and no

292 further degradation was observed with prolonged time, indicating that the reaction of

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293 free Mn(III) with atrazine completed within 5 s or less. This may be due to the very

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294 rapid generation of large amount of free Mn(III), as suggested by the time-resolved
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295 spectroscopy measurements (Sun et al., 2015). Degradation of atrazine with ·OH

296 followed a pseudo first-order kinetics (k = 0.008 s-1) achieving atrazine removal of
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297 75% within 180 s. The degradation rate then slowed down and more than 95% of
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298 atrazine were degraded after 600 s, which followed the ·OH generation kinetics
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299 (Figure S1b).

300
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301 The degradation products of atrazine with free Mn(III) and ·OH were identified by
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302 UPLC/MS/MS. Mn(III) facilitated the efficient N-dealkylation of atrazine, producing

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303 mono and didealkyl atrazine (deethylatrazine (DEA), deisopropylatrazine (DIA), and

304 deethyldeisopropylatrazine (DDA)). There was no evidence for replacement of the

305 ring Cl by OH under our reaction conditions. When atrazine reacted with ·OH, the

306 degradation products were more complex. The major products were hydroxyatrazine,

307 DEA, DIA, DDA meanwhile ammeline and cyanuric acid were also detected. The two

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308 relatively stable products DDA and ammeline were quantified, as shown in Figure 1b

309 and 1c. In the presence of Mn(III), DDA accumulated rapidly to a peak concentration

310 in the first 5 s, consistent with the rapid generation of Mn(III). Unlike with Mn(III),

311 during the degradation of atrazine by ·OH the production of DDA and ammeline were

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312 both detected and with comparable concentrations. The amounts of these two

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313 relatively stable products increased gradually and reached a maximum at 600 s.

314

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315 The degradation pathways were further investigated by measuring the chloride and

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316 TOC removal (Fig. S3). Measurements of Cl- at the end of the each reaction cycle
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317 showed no obvious chloride removal over five reaction cycles with Mn(III), while the

318 dechlorination rate by ·OH was increased gradually from 37% to 60% and almost
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319 remained constant after three reaction cycles. We can infer that dechlorination
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320 occurred at the early stage of atrazine degradation with ·OH, as the C–Cl bond is
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321 relatively weak (331 kJ/mol) and Cl- is a good leaving group (i.e., more susceptible to

322 be cleaved than any other bonds) (Chen et al., 2009). This also explains that treatment
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323 of atrazine by advanced oxidation processes typically yields

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324 dechlorination-hydroxylation products first (Chen et al., 2009; Konstantinou et al.,

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325 2001). It is surprising that during degradation of atrazine by Mn(III), the

326 dechlorination did not happen, with only N-dealkylation occurred. Therefore, we

327 deduce that the reaction between Mn(III) and atrazine may proceed via a nonredox

328 pathway or Mn(III) may have a high selectivity toward the alkylamine functional

329 group of atrazine. Since the amount of Mn(III) was more than 100-fold excess of

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330 atrazine in this study, the reaction selectivity could be excluded.

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332 The TOC removal gradually increased from 1% to 13% in the presence of Mn(III)

333 during the five reaction cycles, and from 0.8% to 31% for ·OH. Degradation of the

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334 major relatively stable intermediate product DDA by Mn(III) and ·OH was also

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335 conducted and the results are shown in Fig. S4. DDA was almost not degraded by

336 Mn(III). In contrast, more than 60% of DDA could be degraded by ·OH within 300 s.

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337 Therefore, we conclude that DDA is the final stable product of atrazine degradation in

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338 the presence of Mn(III). The TOC removal (with maximum of 13%) was from the
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339 volatilization or subsequent oxidation of the alkyl side chains (i.e., ethene), which

340 contain 62.5% of the total C. As a comparison, ring cleavage and further oxidation
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341 occurred in the presence of ·OH which has a higher oxidation potential (E = +2.38 V
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342 at pH 3.0) than Mn(III) (Bossmann et al., 1998). The non-oxidation mechanism
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343 between Mn(III) and atrazine was further evidenced by the reaction of atrazine with

344 KMnO4 (E = +1.70 V at pH 3.5) (Damm et al., 2002), which has a relatively higher
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345 oxidation potential than Mn(III). As shown in Fig. S5, KMnO4 showed little reactivity
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346 with atrazine. Only 25% of atrazine (0.47 µM) was degraded after reacting with
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347 KMnO4 for 3 min (Figure S5(a)). When atrazine at elevated concentration (139.5 µM)

348 reacted with KMnO4, 16% of the total chloride was removed while mineralization

349 was minimum (Figure S5(b)). After 5 cycles of reaction, Cl removal remained the

350 same and the TOC removal was increased to 8%, demonstrating that dechlorination

351 was the main reaction pathway with Mn(VII). Hence, we deduce that degradation of

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352 atrazine with Mn(III) was not an oxidative process like that with KMnO4.

353

354 To further clarify the reaction mechanism of atrazine with Mn(III), UV-vis

355 measurements under different conditions were performed. In this case, 100-fold

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356 excess PP than atrazine was added into the solution with atrazine and NaHSO3 before

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357 the addition of KMnO4. Time-resolved spectroscopy of manganese species under

358 various conditions has confirmed that Mn(III) initially formed in the

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359 permanganate/bisulfite process reacts with organics more rapidly than it complexes

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360 with PP, and both reactions are faster than the disproportionation of Mn(III) (Sun et al.,
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361 2015). This suggests that PP can only trap the Mn(III) that is not initially consumed

362 by the contaminants before its disproportionation. Our additional experiments

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363 demonstrated that PP with concentration below 400-fold excess than atrazine
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364 exhibited no effect on the degradation of atrazine (i.e., same as the case of without PP,
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365 Figure S6). This further suggests that the PP we added couldn’t compete with the

366 contaminants for the newly generated free Mn(III).

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367 As illustrated in Figure 2, after interaction with Mn(III) in the absence of PP, the
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368 intensity of the absorption band at ~214 nm, corresponding to atrazine decreased.
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369 Because the N-dealkylation products of atrazine still have UV-vis absorbance at the

370 absorption region of atrazine, atrazine removal couldn’t be quantified by the UV-vis

371 absorbance. Atrazine removal rate determined by UPLC/MS/MS was 67.8% when the

372 initial concentration of atrazine was 23.3 µM. The atrazine removal rate remained the

373 same in the presence of PP. However, the intensity of the absorption bands at ~260 nm

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374 corresponding to Mn(III)-PP complex had no significant change with or without

375 atrazine, indicating that Mn(III) was not consumed during atrazine degradation and

376 trapped by PP afterwards (Figure 2). When the initial concentration of atrazine

377 increased to 46.6 µM, about 61.4% of atrazine was removed; the UV-Vis absorbance

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378 of Mn(III)-PP still remained almost unchanged with or without atrazine (Figure S7).

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379 In this sense, Mn(III) acted as a catalyst rather than an oxidant. This further confirmed

380 that Mn(III) and atrazine reacted via a nonredox pathway.

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381

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382 Figure 3 depicts the proposed degradation pathways of atrazine by Mn(III), which
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383 is different from that with ·OH (Fig. S8). It is known that atrazine, with

384 electron-abundant ring-N and amino groups, has a high tendency for electron transfer
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385 reactions (Welhouse and Bleam, 1993). A possible first step in the transformation
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386 reaction could be coordination of Mn(III) to the amine substituents of atrazine via its
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387 lone pair to form an N–Mn(III) bridge. The terminal OH ligands of Mn(III) or water

388 molecules can then attract a proton from the β-carbon of the N-bound alkyl group.
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389 Subsequent β-elimination of the alkylamine is promoted by imido N=Mn(III) double

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390 bond formation as Mn(III) can form double bonds with O or N ligands by accepting π
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391 electrons into its empty d orbitals (Uhrecký et al., 2015). The –HN=Mn-OH fragment

392 then rearranges to -H2N-Mn=O, and dissociation of the bound amine completes the

393 dealkylation reaction. Therefore, electrons and protons are shuttled transiently via the

394 Mn(III) with no net redox reaction. The products of atrazine degradation with Mn(III)

395 were consistent with those found during atrazine degradation by δ-MnO2 in an earlier

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396 work (Shin and Cheney, 2005), which also catalyzed a nonredox reaction of the

397 adsorbed atrazine, producing dealkylated products of DEA, DIA, and DDA as well as

398 heat (exothermic reaction), with no soluble manganese released.

399 Organics with functional groups that have lone pair electrons such as N or O could

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400 bond with Mn(III). If the Mn(III) bonding groups have hydrogens on the β-carbon, the

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401 organics could be degraded by Mn(III) via a β-elimination mechanism with no net

402 redox reaction. Degradation of another triazine herbicide ametryn by free Mn(III) and

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403 KMnO4 was also conducted, it exhibited the same pattern as atrazine (Figure S9). The

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404 degradation products identified by UPLC/MS/MS were also N-dealkylation products.
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405 So we deduce that this non-oxidative mechanism may be applied to some other

406 organic contaminants with similar functional groups like atrazine.

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407
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408 3.2. Oxidative reaction of 4-chlorophenol with free Mn(III)

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409 The degradation of 4-chlorophenol by free Mn(III) and ·OH and the formation of

410 major degradation products during the processes are shown in Figure 4. Both Mn(III)
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411 and ·OH can rapidly degrade 4-chlorophenol, but the degradation patterns were quite
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412 different. 4-chlorophenol completely disappeared within 5 s and 180 s, respectively,

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413 in the presence of Mn(III) and ·OH. The kinetics of 4-chlorophenol degradation by

414 Mn(III) was too rapid to obtain while its degradation by ·OH followed a pseudo

415 first-order kinetics (k=0.056 s-1).

416

417 The degradation pathways of 4-chlorophenol by Mn(III) and ·OH were further

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418 studied by tracking the formation and destruction of the degradation intermediates

419 with UPLC/MS/MS (Figure 4b,c). The major products were hydroquinone,

420 1,2,4-trihydroxybenzene, and 4-chlorocatechol either with Mn(III) or ·OH, although a

421 minor product, maleic acid, was also detected in the ·OH process. This indicates

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422 that ·OH substitution is the main mechanism of 4-chlorophenol degradation either

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423 with Mn(III) or ·OH. Chloride measurements showed that about 12% of Cl was

424 removed after first reaction cycle with Mn(III) and remained the same for five cycles

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425 (Figure S10(a)). While for ·OH, the dechlorination rate increased from 23% to 58%

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426 over five reaction cycles. The TOC removal increased from 5% to 22% for Mn(III)
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427 and from 8% to 33% for ·OH over the five reaction cycles (Figure S10(b)). These

428 results suggest that 4-chlorophenol degradation by Mn(III) was via an oxidation
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429 mechanism (i.e., dechlorination, OH substitution, and further degradation through

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430 ring-opening and mineralization), the same as by ·OH. The mineralization of

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431 4-chlorophenol with ·OH was about 1.5 times higher than that with Mn(III). This is

432 mainly because ·OH has a much higher oxidation capacity than Mn(III). It is
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433 interesting that KMnO4, which hardly degrades atrazine, can completely oxidize
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434 4-chlorophenol within 5 s, and the dechlorination and mineralization efficiency were
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435 about 1.5 ~ 2 times higher than Mn(III) (Figure S11). Thus the reactions of Mn(III)

436 with atrazine and 4-chlorophenol appear to proceed via two different mechanisms.

437

438 The oxidation mechanism of 4-chlorophenol with Mn(III) was further investigated

439 by UV-vis absorption spectra (Figure 5). After interaction with Mn(III),

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440 4-chlorophenol was rapidly and completely removed, with the absorption band of the

441 Mn(III)-PP complex (260 nm) disappeared simultaneously, indicating that Mn(III)

442 was consumed during the 4-chlorophenol degradation. This is in sharp contrast to the

443 Mn(III)-PP pattern during atrazine degradation, further suggesting the two different

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444 reaction mechanisms.

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445

446 Because one of the LUMO orbitals (eg*) of Mn(III) is not occupied, a geometry

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447 change towards square planar can occur, which is known as the Jahn-Teller effect

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448 (Stone and Morgan, 1984; Xyla et al., 1992). One electron transfer with free radical
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449 generation for organic reductants is expected in Mn(III) redox reactions (Nowack and

450 Stone, 2002; Snider, 1996; Stone and Morgan, 1984; Xyla et al., 1992;). On the basis
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451 of previous studies (Stone, 1987; Zhang and Huang, 2003) and new results from this
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452 study, we propose the following pathway for 4-chlorophenol degradation by Mn(III)
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453 (Figure 6). The ring position was attacked preferentially by Mn(III) as Mn(III) species

454 are electrophilic (Pandey et al., 2015), and the –Cl on the ring was substituted by OH,
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455 yielding hydroquinone. This is likely due to that the p-Cl substituent of chlorophene is
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456 susceptible to substitution by hydroxide as it is weakly electron withdrawing (Zhang

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457 and Huang, 2003), and consequently increases the variety of product formation.

458 Meanwhile, the –H on the ring can also be substituted by OH. The OH substitution

459 products can be further transformed through a multistep process including

460 hydroxylation, ring-opening and mineralization to CO2.

461

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462 3.3. Reactions of atrazine and 4-chlorophenol with Mn(III)-PP

463 Figure 7 shows the degradation of atrazine and 4-chlorophenol by Mn(III)-PP

464 complex. The Mn(III)-PP complex was obtained by adding 50 times excess of PP and

465 allowed to react for 1 h to completely trap the free Mn(III) in the

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466 permanganate/bisulfite process before the addition of contaminants. Previous studies

have shown that one to one pairing complex MnHP2O7 (K = 5 × 1011) should yield

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467

468 the major complex species between Mn(III) and pyrophosphate (Nico and Zasoski,

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469 2000). Therefore, the amount of pyrophosphate was sufficient enough to complex all

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470 of the Mn(III) generated. After complexed by pyrophosphate, Mn(III) showed almost
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471 no reactivity to atrazine. This is because the empty d orbitals of Mn(III) were

472 occupied by the O of pyrophosphate. As a result, the N–Mn(III) bridge between

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473 atrazine and Mn(III) couldn’t form and therefore the electron and proton transfers
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474 between them couldn’t happen. However, 85% of the 4-chlorophenol could be
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475 degraded within 180 s when reacted with Mn(III)-PP complex, indicating that

476 Mn(III)-PP complex could oxidize 4-chlorophenol, although at a slower rate than free
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477 Mn(III) (completely degraded within 5 s). This is due to the lower oxidation potential
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478 of Mn(III)-PP (1.15 V) (Klewicki and Morgan, 1998) than free Mn(III). Since
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479 pyrophosphate is a stronger ligand than water, a substitution of pyrophosphate for

480 hydrated groups will raise the relative energy of the Mneg orbitals thus decrease

481 Mn(III)’s oxidizing potential (Nico and Zasoski, 2000).

482

483 The above results indicate that the intramolecular redox reactions of Mn(III) with

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484 organics may be less influenced by complexing ligands as the reactions can occur

485 with both noncomplexed and complexed Mn(III) species. In contrast, the

486 non-oxidative pathways could only occur with noncomplexed Mn(III) species (i.e.,

487 with ligands like H2O and OH− only), and are easy to be affected by coexisting ligands.

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488 The non-oxidative degradation of organics may tend to occur with noncomplexed

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489 Mn(III) intermediates or on the surfaces of Mn(III)-rich MnO2, Mn(III/IV) oxides by

490 bonding to the surface-Mn(III) centers in the environment.

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491

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492 4. Conclusion
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493 Mn(III) is a strong oxidant for one electron transfer reactions, which could play

494 important roles in water/wastewater treatment processes and biogeochemical redox

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495 processes. Dissolved Mn(III) can efficiently degrade organics via a non-oxidative or
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496 oxidative pathway. This depends on the structure and functional groups of the
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497 organics. For some organics, the non-oxidative and oxidative reaction may occur

498 simultaneously. Furthermore, the non-oxidative reactions between dissolved Mn(III)

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499 and organics are more susceptible to ligands such as pyrophosphate which readily
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500 complex with Mn(III). The complexation makes Mn(III) not accessible to bond with
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501 organics and therefore lose reactivity. However, the complexation has little effects on

502 the oxidative reactions, as the Mn(III) complexes can still oxidize some organics

503 although at a slower rate compared to free Mn(III). This study not only helps to

504 explain the observed differences in reactions of organic contaminants with Mn(III)

505 intermediates, complexes and various manganese compounds during water treatment

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506 but also has important implications for predicting the fate and transport of organic

507 contaminants in Mn-rich environments.

508

509 Acknowledgement

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510 This work was supported in parts by the National Natural Science Foundation of

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511 China (51308312, 21607131 and 41301241) and the Natural Science Foundation of

512 Zhejiang Province (LR16E08003).

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513

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675 and modeling. Mar. Chem. 117(1), 59-70.

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676 Zhang, H., Chen, W. R., Huang, C. H., 2008. Kinetic modeling of oxidation of
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677 antibacterial agents by manganese oxide. Environ. Sci. Technol. 42(15),

678 5548-5554.

679 Zhang, H., Huang, C. H., 2003. Oxidative transformation of triclosan and chlorophene

680 by manganese oxides. Environ. Sci. Technol. 37(11), 2421-2430.

681
682

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683

(a)

Cl

N N

N N N
H H

PT
Atrazine

RI
U SC
AN
(b) (c)
M
D
TE

Figure 1. Degradation kinetics of atrazine (0.47 µM) with Mn(III) (KMnO4: 100 µM,
EP

NaHSO3: 500 µM) and ·OH (H2O2: 100 µM, FeSO4: 200 µM) at pHini 3.5 (a), and the
C

evolution of relatively stable products during atrazine degradation by Mn(III) (b)

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and ·OH (c).

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685

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686

PT
RI
U SC
AN
Figure 2. Evolution of the UV-Vis spectra of atrazine (in the absence of PP) and

Mn(III)-PP (with and without atrazine) in permanganate/bisulfite process sampled at

M

3min (PP was added to the reaction solution in advance to trap the free Mn(III)).
D

687
TE

H H H H
H H
β-elimination
EP

R N C C H R N+ + C C

H H Mn(III) H H
Mn

Mn(III)-OH
( II
C

I)

H 2O
CO 2 + H2O + Mn(II)
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R NH2 + Mn(III)-OH
PP

complexation disproportionation

Mn(III)-PP Mn(II) + Mn(IV)

Figure 3. Proposed degradation pathways of atrazine by Mn(III). Here, R represents

the other side structure of atrazine. Dash line represents a possible reaction pathway.

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(a)

PT
RI
U SC
(b) (c)
AN
M
D
TE

Figure 4. Degradation kinetics of 4-chlorophenol (39.4 µM) with Mn(III) (KMnO4:

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100 µM, NaHSO3: 500 µM) and ·OH (H2O2: 100 µM, FeSO4: 200 µM) at pHini 3.5 (a)

and the evolution of major degradation products of 4-chlorophenol by Mn(III) (b)

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and ·OH (c).

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688
689

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690

PT
RI
U SC
AN
Figure 5. Evolution of the UV-Vis spectra of 4-chlorophenol (in the absence of PP)
M

and Mn(III)-PP (with and without 4-chlorophenol) in permanganate/bisulfite process

D

sampled at 3min (PP was added to the reaction solution in advance to trap the free
TE

Mn(III)).

691
EP

692
C
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Cl

Mn(III) + Cl- + Mn(II)

OH OH

H2O

Cl OH

PT
Mn(II) +

RI
OH OH

H2O Mn(III)

SC
Cl OH

+ Mn(II)

U
OH
OH OH
AN
Mn(III) H2O

OH
M

H2O Mn(III)
Mn(II) + Cl- + Ring cleavage
OH OH
D

OH OH
TE

Figure 6. Proposed pathways for 4-chlorophenol degradation by Mn(III).

693
EP

694
C
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PT
RI
U SC
Figure 7. Degradation of atrazine (23.3 µM) and 4-chlorophenol (27.3 µM) with
AN
Mn(III)-PP (85.9 µM) at pHini 3.5.
M

695
D

696
TE
C EP
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Highligts

Mn(III) can work as either a catalyst or an oxidant in reactions with organics.

Free Mn(III) facilitated N-dealkylation of atrazine through non-redox reaction.

PT

Free Mn(III) degraded 4-chlorophenol via intramolecular redox processes.

RI

Mn(III)-pyrophosphate degraded 4-chlorophenol but not atrazine.

U SC
AN
M
D
TE
C EP
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