Journal Pre-proof

Release characteristics and mechanisms of sediment phosphorus in contaminated

and uncontaminated rivers: A case study in South China

Rui Li, Lei Gao, Qirui Wu, Zuobing Liang, Lei Hou, Zhigang Yang, Jianyao Chen, Tao
Jiang, Aiping Zhu, Manzi Li

PII: S0269-7491(20)36438-1
DOI: https://doi.org/10.1016/j.envpol.2020.115749
Reference: ENPO 115749

To appear in: Environmental Pollution

Received Date: 22 July 2020

Revised Date: 22 September 2020
Accepted Date: 24 September 2020

Please cite this article as: Li, R., Gao, L., Wu, Q., Liang, Z., Hou, L., Yang, Z., Chen, J., Jiang, T., Zhu,
A., Li, M., Release characteristics and mechanisms of sediment phosphorus in contaminated and
uncontaminated rivers: A case study in South China, Environmental Pollution, https://doi.org/10.1016/
j.envpol.2020.115749.

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Rui Li: Conceptualization, Methodology, Investigation, Writing - Original Draft,
Writing-Review & Editing, Formal analysis
Lei Gao: Conceptualization, Methodology, Investigation, Writing - Review & Editing,
Funding acquisition, Validation
Qirui Wu: Investigation, Methodology
Zuobing Liang: Investigation
Lei Hou: Investigation, Funding acquisition
Zhigang Ynag: Investigation
Jianyao Chen: Conceptualization, Writing - Review & Editing, Validation, Funding
acquisition
Tao Jiang: Investigation
Aiping Zhu: Investigation
Manzi Li: Investigation

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 1 Release characteristics and mechanisms of sediment phosphorus in

2 contaminated and uncontaminated rivers: A case study in South China

3 Rui Li a, Lei Gao a*, Qirui Wu a, Zuobing Liang a, Lei Hou b, Zhigang Yang a, Jianyao
4 Chen a**, Tao Jiang a, Aiping Zhu a, Manzi Li a
5 a
School of Geography and Planning, Sun Yat-sen University, Guangzhou 510275, China
6 b
College of Ecology and Environment, Southwest Forestry University, Kunming 650224, China

7 Abstract

8 Phosphorus (P) cycling present in sediments associated with iron (Fe), manganese (Mn)

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9 and sulfur (S) geochemical processes may cause secondary pollution in overlying water.

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10 Understanding the mechanisms of P release from sediments should help to restore water
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11 quality. This study used the diffusive gradients in thin film (DGT) technique to
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12 investigate the seasonal variance in the lability, remobilization mechanisms, and release

13 characteristics of sediment P in the uncontaminated Xizhi River and the severely

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14 contaminated Danshui River, South China. P accumulation in sediments contributed to

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15 higher DGT-labile P concentrations in contaminated reaches, and the highest labile P

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16 concentrations were generally observed in summer season at each site. The significant

17 positive relationships (p < 0.05) between labile Fe and P confirmed the Fe-P coupling

18 release mechanism in uncontaminated sediments. Stronger relationships between labile

19 Mn and P at contaminated sites indicated that Mn oxides played an important role in P

20 remobilization. However, sulfate reduction associated with microbial activities (crucial

21 genera: Desulfobulbus, Desulfomicrobium and Desulforhabdus) was considered to

22 decouple the Fe & Mn-P cycling relationship, promoting P release at contaminated sites.

23 The effluxes of sediment P were much higher in the Danshui River (mean 0.132 mg·cm–
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24 ·d–1) than in the Xizhi River (mean 0.038 mg·cm–2·d–1). And hot season led to growth

25 in P effluxes that was much greater in contaminated river.

26

27 Main finding of the work:

28 Reductive dissolution of Mn oxides played an important role in controlling P release

29 from sediment grains to interstitial water at contaminated sites.

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31 Keywords -p
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32 Diffusive gradients in thin film; Sediment; P legacy; Fe/Mn-P coupling; Sulfate
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33 reduction; Diffusive flux

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* Corresponding author.
E-mail address: nvtoo@sina.com (L. Gao)
**Corresponding author.
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E-mail address: chenjyao@mail.sysu.edu.cn (J. Chen)

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34 1. Introduction

35 Excessive nutrients discharged into water bodies can result in the rapid growth

36 and reproduction of phytoplankton, which can subsequently consume large amounts of

37 oxygen and release toxins, threatening other aquatic organisms and human health via

38 the food chain (Codd, 2000; Kokociński et al., 2009). Nitrogen (N) is essential in the

39 process of protein synthesis and may be the key factor of eutrophication in some water

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40 bodies (Howarth and Marino, 2006). Nonetheless, phosphorus (P) is generally

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41 considered the limiting nutrient in algal outbreaks (Schindler, 1974; Jilbert et al., 2020),
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42 and measures to control the input of P are needed for many eutrophic lake (Conley et
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43 al., 2009). However, some water bodies still do not recover from eutrophication because

44 of endogenous P release from historically accumulated P in sediments (Ni and Wang,

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45 2015), even if the pollutants discharged by human activities have been effectively
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46 controlled (Tu et al., 2019). The P legacy in sediments has become a barrier to
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47 eutrophication restoration in aquatic environments (O'Connell et al., 2020).

48 Phosphorus entering water is deposited in the sediments after adsorption onto

49 suspended particles and flocculation. Under such a scenario, sediments act as P "sink",

50 however, sediments are not only the ultimate fate of P but also the places where P starts

51 its geochemical cycle (Dai et al., 2007). Changes in hydrodynamic conditions and the

52 aquatic environment can induce the remobilization of sediment P and its movement into

53 the water column driven by hydraulic or concentration gradients, where it is reused by

54 plankton (Ding et al., 2016; Wang et al., 2018). Fe and Mn oxides are key factors
55 controlling the mobility and release of P in sediments (Smith et al., 2011; Giles et al.,

56 2016; Defforey and Paytan, 2018). A decrease in the redox state causes the reductive

57 dissolution of Fe and Mn oxides, releasing P adsorbed on them simultaneously

58 (Shahandeh et al., 2003; Ding et al., 2012). When the co-released Fe, Mn, and P migrate

59 to the sediment-water interface (SWI) with sufficient oxygen, Fe and Mn are

60 re-oxidized and reprecipitate as a “curtain” that sequesters the upward moving P

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61 (Herzsprung et al., 2010; Gao et al., 2020). Under fluctuating redox conditions, a small

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62 amount of P is still released from the sediment solids into the water column (Parsons et
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63 al., 2017).
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64 Knowledge of the distribution of chemicals in sediment is important for

65 understanding the potential environmental behavior of target elements (Hieltjes and

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66 Lijklema, 1980; Ruttenberg, 1992). However, traditional sampling and ex-situ analysis
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67 may distort the research results due to changes in physicochemical properties during
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68 sediment sample transportation and pretreatment (Lukkari et al., 2007). The diffusive

69 gradient in thin film (DGT) technique was first proposed for measuring trace metals in

70 natural water bodies (Davison and Zhang, 1994), and it can also be used to determine

71 the labile P in various media (Xu et al., 2013; Menezes-Blackburn et al., 2016; Almås et

72 al., 2017). Compared to traditional measurement methods, DGT accurately reflects the

73 in-situ bioavailability and mobility of the target substance on a micrometer scale (Zhang

74 et al., 2014; Almeida et al., 2019). Using DGT, the apparent diffusive P flux across the

75 SWI calculated from the labile P concentration gradient reflects the potential for P
76 release (Ding et al., 2015; Gao et al., 2016; Chen et al., 2019b). The sulfide (S2–)

77 produced by sulfate-reducing bacteria (SRB) will react with Fe3+, precipitating as FeS

78 and breaking Fe-P coupling in sediments in the process (Sun et al., 2016; Ma et al.,

79 2017). A better correlation between Fe and P than that between Mn and P was found in

80 laboratory incubation experiments examining Lake Taihu (Chen et al., 2019a). The

81 reductive dissolution of Fe oxide is widely regarded as the main mechanism controlling

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82 P release in sediments, whereas there is little information on the effects of redox cycling

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83 of Mn oxides on the mobility and release of sediment P. Furthermore, seasonal variation
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84 in release characteristics of sediment P and associated driving force remained unclear.
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85 This study selected the Xizhi River and one of its main tributaries, the Danshui

86 River as research area to (1) investigate the spatiotemporal distribution of sediment

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87 (labile) P using DGT, (2) illuminate the main remobilization mechanisms of sediment P
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88 with microbial activity and identify the key factors involved, and (3) quantify the
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89 transportation flux of P at the SWI.

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91 2. Materials and Methods

92 2.1. Study area

93 The Xizhi River in the southern part of Guangdong Province, South China, has a

94 watershed covering 4,140 km2 and a length of 176 km. It has a subtropical monsoon

95 climate and is dominated by sandstone lithology. The river originates from the

96 Baipenzhu Reservoir and flows into the Dongjiang River, an important water source for
 97 megacities Huizhou, Dongguan, and Shenzhen (Fig. 1). The Danshui River is the largest

98 tributary of the Xizhi River and flows through Shenzhen and Huizhou, highly urbanized

99 and industrialized areas in the GBA. Consequently, the water quality in the Xizhi River

100 watershed is of great importance for the safety of the domestic water supply. However,

101 domestic and industrial wastewater discharge over the past four decades have reduced

102 the river water quality and led to the tremendous accumulation of pollutants in the

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103 riverine sediments (Hou et al., 2018). Sampling site X2 located downstream from the

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104 Baipenzhu Reservoir (Fig. 1) can be considered a background site with relatively weak
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105 anthropogenic disturbance. Sites D1, D2, and D3 were in the upper, middle, and lower
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106 reaches of the Danshui River, respectively. The Danshui River is in a state of moderate

107 eutrophication (Hou et al., 2018) and polluted by heavy metals such as Mn, Zn, Cu, and
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108 Cr at concentrations of 714.00, 993.50, 289.50, and 301.50 mg·kg–1 respectively (Wang
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109 et al., 2015). Site X1 was located at the outlet of the Xizhi River and was used to reveal
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110 the potential impact of sediment P release on the Dongjiang River.

111 2.2. Collection and pretreatment of water and sediment samples

112 Duplicate sediment cores were collected using a gravity sampler at each site in

113 January, July, and November 2019. One intact sediment core was stored in

114 polycarbonate tubes with an inner diameter of 6.5 cm and length of 80 cm and

115 equilibrated in a thermostatic incubator without light after transport to the laboratory for

116 DGT. Using the other sediment core, surface sediments (12 cm) were sliced at 1-cm

117 intervals and placed in centrifuge tubes. The sediment oxidation-reduction potential
118 (ORP) was determined by a pen-type meter (SX 630; Sanxin, Shanghai, China) from the

119 sub-samples. Wet sediments were centrifuged for 15 minutes at 3000 g to separate the

120 interstitial water. Then, the remaining sediments were ground and sieved with a 20

121 mesh (removing gravel and plant debris) and a 100 mesh after freeze-drying for particle

122 size analysis and subsequent chemical analysis. Overlying river water was also collected

123 in each sampling campaign. The physicochemical properties (EC, pH, ORP, and DO) of

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124 the overlying and interstitial water were measured with a portable meter (HQ40d; Hach,

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125 Loveland, CO, USA). Then, the water samples were filtered through 0.22-μm polyether
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126 sulfone membranes for subsequent analysis.
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127 2.3. Chemical analysis of water samples and sediments

128 The ammonia nitrogen (NH3-N) concentrations of the water samples were
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129 measured in situ spectrophotometrically (HI-93733; Hanna, Italy). Dissolved organic

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130 carbon (DOC) was determined using a TOC analyzer (Elementar Analysensysteme
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131 GmbH, Langenselbold, Germany). The sulfate concentrations were measured by ion

132 chromatography (ICS 900; Dionex, Sunnyvale, CA, USA).

133 An approximately 0.25-g sediment sample was treated with 10% HCl and 10%

134 H2O2 to remove organic matter and carbonates, respectively, before measuring particle

135 size using a laser particle analyzer (Mastersizer 2000; Malvern Instruments, Malvern,

136 UK). About 40 mg of sediment was acidified with 1 M HCl to remove the carbonates

137 and dried at 60°C, then the total organic carbon (TOC) of sediments was determined

138 using an Elementar vario TOC analyzer (Elementar Analysensysteme GmbH,

139 Langenselbold, Germany). The total phosphorus (TP) content was digested with a

140 mixture of concentrated sulfuric acid and 70% perchloric acid and then measured using

141 a molybdenum blue spectrophotometry method (Dick and Tabatabai, 1977).

142 2.4. DGT deployment and analysis

143 The DGT technique, based on Fick’s first law of diffusion, was invented by

144 Davison and Zhang (1994) to determine the labile fraction of a target element in

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145 sediment (Ding et al., 2016). The principle and structure of the DGT probe can be found

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146 elsewhere (Ding et al., 2015). The concentration of labile elements (CDGT) is calculated
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147 with the following equations:
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148 = (1)

∆
149 = (2)
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150 where M is the accumulated mass of the target element in the binding gel (mg), Ce is the
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151 concentration of the target element in the elution solution (mg·L–1), Ve is the volume of
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152 elution solution (mL), fe is the elution factor, Δg is the thickness of the diffusion layer

153 (cm), D is the diffusion coefficient of the target element in the diffusion gel (cm2∙s–1),

154 t is the deployment time (s), and A is the exposure area of the device (cm2).

155 Chelex and ZrO-AgI DGT probes were purchased from

156 www.dgtresearch.com.cn and www.easysensor.net, respectively. All DGT probes were

157 deoxygenated with nitrogen in 0.01 mol·L–1 NaCl solution for 16 h before use. A small

158 mark was made on the probe to form the 20 × 18 and 130 × 18 mm exposure areas in

159 the overlying water and sediments, respectively. Then, the Chelex and ZrO-AgI DGT
160 probes were bound back-to-back and gradually inserted into the sediment cores until the

161 mark reach the SWI. The sediment cores containing the DGT probes were kept in a dark

162 incubator at a specific temperature (18, 29, 25°C in January, July, November,

163 respectively) as measured during sampling. All DGT probes were retrieved after 24 h

164 and thoroughly rinsed with ultrapure water before subsequent use.

165 For two-dimensional high-resolution imaging and determination of the vertical

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166 profile of labile S [∑S(Ⅱ)] in sediments, the accumulated mass of S per unit area (M/A)

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167 in ZrO-AgI binding gels was determined using a colorimetric technique and calculated
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168 by the following equation (Ding et al., 2012):
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169 = −7.23 × ln( ) (3)

170 where G is the grayscale intensity of ZrO-AgI binding gels. The concentration of
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171 ∑S(Ⅱ) could be calculated with Eq. (2).

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172 Subsequently, the ZrO-AgI and Chelex binding gels were sliced at vertical
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173 10-mm intervals using a ceramic knife, and the respective sliced gels were eluted with 4

174 mL of 0.2 M NaOH-0.5M H2O2 at 4°C for 4 h and 2 mL of 1 M HNO3 for 24 h. In this

175 research, the elution factors of P, Fe and Mn were 0.862, 0.800 and 0.800, respectively,

176 according to operation manual determined by manufacture. The concentration of P

177 eluted from the ZrO-AgI gel was determined by molybdenum blue spectrophotometry,

178 and the extraction solution from Chelex gel was diluted to 5 mL to measure the Fe and

179 Mn concentrations using ICP-AES. The concentrations of DGT-labile P, Fe, and Mn

180 were calculated using Eqs. (1) and (2).

181 2.5. Apparent diffusion flux model

182 To examine the apparent diffusion flux across the SWI, a model based on Fick’s

183 first law of diffusion was used (Ding et al., 2015). According to the vertical distribution

184 of DGT-labile P, the apparent flux can be calculated as the sum of the diffusion fluxes

185 from the overlying water and sediment to the SWI:

% &'( % &'(
186 = ! + # = −$! ( ) − -$# ( ) (4)
%)* (+, ) %). (+, )

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187 $# = /0 (5)

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188 where Jw and Js are the flux of P from the overlying water and sediment to the SWI,
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189 respectively; and Dw and Ds are the diffusions coefficient of P in water and sediment,
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190 respectively, calculated using Eq. (5) (Ullman and Aller, 1982; Gao et al., 2016). The

191 formation resistivity factor was determined by φ (F = 1/φ3 when φ ≥ 0.7, otherwise, F =
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192 1/φ2) (Li and Gregory, 1973). (δCDGT/δXw)x=0 and (δCDGT/δXs)x=0 represent the
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193 concentration gradients of DGT-labile P in the overlying water and sediment,

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194 respectively.

195 2.6. Microbiological analysis

196 According to different concentrations of labile S in specific sediment layers, 11

197 wet sediment samples (X1 at 1 and 11 cm; X2 at 3, 6, and 11 cm; D1 at 1, 9, and 11 cm;

198 D2 at 1, 6, and 11 cm; and D3 at 1 and 11 cm) were collected in July and examined

199 using 16S rDNA high-throughput sequencing technology to examine the sediment

200 microbial community (Zhu et al., 2019). First, 25 mg of wet sediment was ground with

201 liquid nitrogen. Then, total DNA from the sediments was extracted using the MO BIO
202 PowerSoil DNA Isolation Kit (MO BIO, Carlsbad, CA, USA). The quality of the

203 extracted DNA was checked using agarose gel electrophoresis, and the DNA was stored

204 at –20°C for further analysis. DNA concentrations were determined using a Qubit 2.0

205 fluorometer. A primer set (515F and 806R) targeting the V4 region of the bacterial 16S

206 rRNA was used to amplify this sequence. PCR amplicons were sequenced on the

207 Illumina MiSeq platform of the Beijing Genomics Institute (Beijing, China). QIIME and

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208 USEARCH software were used for sequence analysis, with the default settings for the

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209 Illumina process. Then, the UPARSE pipeline was used to assign taxonomy at 97%
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210 similarity levels through the Ribosomal Database Project Naïve Bayesian Classifier
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211 v.2.2 trained on the Greengenes database; a 0.8 confidence level was used for critical

212 values. From the microbial sequencing results, the abundance values of different
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213 sulfate-reducing bacteria (SRB) genus were obtained.

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214 2.7. Statistical analysis

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215 All statistical analyses were performed using IBM SPSS software (ver. 22.0;

216 SPSS, Chicago, IL, USA). The differences in environmental variables among sampling

217 sites were determined using one-way analysis of variance (ANOVA) with the

218 multiple-sample Kolmogorov-Smirnov test. Spearman’s correlation analysis was used

219 to identify the relationships between variables and correlations were considered

220 significant at p < 0.05 (Spearmen, 1904).

221
222 3. Results and Discussion

223 3.1 Physicochemical properties of the overlying water and sediments

224 Table 1 shows the physicochemical properties of the overlying water at each

225 sampling site in the different sampling campaigns. Water temperatures were in the

226 range 17.9–19.1, 28.7–29.4, and 24.2–25.6°C in January, July, and November,

227 respectively. River water was slightly alkaline with a mean pH of 7.33. EC varied from

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228 0.05 to 0.75 mS·cm–1 with the lowest value being found at site X2, implying the natural

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229 water condition of the Xizhi River watershed. The DO concentration was the lowest in
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July (3.19–6.52 mg·L–1) and had a significant negative relationship with temperature (R
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230
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231 = –0.878, p < 0.001, n = 15), which was attributed to the lower solubility of oxygen

232 with increasing temperature. NH3-N concentrations were generally lower at site X2
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233 (0.8–1.7 mg· L–1) than at other sites (2.5–8.8 mg·L–1) during all sampling campaigns,
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234 reflecting the contamination of the Danshui River.

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235 Figure S1 shows the particle composition of clay (< 4 μm), silt (4–63 μm), and

236 sand (> 63 μm) of the sediment cores. Fine particles (< 63 μm) of clay and silt were the

237 major component of sediments from the Xizhi River, whereas sediments were coarser at

238 sites D1–D3 in the Danshui River. The ORP dropped sharply from the overlying water

239 to the sediments and remained relatively stable downward (Fig. S2). Generally, the ORP

240 in surface sediments (0 to –40 mm) in July was lower than in January and November,

241 except at site X1 (Table S1), which was mainly ascribed to faster organic matter

242 decomposition and oxygen consumption under the high temperatures at these sites.
243 3.2 Distribution of TOC and TP in sediments

244 As shown in Figure S3, the sediment TOC ranged from 2990 to 35,800 mg·kg–1

245 with a downward decreasing trend, except for profile D3. The TOC contents at 5 sites

246 were in a following order as D3 > D1 > D2 > X1 > X2 (p < 0.05). Organic matter was

247 generally significantly related to fine particles, such as clay components. Consequently,

248 the lowest TOC contents at site D2 could be attributed to its predominantly coarse

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249 particles. However, coarser grains with higher TOC content were found at sites D1 and

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250 D3, implying that the grain-size effect was not the main factor controlling the
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251 distribution of TOC in the study area, confirming the anthropogenic input of industrial
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252 wastewater and municipal sewage into the Danshui River.

253 The sediment TP content was in the range 310–5710 mg·kg–1 and its spatial
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254 distribution was similar to that of TOC (Fig. S3). The significant positive correlation (p
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255 < 0.001, n = 60) between TP and TOC suggested a common source. The TP contents
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256 followed a decreasing order as D3 > D1 > D2= X1 = X2 (p < 0.05). It was worth noting

257 the mean TP contents at sites D1 (2240 mg·kg–1) and D3 (4390 mg·kg–1) exceeded the

258 severe effect level (2000 mg·kg–1) (Fletcher et al., 2008), indicating a severe P

259 contamination in the Danshui River. Based on TOC and TP contents in sediments, D1,

260 D2, D3 and X1 can be clustered into severely contaminated sites, whereas, X2 can be

261 considered as a clean site. Ding et al. (2015) reported that sediment with much

262 accumulated P had great release potential. Consequently, sediment severely polluted by

263 P might induce secondary pollution of the overlying water in the Danshui River.
264 However, considering only the TP content does not accurately reflect the potential

265 mobility of P in sediments. This requires a deep investigation of the labile fraction of

266 sediment P and its associated remobilization mechanisms in the study area.

267 3.3 Spatiotemporal distribution of DGT-labile P, Fe and Mn

268 Figure 2 shows the vertical distribution of the DGT-labile P concentration in the

269 overlying water and sediment profiles. The labile P concentrations were much lower in

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270 the overlying water (mean 40.10 μg·L–1) than in sediments (mean 229.87 μg·L–1).

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271 Overall, the labile P concentration had little vertical fluctuation in the sediments and
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272 similar distribution patterns at sites X1 and X2 in the three sampling campaigns.
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273 Vertically, the labile P concentration generally increased with depth at site D1 in

274 January, at site D2 in January and November, and at site D3 in all sampling campaigns.
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275 The vertical distribution of the labile Fe and Mn was similar to the labile P at these
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276 sediment cores (Fig. 2). Otherwise, the labile P concentrations increased in the upper
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277 layers and then decrease, and the peak labile P concentrations were found near the SWI

278 (0 to –50 mm) at site D1 in July and November, and at site D2 in July. In surface

279 sediments, marked degradation of organic matter during the early diagenetic process

280 was identified as the main cause of the reduction of iron oxides and subsequent P

281 release from sediment solids to interstitial water (Krom and Berner, 1981; Ding et al.,

282 2012; Ma et al., 2017). This is supported by the rapid fall in ORP (from positive to

283 negative) near the SWI at all sites. Furthermore, the labile P concentrations were higher

284 in July than in January and November at sites D1 to D3. An increase in temperature
285 would promote the mineralization of OM, accelerating the reductive dissolution of Fe

286 and Mn oxides (Lovely and Phillips, 1986) and material exchanges between different

287 phases. As shown in Figure S4, the mean labile P concentrations in the three campaigns

288 were significantly higher at sites D1 and D3 than at the other sites (p < 0.05), reflecting

289 a relatively higher release potential of sediment P in the Danshui River.

290 3.4 Coupling between P and Fe & Mn

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291 Many studies have reported that Fe oxide is the key factor controlling the release

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292 of P in sediments (Sun et al., 2016; Chen et al., 2019a; Chen et al., 2019b). In the
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293 present study, the labile Fe, Mn, and P concentrations determined by DGT were used to
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294 discriminate the roles of Fe and Mn in P remobilization. At site X2, where the aquatic

295 environment had negligible contamination, labile P had a better linear relationship with
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296 labile Fe than labile Mn in surface sediments (0 to –40 mm) or the entire profile (Fig.
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297 3). This confirmed the co-release of Fe and P induced by reductive dissolution of Fe
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298 oxides in non-contaminated areas. A previous investigation found that the surface layer

299 (0 to –30 mm) of sediment cores in Lake Taihu is an important zone of Fe reduction,

300 where abundant Fe and P are released synchronously (Ding et al., 2015; Fan et al.,

301 2018). Significant coupling relationships between Fe and P were observed near the SWI

302 in January (0 to -40 mm) and July (0 to -30 mm), and for the whole profile in November

303 at site X2, respectively.

304 Regarding contaminated sites (X1, D1, D2, and D3), three relationships between

305 labile Fe & Mn and P were observed in surface sediments or entire cores (Fig. 3, 4).
306 Firstly, labile P had a positive relationship with labile Fe and Mn in most sediment

307 cores (e.g. site X1 in July and November, site D1 in January, site D2 in July and

308 November and site D3 in January and November), which indicated that Mn was an

309 important factor controlling remobilization of P in sediments. Secondly, labile P

310 positively related to Mn (p<0.05 or p<0.01) with higher R2 values at site X1 in January

311 (0.819), at sites D1 (0.384) and D3 (0.717) in July compared to those between labile P

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312 and Fe (p>0.05). The better correlation between labile Mn and P implied that reductive

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313 dissolution of Mn oxides played a more crucial role in release of P from sediment grains
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314 to interstitial water at these contaminated sites. According to ideal reduction order in
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315 anaerobic sediment, reductive dissolution of Mn oxides and associated release of

316 adsorbed P will take place prior to those of Fe oxides as the former is more sensitive to
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317 changes in redox conditions (Postma and Appelo, 2000). Thirdly, labile P negatively
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318 associated with labile Fe & Mn at site D1 in November (p<0.01) and at site D2 in
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319 January, indicating Fe and Mn loss in the interstitial water during P release (Ma et al.,

320 2017; Gao et al., 2020). Previous research suggested that formation of metal sulfides

321 precipitates, such as FeS and MnS, were mainly responsible for this negative correlation

322 (Sun et al., 2016).

323 3.5 Difference in sulfate reduction intensity among sites

324 As shown in Figure S5, the sulfate concentrations in the overlying water were

325 2.81−128.66 mg·L–1 and generally decreased with sediment depth. A sharp decrease

326 was found below the SWI at sites D1−D3. By contrast, the labile S (II) concentration
327 increased distinctly in sediments, with the highest values near the SWI in July (Fig. 2).

328 In the Xizhi River, however, there was no obvious seasonal variance in sulfate and the

329 labile S concentrations were much lower.

330 As shown in Figure 5, there was a significant difference in the SRB community

331 composition between the two river basins in July. In the Xizhi River,

332 Thermodesulfovibrio was the main SRB genus (relative abundance 1.44–6.36%) and it

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333 was more abundant near the SWI. In comparison, the relative abundance of

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334 Thermodesulfovibrio in the Danshui River (0.002–0.144%) was much lower.
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335 Desulfobulbus (relative abundance 0.09–0.73%), Desulfomicrobium (relative abundance
lP

336 0.09–0.24%), and Desulforhabdus (relative abundance 0.05–0.18%) are three crucial

337 SRB genera with a significant relationship (p < 0.05) with labile S in the Danshui River
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338 (Table S2). Conversely, Thermodesulfovibrio had a significant negative relationship (p

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339 < 0.05) with labile S. This might be due to the sampling temperature in July (29°C),
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340 which is within the optimum temperature range for Desulfomicrobium (28–37°C) and

341 Desulfobulbus (28–39°C) (Widdel and Hansen, 1992), while 65°C is optimal for

342 Thermodesulfovibrio (Henry et al., 1994). Thus, the intensity of sulfate reduction in July

343 is stronger in the Danshui River than in the Xizhi River.

344 3.6 Decoupling of Fe & Mn-P associated with sulfate reduction

345 The distributions of labile P and labile S in the vertical profile were roughly

346 synchronous (Fig. 2). Ding et al. (2012) reported the co-release of phosphate and

347 dissolved sulfide due to the simultaneous reduction of Fe oxides and sulfate during the
348 mineralization of organic matter in sediments [Eqs. (6) and (7)], leading to the

349 subsequent release of Fe-bound P (Berner, 1984). Interestingly, the labile P

350 concentration increased downward with decreasing labile Fe at X1 and D2 in January, at

351 D1 in July and November, and at D3 in July (Fig. 3). Negative relationships between

352 labile P and Mn were observed at X2 and D1 in November and at D2 in January (Fig.

353 4). These phenomena might be associated with the formation of metal sulfides (MnS

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354 and FeS) [Eqs. (8) and (9)] (Wang et al., 2014), leading to Fe2+ and Mn2+ loss after the

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355 co-release of Fe, Mn, and P. Gao et al. (2009) observed the formation of iron sulfide
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356 minerals in sub-tidal marine sediments, and Mn was incorporated into labile sulfides,
lP

357 such as greigite and pyrite compounds. The bulk of P originally adsorbed on the Fe &

358 Mn oxides would be liberated due to the low adsorption affinity of FeS and MnS for P.
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359 Specifically, FeS could be transformed into more stable authigenic pyrite (FeS2) by the
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360 addition of zero-valent sulfur [Eq. (10)] (Berner, 1984; Gao et al., 2020). As a result,
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361 labile Fe and Mn was consistently consumed, while P accumulated in the interstitial

362 water, eventually leading to the decoupling of Fe & Mn-P cycling in sediments.
8
CH O + 4FeOOH + H O → 4Fe + HCO9 + 7OH (6)
2CH O + SO; → 2HCO9 + H S (7)
2FeOOH + 3H S → 2FeS + S + 4H O (8)
MnO + 2H S → MnS + S + 2H O (9)
FeS + S → FeS (10)
363 3.7 Potential mobility of P on solid phase

364 The P mobility in sediments is strongly dependent on the Fe:P ratio because the

365 Fe oxides produced by excess Fe2+ under oxidative conditions can sequester the released

366 P, and the Fe:P ratio of 15 in sediment is found to be a critical threshold value for

367 preventing upward diffusion of P in the interstitial water (Jensen and Andersen, 1992).

368 However, utilization of the total Fe:P ratio will overestimate the adsorption capacity of

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369 sediments, as only active Fe oxyhydroxides have sufficient capacity to adsorb released

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370 P (Slomp et al., 1996). In the oxidative hydrolysis of Fe and the concomitant
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371 precipitation of P, the precipitation of one P molecule needs at least two Fe atoms (Fan
lP

372 et al., 2018). Therefore, the labile Fe : P molar ratio in the interstitial water was a better

373 indicator of the potential mobility of P (Ding et al., 2016). In the present study, the Fe:P
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374 molar ratios determined by the slope of fitting curve were distinctly higher in the Xizhi
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375 River (62.67−346.65) than in the Danshui River (6.96−55.08) (Fig. 3), suggesting that
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376 regeneration of Fe oxides near the oxic SWI would scavenge the upward release of

377 sediment P in the Xizhi River. The formation of “Iron curtain (Fe oxides)” in surface

378 sediments was supposed to effectively impede the diffusion of the interstitial water P

379 into the overlying water (Ma et al., 2017; Gao et al., 2020). Conversely, the release of

380 sediment P to the overlying water would more readily take place in the Danshui River.

381 3.8 Apparent diffusion flux of labile P characterized by DGT

382 As shown in Figure 6a, sediment P tended to migrate upward at all sites with

383 diffusion fluxes of 0.021−0.159, 0.022−0.277, and 0.00009−0.132 mg·cm–2·d–1 in

384 January, July, and November, respectively. The mean apparent diffusion flux of labile P

385 was higher in July (0.148 mg·cm–2·d–1) than in January (0.078 mg·cm–2·d–1) and

386 November (0.057 mg·cm–2·d–1). With the relatively higher water temperature in July

387 (28.1−29.4°C) compared to January (17.9−19.1°C) and November (24.4−25.6°C),

388 stronger reduction of Fe & Mn oxides and sulfates promoted desorption of P on

389 sediment solids. Furthermore, the rising water level during the rainy season (April to

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390 September) leads to more hypoxic sediments conducive to the reduction of Fe & Mn

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391 oxides. The lower labile P concentrations in the overlying water elevated the
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392 concentration gradients across the SWI and subsequently increased its diffusion flux.
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393 The apparent diffusion fluxes of labile Fe (Fig. S6a) were positively related to that of

394 labile P (p < 0.05), verifying the Fe-P coupling release mechanism. Although there was
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395 no significant relationship between the apparent diffusion fluxes of labile Mn (Fig. S6b)
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396 and labile P, the effect of Mn oxide reduction on sediment P release should not be
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397 ignored. Sediments from the Danshui River had an obviously higher efflux (mean 0.132

398 mg·cm–2·d–1) than the Xizhi River (0.038 mg·cm–2·d–1), which was attributed mainly to

399 its larger P pool (range 560−2396 mg·kg–1). This was consistent with previous findings

400 that the internal loading of P is greater in contaminated areas (Zhu et al., 2013; Ding et

401 al., 2015).

402 The mean effluxes of sediment P in three sampling campaigns followed a

403 decreasing order as D1 (0.172 mg·cm–2·d–1) > D3 (0.163 mg·cm–2·d–1) > X1 (0.062

404 mg·cm–2·d–1) > D2 (0.060 mg·cm–2·d–1) > X2 (0.014 mg·cm–2·d–1). Meanwhile,

405 effluxes of P at sites D1 and D3 were higher than those in Lake Taihu (0.095 mg·cm–

2
406 ·d–1) (Ding et al., 2015), Lake Dongting (0.067 mg·cm–2·d–1) (Gao et al., 2016), and the

407 Pearl River Estuary (0.040 mg·cm–2·d–1) (Gao et al., 2020), where sediment P

408 concentrations are much lower (range 304−1553, 520−890, and 249−732 mg·kg–1,

409 respectively) than at these two sites (range 1391−5715 mg·kg–1). However, at a specific

410 site in Lake Taihu (Ding et al., 2015) where the sediment P concentration was 1210

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411 mg·kg–1, the observed efflux (0.650 mg·cm–2·d–1) was much higher than that at sites D1

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412 and D3. -p
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413
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414 4. Conclusions

415 This study used the DGT technique to explore the lability, remobilization, and
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416 release of sediment P. At contaminated sites, excessive P accumulation in sediments

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417 contributed to higher labile P concentrations, leading to greater effluxes of sediment P.

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418 At each site, the highest labile P concentrations and effluxes were generally observed in

419 July. Mn played a considerable role in P release from sediment grains to interstitial

420 water in contaminated reaches, although coupling of Fe and P was found in most

421 sediment cores. The vulnerability of Mn oxides to changeable redox conditions brings

422 huge challenges to the governance of water environments. Especially at contaminated

423 sites, intense sulfate reduction decoupled the Fe & Mn and P relationships, promoting

424 the release of P. Consequently, sufficient attention should be paid to the restoration and

425 treatment of sediments to keep the safety of water supply to the GBA downstream.
426

427 Acknowledgements

428 The authors are very grateful to reviewers for providing invaluable suggestion

429 and comment. This work was financially supported by the Natural Science Foundation

430 of China (Project No. 42077376, 41771027, and 41961144027), the Scientific and

431 Technological Innovation Project of the Water Sciences Department of Guangdong

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432 Province (2020-09), CRRP2019-09MY-Onodera from APN and the Application and

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433 Fundamental Research Project of Yunnan Province, China [2017FG001(-039)].
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434
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606
Table 1. Physicochemical properties of the overlying water from the Xizhi River and

the Danshui River (January, July and November 2019).

Site Month T( ) pH EC (ms·cm–1) DO (mg·L–1) DOC (mg·L–1) NH3-N (mg·L–1)

Jan. 18.8 7.50 0.25 7.98 3.67 3.4

X1 Jul. 29.2 7.08 0.133 5.31 5.83 2.5

Nov. 24.2 7.61 0.31 6.20 6.02 5.0

Jan. 19.1 7.45 0.074 8.29 2.86 1.7

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X2 Jul. 28.7 6.54 0.05 6.52 6.46 0.8

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Nov. 25.6 7.34 0.072 7.77 4.70 1.2

Jan. 17.9 7.43 0.59 -p9.35 6.78 8.5

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D1 Jul. 28.7 6.93 0.37 3.19 9.90 4.2
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Nov. 24.7 7.51 0.59 5.52 7.66 4.1

Jan. 18.6 7.49 0.72 9.29 6.88 8.8

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D2 Jul. 28.7 7.01 0.4 4.43 4.36 5.0

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Nov. 25.1 7.60 0.66 6.04 6.65 6.2

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Jan. 18.7 7.76 0.63 9.24 6.76 6.3

D3 Jul. 29.4 6.98 0.41 3.85 4.71 2.9

Nov. 24.4 7.76 0.75 7.76 8.09 3.2

Mean 24.1 7.33 0.40 6.72 6.09 4.3

Minimum 17.9 6.54 0.05 3.19 2.86 0.8

Maximum 29.4 7.76 0.75 9.35 9.90 8.8

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Fig.1. Map of the study area and sampling sites (X1, X2 are located in the Xizhi River,

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and D1, D2, and D3 are located in the Danshui River).
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 DGT-labile P (μg·L-1) DGT-labile P (μg·L-1) DGT-labile P (μg·L-1) DGT-labile P (μg·L-1) DGT-labile P (μg·L-1)
0 150 300 450 600 750 0 150 300 450 600 750 0 150 300 450 600 750 0 150 300 450 600 750 0 150 300 450 600 750
20 20 20 20 20
X1 X2 D1 10 D2 D3
10 10 10 10
0 0 0 0 0
-10 -10 -10 -10 -10
-20 -20 -20 -20 -20

Depth (mm)
Depth (mm)

Depth (mm)
Depth (mm)

Depth (mm)
-30 -30 -30 -30 -30
-40 -40 -40 -40 -40
-50 -50 -50 -50 -50
-60 -60 -60 -60 -60
-70 -70 -70 -70 -70
-80 -80 -80 -80 -80
-90 -90 -90 -90 -90
-100 -100 -100 -100 -100
-110 -110 -110 -110 -110
Jan. Jul. Fe (μg·L
DGT-labile Nov. -1) Jan. Nov. -1) Jan.
Jul. Fe (μg·L Nov. -1) Jan.
Jul. Fe (μg·L Nov. -1) Jan.
Jul. Fe (μg·L Jul. Fe (μg·L
Nov. -1)
DGT-labile DGT-labile DGT-labile DGT-labile
0 10000 20000 30000 0 10000 20000 30000 0 10000 20000 30000 0 10000 20000 30000 0 10000 20000 30000
20 20 20 20 20
10 X1 10 X2 10 D1 10 D2 10 D3
0 0 0 0 0

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-10 -10 -10 -10 -10
-20 -20 -20 -20 -20

Depth (mm)
Depth (mm)

Depth (mm)

Depth (mm)
Depth (mm)

-30 -30 -30 -30 -30

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-40 -40 -40 -40 -40
-50 -50 -50 -50 -50
-60 -60 -60 -60 -60
-70 -70 -70 -70 -70
-80
-90
-100
-80
-90
-100
-80
-90
-100
-p -80
-90
-100
-80
-90
-100
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-110 -110 -110 -110 -110
Jan. Jul. Mn Nov.
DGT-labile Jan. Jul. MnNov.
(μg·L-1) DGT-labile Jan. Jul. MnNov.
(μg·L-1) DGT-labile Jan. Jul. Mn Nov.
(μg·L-1) DGT-labile Jan. Jul. Mn Nov.
(μg·L-1) DGT-labile (μg·L-1)
0 1000 2000 3000 4000 0 1000 2000 3000 4000 0 1000 2000 3000 4000 0 1000 2000 3000 4000 0 1000 2000 3000 4000
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20 20 20 20 20
X1 X2 D1 D2 D3
10 10 10 10 10
0 0 0 0 0
-10 -10 -10 -10 -10
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-20 -20 -20 -20 -20

Depth (mm)
Depth (mm)

Depth (mm)
Depth (mm)

Depth (mm)

-30 -30 -30 -30 -30

-40 -40 -40 -40 -40
-50 -50 -50 -50 -50
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-60 -60 -60 -60 -60

-70 -70 -70 -70 -70
-80 -80 -80 -80 -80
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-90 -90 -90 -90 -90

-100 -100 -100 -100 -100
-110 -110 -110 -110 -110
Jan. Jul. Nov. Jan. Jul. Nov. Jan. Jul. Nov. Jan. Jul. Nov. -1 Jan. Jul. S (μg·L
DGT-labile Nov. -1)
DGT-labile S (μg·L-1) DGT-labile S (μg·L-1) DGT-labile S (μg·L-1) DGT-labile S (μg·L )
0 100 200 300 400 0 100 200 300 400 0 100 200 300 400 0 100 200 300 400 0 100 200 300 400
20 20 20 20 20
X1 X2 D1 10 D2 10 D3
10 10 10
0 0 0 0 0
-10 -10 -10 -10 -10
-20 -20 -20 -20 -20
Depth (mm)
Depth (mm)

Depth (mm)

Depth (mm)
Depth (mm)

-30 -30 -30 -30 -30

-40 -40 -40 -40 -40
-50 -50 -50 -50 -50
-60 -60 -60 -60 -60
-70 -70 -70 -70 -70
-80 -80 -80 -80 -80
Jan.
-90 -90 -90 -90 -90
Jul.
-100 -100 -100 -100 -100 Nov.
-110 -110 -110 -110 -110

Fig.2. Vertical distributions of DGT-labile P, Fe, Mn and S in overlying water and

sediment profiles from the Xizhi River and the Danshui River. Black dotted line
represents the sediment-water interface (SWI).
 Jan. Jul. Nov.
180 180 180
X1 X1

DGT-labile Fe (μmol·L-1)
X1

DGT-labile Fe (μmol·L-1)
DGT-labile Fe (μmol·L-1) y = -70.61x + 76.97
R² = 0.046, p=0.644 y = -183.18x + 116.03
R² = 0.516, p=0.069
120 120 y = 346.65x - 5.02 (-50 to -110 mm) 120 (-50 to -110 mm)
R² = 0.956**
(0 to -40 mm)
y = 163.66x - 13.51
60 60 60
y = -3.63x + 133.31 R² = 0.397, p=0.255
R² = 0.033, p=0.572 (0 to -40 mm)
(0 to -110 mm)
0 0 0
0 3 6 9 0 3 6 9 0 3 6 9
250 DGT-labile P (μmol·L-1) 250 DGT-labile P (μmol·L-1) 250 DGT-labile P (μmol·L-1)
DGT-labile Fe (μmol·L-1)

DGT-labile Fe (μmol·L-1)
DGT-labile Fe (μmol·L-1)
X2 X2 y = -21.14x + 167.41 X2
R² = 0.143, p=0.242 y = 63.68x - 36.18
200 200 200
(-40 to -110 mm) R² = 0.744**
y = 16.73x + 162.69
(0 to -110 mm)
150 R² = 0.209, p=0.303 150 150
(-50 to -110 mm)
100 100 100
y = 149.22x - 308.42 y = 62.67x - 48.77
50 R² = 0.826* 50 R² = 0.952* 50
(0 to -40 mm) (0 to -30 mm)

of
0 0 0
0 1 2 3 4 0 1 2 3 4 0 1 2 3 4
500 DGT-labile P (μmol·L-1) 500 DGT-labile P (μmol·L-1) 500 DGT-labile P (μmol·L-1)

ro
DGT-labile Fe (μmol·L-1)
DGT-labile Fe (μmol·L-1)

DGT-labile Fe (μmol·L-1)
D1 D1 D1
y = -5.22x + 314.01
400 400
R² = 0.095, p=0.329400
(0 to -110 mm) y = -24.05x + 437.64
300 300

200
y = 55.08x - 279.03
R² = 0.754**
(0 to -110 mm)
200
-p 300

200
R² = 0.679**
(-10 to -110 mm)
re
100 100 100

0 0 0
lP

0 10 20 30 0 10 20 30 0 10 20 30
400 DGT-labile P (μmol·L-1) 400 DGT-labile P (μmol·L-1) 400 DGT-labile P (μmol·L-1)
DGT-labile Fe (μmol·L-1)

D2
DGT-labile Fe (μmol·L-1)

DGT-labile Fe (μmol·L-1)

D2 D2
300 y = -11.15x + 198.78 300 y = 19.52x + 13.82 300
R² = 0.179, p=0.206 y = 17.67x - 5.07
na

R² = 0.439* R² = 0.383*
(0 to -110 mm) (0 to -110 mm)
200 200 200 (0 to -110 mm)

100 100 100

ur

0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Jo

250 DGT-labile P (μmol·L-1) 250 DGT-labile P (μmol·L-1) 250 DGT-labile P (μmol·L-1)

D3
DGT-labile Fe (μmol·L-1)
DGT-labile Fe (μmol·L-1)

DGT-labile Fe (μmol·L-1)

D3 D3
200 200 200 y = 0.39x + 96.56
y = 7.29x - 9.84 y = -33.62x + 696.22 R² = 0.025, p=0.711
150 R² = 0.488* 150 R² = 0.751** 150 (-40 to -110 mm)
(0 to -110 mm) (-10 to -110 mm)
100 100 100
y = 6.96x - 15.03
50 50 50 R² = 0.974*
(0 to -30 mm)
0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
DGT-labile P (μmol·L-1) DGT-labile P (μmol·L-1) DGT-labile P (μmol·L-1)

Fig.3. Linear fits between DGT-labile Fe and P in sediments from the Xizhi River and
the Danshui River in the three sampling campaigns. Blue, significant positive
relationship in surface sediments or the entire profile; black, no significant positive
relationship in surface sediments or the entire profile; red, the relationship in deep
sediments. (The point with depth 0 mm was not used for linear fit at D3 in July; * and
** represent significant correlation at p <0.05 and 0.01, respectively)
 Jan. Jul. Nov.
40 40 40
DGT-labile Mn (μmol·L-1)

DGT-labile Mn (μmol·L-1)
DGT-labile Mn (μmol·L-1)
X1 X1 y = 11.37x + 3.65 X1
R² = 0.119, p=0.449
30 30 30 y = -14.46x + 11.58
y = 234.16x - 14.35 (-50 to -110 mm) R² = 0.219, p=0.290
R² = 0.819**
y = 11.50x + 11.45 (-50 to -110 mm)
(0 to -110 mm) R² = 0.069, p=0.670
20 20 20
(0 to -40 mm) y = 47.45x + 1.40
R² = 0.761*
10 10 10 (0 to -40 mm)

0 0 0
0 3 6 9 0 3 6 9 0 3 6 9
40 DGT-labile P (μmol·L-1) 40 DGT-labile P (μmol·L-1) 40 DGT-labile P (μmol·L-1)

DGT-labile Mn (μmol·L-1)

DGT-labile Mn (μmol·L-1)
DGT-labile Mn (μmol·L-1)

X2 X2 X2
y = 9.27x + 2.15 y = 3.00x + 10.27 y = -8.97x + 31.79
30 30 R² = 0.043, p=0.620 30 R² = 0.654**
R² = 0.585, p=0.132
(0 to -40 mm) (-40 to -110 mm) (0 to -110 mm)
20 20 20

y = 4.86x + 9.48
10 10 y = 8.44x - 2.21 10
R² = 0.237, p=0.268
R² = 0.816, p=0.097
(-50 to -110 mm)
(0 to -30 mm)

of
0 0 0
0 1 2 3 4 0 1 2 3 4 0 1 2 3 4
60 DGT-labile P (μmol·L-1) 60 DGT-labile P (μmol·L-1) 60 DGT-labile P (μmol·L-1)
DGT-labile Mn (μmol·L-1)

DGT-labile Mn (μmol·L-1)
DGT-labile Mn (μmol·L-1)

D1

ro
D1 D1
y = 0.73x + 4.24
40 40 R² = 0.384* 40 y = -1.58x + 30.73
R² = 0.737**

20
y = 6.11x - 25.96
R² = 0.615**
(0 to -110 mm) 20
-p(0 to -110 mm)

20
(-10 to -110 mm)
re
0 0 0
0 10 20 30 0 10 20 30 0 10 20 30
lP

60 DGT-labile P (μmol·L-1) 60 DGT-labile P (μmol·L-1) 60 DGT-labile P (μmol·L-1)

DGT-labile Mn (μmol·L-1)

DGT-labile Mn (μmol·L-1)
DGT-labile Mn (μmol·L-1)

D2 D2 D2
y = 1.31x + 11.07
40 y = -0.34x + 43.20 40 R² = 0.281, p =0.077 40 y = 1.94x + 4.78
na

R² = 0.002, p=0.680 (0 to -110 mm) R² = 0.743**

(0 to -110 mm) (0 to -110 mm)
20 20 20
ur

0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Jo

25 DGT-labile P (μmol·L-1) 25 DGT-labile P (μmol·L-1) 25 DGT-labile P (μmol·L-1)

DGT-labile Mn (μmol·L-1)

DGT-labile Mn (μmol·L-1)
DGT-labile Mn (μmol·L-1)

D3 D3 D3 y = 0.20x + 13.54
20 20 20 R² = 0.096, p=0.455
y = 0.55x + 6.29 (-40 to -110 mm)
R² = 0.399* y = 0.68x + 3.07
15 15 R² = 0.717** 15
(0 to -110 mm)
(0 to -110 mm)
10 10 10
y = 0.14x + 9.81
5 5 5 R² = 0.837, p =0.085
(0 to -30 mm)
0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
DGT-labile P (μmol·L-1) DGT-labile P (μmol·L-1) DGT-labile P (μmol·L-1)

Fig.4. Linear fits between DGT-labile Mn and P in sediments from the Xizhi River
and the Danshui River in the three sampling campaigns. Blue, significant positive
relationship in surface sediments or the entire profile; black, no significant positive
relationship in surface sediments or the entire profile; red, the relationship in deep
sediments. (The point with depth 0 mm was not used for linear fit at D1 in November;
* and ** represent significant correlation at p <0.05 and 0.01, respectively)
 8

7 Desulfatiglans

Relative abundance of SRB (%)

Desulfarculus
6
Desulfatirhabdium
5
Desulfoprunum

4 Desulfobacca

Desulforhabdus
3
Desulfomicrobium
2
Desulfobulbus
1 Thermodesulfovibrio

0
X1 X1 X2 X2 X2 D1 D1 D1 D2 D2 D2 D3 D3
(1 cm) (11 cm) (3 cm) (6 cm) (11 cm) (1 cm) (9 cm) (11 cm) (1 cm) (6 cm) (11 cm) (1 cm) (11 cm)
Sampling site (depth)

Fig.5. Relative abundance of sulfate-reducing bacteria (SRB) at the genus level in

of
sediments from the Xizhi River and Danshui River in July. (Depth of sampling layer

ro
indicated in parenthesis)

-p
re
lP
na
ur
Jo
 0.3
a
Apparent DGT-labile P diffusion flux

0.2
(mg·cm-2·d-1)

0.1

0.0
X1 X2 D1 D2 D3
Jan. Jul. Nov.
6.0
b
Apparent DGT-labile Fe diffusion flux

of
5.0

ro
4.0
(mg·cm-2·d-1)

3.0
-p
re
2.0
lP

1.0

0.0
na

X1 X2 D1 D2 D3
0.6
c
Apparent DGT-labile Mn diffusion flux

ur

0.5

0.4
Jo
(mg·cm-2·d-1)

0.3

0.2

0.1

0.0
X1 X2 D1 D2 D3

Fig.6. Apparent diffusion flux of (a) labile P, (b) labile Fe and (c) labile Mn across the
SWI (from sediments to overlying water) in the three sampling campaigns.
Fe-P coupling release was the major mechanism leading to remobilization of sediment P
Reductive dissolution of Mn oxides was responsible for P release in polluted sediment
Sulfate reduction related to specific microbial activity triggered decoupling Fe/Mn-P
Upward diffusion fluxes of P and Fe were greater at polluted sites in summer seasons

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Jo
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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