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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
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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1 Release characteristics and mechanisms of sediment phosphorus in
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
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
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
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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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* Corresponding author.
E-mail address: nvtoo@sina.com (L. Gao)
**Corresponding author.
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35 Excessive nutrients discharged into water bodies can result in the rapid growth
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
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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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
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
58 (Shahandeh et al., 2003; Ding et al., 2012). When the co-released Fe, Mn, and P migrate
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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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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
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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
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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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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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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128 The ammonia nitrogen (NH3-N) concentrations of the water samples were
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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
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
140 mixture of concentrated sulfuric acid and 70% perchloric acid and then measured using
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).
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.
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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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170 where G is the grayscale intensity of ZrO-AgI binding gels. The concentration of
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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,
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
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
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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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194 respectively.
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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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
219 to identify the relationships between variables and correlations were considered
221
222 3. Results and Discussion
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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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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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.
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
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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
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
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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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
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
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
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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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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
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
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,
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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
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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.
382 As shown in Figure 6a, sediment P tended to migrate upward at all sites with
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
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
403 decreasing order as D1 (0.172 mg·cm–2·d–1) > D3 (0.163 mg·cm–2·d–1) > X1 (0.062
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
of
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
lP
414 4. Conclusions
415 This study used the DGT technique to explore the lability, remobilization, and
na
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
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
of
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)].
-p
re
434
lP
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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
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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)
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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
lP
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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Depth (mm)
Depth (mm)
Depth (mm)
Depth (mm)
Depth (mm)
Depth (mm)
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)
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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)
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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)
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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)
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
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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)
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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)
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0 0 0
0 10 20 30 0 10 20 30 0 10 20 30
lP
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
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
Jo
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
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)
of
sediments from the Xizhi River and Danshui River in July. (Depth of sampling layer
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indicated in parenthesis)
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lP
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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
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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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lP
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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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