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Article

Characteristics of Sedimentary Organic Matter and Phosphorus in Minor Rivers Discharging into Zhejiang Coast, China

1
Ocean College, Zhejiang University, Zhoushan 316021, China
2
College of Ocean and Earth Sciences, Xiamen University, Xiamen 361102, China
*
Authors to whom correspondence should be addressed.
Geosciences 2020, 10(9), 357; https://doi.org/10.3390/geosciences10090357
Submission received: 6 August 2020 / Revised: 28 August 2020 / Accepted: 2 September 2020 / Published: 5 September 2020
(This article belongs to the Section Geochemistry)

Abstract

:
In this study, the spatial distribution of lignin-derived phenols, bulk elemental composition and different phosphorus (P) species in surface sediments along six rivers discharging into Zhejiang coast, Southeast China, were investigated to improve the understanding of the carbon and P dynamics in these small river systems. The Shuang, Jiao, Ximen, Feiyun and Ao Rivers have total organic carbon (TOC) ranging from 0.29% to 2.77% and Λ (total lignin in mg/100 mg TOC) ranging from 0.24 to 4.24; Qiantang River has the lowest Λ (0.08–0.19) but the highest TOC (1.05%–6.46%). Jiao, Ximen, Feiyun and Ao Rivers have mean the total P (TP) and bioavailable P (BAP) of 34 to 124 mg/kg and 29 to 89 mg P/kg, and mean OC/OP molar ratio of 397–917. Qiantang River has the lowest mean TP and BAP of 13 mg P/kg and 7 mg P/kg, and highest OC/OP of 18,753; whereas Shuang River has the highest mean TP and BAP of 645 mg P/kg and 559 mg P/kg, and lowest mean OC/OP of 90. The lowest Λ, TP and BAP, but highest OC/OP, in the Qiantang River could be due to tidal bore causing rapid cycling of carbon and P. Trends of slight decrease in abundance of OC, Λ, TP and BAP, but increasing ratios of vanillic acid to vanillin [(Ad/Al)v], syringic acid to syringaldehyde [(Ad/Al)s] and OC/OP farther downstream of the rivers indicate a continuous decomposition of organic matter during transport along the rivers.

1. Introduction

Rivers are home to various organisms, animals and plant species, providing livelihood to human and serving as a regulator of carbon and nutrient [1,2]. However, many of the world’s rivers have become ‘sick rivers’ because of human activities such as deforestation, river engineering, overfishing and pollution [3,4,5]. The presence of dams [6] and extreme weather affect the chemical and biological compositions of river systems. As a consequence, many plant and animal species are facing extinction. Loss of buffering capacities of rivers has increased pollution in coastal zones [1]. Many studies have been carried out for larger rivers [7,8,9,10], while small rivers were given less priorities though they undergo severe degradation in recent decades and they will likely disappear first compared to large rivers.
Various studies on bulk elemental composition, stable carbon isotope and biomarkers in sediments and particulate organic matter (POM) have improved the understanding on the biogeochemistry of sedimentary organic matter in lakes [11,12], coastal zones and oceans [13,14,15], as well as river systems [9,10]. Studies have found phytoplankton to be the major source of POM downstream of the Mississippi, Colorado, Rio Grande and Columbia Rivers [16]. On the other hand, detection of older POM in the Hudson-Mohawk river systems was due to the contribution of older soil organic matter [17]. The mainstream of a small mountainous river, Lanyang Hsi, has POM characteristics of soil and rock materials, but its tributaries showed signal of plant materials [18]. Elsewhere, deforestation has resulted in the presence of highly degraded lignin materials in the Rio Tapajos [19]. Downstream Kapuas River has high sedimentary organic carbon (OC), but not corresponding high lignin content, indicating contribution of OC from anthropogenic sources [9]. The sediments along the Yangtze River have organic matter of plant and soil origins and showed effects from local inputs [10].
Sedimentary phosphorus (P) species have also been studied extensively in rivers [20,21] as only certain P forms are associated with P pollution in the aquatic environments [22,23]. Extremely polluted rivers are loaded with high sedimentary TP, NaOH-P (or Fe/Al-P, the P fraction which composed the loosely bound P and P bound to hydrated oxides of Al and non-reducible Fe), and organic P (OP) fractions [24]. Another study found a significant correlation between P release rate and NaOH-P fraction, indicating the importance of the iron-bound P contributing to the P in the water. This bioavailable Fe-P pool was released from sediments during hypoxia and caused an increase in primary production in coastal zone [25].
In this study, surface sediments from six rivers discharging into the Zhejiang coast were determined for lignin-derived phenols, bulk elemental composition and different P species. Lignins are complex molecules present only in vascular plant tissues, and thus, lignins are used as biomarkers for land-derived or terrestrial organic matter. Some lignin monomers produced upon CuO oxidation can be indicative of vegetation types and lignin decomposition stage. For example, the ratios of syringyl/vanilyl (S/V) and cinnamyl/vanillyl (C/V) phenols are indicators of angiosperm versus gymnosperm, and non-woody versus woody tissues; the vanillic acid/vanillin and syringic acid/syringaldehyde ratios, abbreviated as (Ad/Al)v and (Ad/Al)s, are indicators of decomposition stage of lignin materials [26]. Likewise, TOC/TN molar ratio is also used as an indicator of organic matter sources, as terrestrial organic matter has relatively higher TOC/TN (> 23) than marine organic matter (5–12) [27]. The sedimentary P species elucidated in this study include the NaOH-P, HCl-P or apatite P, inorganic P (IP), OP and TP. The NaOH-P fraction is composed of the loosely adsorbed, exchangeable and water soluble P, as well as the Fe-P, which is pH- and redox-sensitive, and is a source of internal P loading during anoxic conditions. OP is released during aerobic decomposition of organic matter and HCl-P is the most stable P form [28,29]. Thus, understanding the sources, distribution and chemical stability of sedimentary organic matter and P will improve our knowledge on the carbon and P dynamics in these small river systems.

2. Materials and Methods

2.1. Study Areas and Sampling

Surface sediments were collected from along six rivers that discharge into the Zhejiang coast: Qiantang River in Hangzhou, Shuang River in Ningbo, Jiao River in Taizhou and Ximen, Feiyun and Ao Rivers in Wenzhou. The Qingshan Bay off the Shuang River mouth and some locations at the Leqing Bay off Ximen Island were also sampled. The sampling information and locations are given in Appendix A (Table A1) and Figure 1. The distance between two sampling locations was 0.15–11.31 km but mostly 1–2 km. The sampling locations along the middle part of the rivers were accessed by boat and the surface sediments were collected using a grab sampler. The sediments were stored frozen at −20 °C, freeze dried and homogenised using a mortar and pestle.

2.2. Analytical Methods

2.2.1. Bulk Elemental and Lignin Analysis

Dry sediment was added to an excess of 1 N HCl and let to stand overnight to remove the inorganic carbon. The residues were dried in oven at 50 °C for two days, homogenised using a mortar and pestle. They were weighed precisely into tin foil and crimped into pellets, and determined for TOC and TN using a LECO-CHN 932 elemental analyser (Elementar, Germany). BCSS-1 and NIST-1 were used as the standard reference materials. The precision for TOC and TN was <5%.
Lignin analysis was carried out based on the CuO oxidation method. Precisely 0.5 g dry sediment and 1.0 g CuO powder were weighed into a 25 mL polytetrafluoroethylene (PTFE) vessel. Precisely 10 mL of 2 M aqueous NaOH in a test tube was bubbled with N2 for 3 min. The PTFE vessels, test tubes and their contents were purged with N2 for a few minutes in a glove bag, the NaOH solution was then poured into the contents of the PTFE vessel, and the vessel was capped. The vessels were then heated from room temperature to 170 °C for 3 h and manually shaken every hour. After 3 h, the vessels were allowed to cool. The contents of the vessel were washed three times with 20 mL of 1 M NaOH and centrifuged. The supernatants were combined, acidified to pH 1 with 6 M HCl and extracted three times with 20 mL ethyl acetate. The extracts were then dried with anhydrous Na2SO4, filtered through Whatman filter paper, and spiked with 100 μL ethyl vanillin as the internal standard. This was concentrated to 1–2 mL and N2 blown down. The oxidation product was dissolved in equal amounts of pyridine and bis-(trimethylsilyl) trifluoroacetamide with 10% trimethylchlorosilane and derivatised at 90 °C for 10 min. The solution was ready to be analysed by gas chromatography HP5880A (Agilent Technologies, USA) with flame ionisation detection. The column temperature increased from 100 °C to 300 °C at 4 °C min−1.

2.2.2. Sedimentary P Species

Determination of different sedimentary P species was carried out based on the ‘Standards, Measurements and Testing (SMT)’ method by Ruban et al. [30,31] to elucidate different sedimentary P fractions such as NaOH-P, HCl-P, OP and IP. Precisely 200 mg of sediment was added with 20 mL of 1 M NaOH, shaken for 16 h and then centrifuged at 2000 g for 15 min and the supernatant was determined for NaOH-P or Fe/Al-P. The sediment residue was washed with 12 mL of 1 M NaCl, stirred for 5 min and centrifuged at 2500 rpm for 15 min. The supernatant from this step was discarded. After that, the residue was added with 1 M HCl, shaken for 16 h, centrifuged and the supernatant was measured for HCl-P.
Another set of dry sediment was weight to 200 mg and added with 10 mL of 1 M HCl. This was extracted by shaking for 16 h, centrifuged and the supernatant was determined for IP. The residue was washed twice with distilled water and centrifuged. The residue was then combusted at 500 °C for 6 h, added with 20 mL of 1 M HCl and extracted by shaking for 16 h. The following day, this was centrifuged and the supernatant was determined for OP. Total P was the sum of IP and OP. P was determined using the molybdate blue method at a wavelength of 885 ɳm. P concentration was determined based on the absorbance of the sample extract and calculated as follows: C = SV, where C = concentration of P in mg P/kg, S = concentration of sample obtained from the calibration curve (mg/kg) and V = volume of solvent used [30,31]. All solutions were stored in plastic containers as a precautionary measure. We presume there will be no silicate interference throughout the process, as the tartrate in the working reagent could also prevent reaction between silicate and ammonium molybdate [32].

3. Results

3.1. Sedimentary Organic Matter

The complete results of lignin parameters, TOC and TOC/TN molar ratios are given in Appendix A (Table A2). The Qiantang River has the highest %TOC (ranged from 1.05% to 6.46%) compared to the other five rivers (0.29%–2.77%). Similarly, the percentage of TN was also the highest in Qiantang River (0.21%–1.36%), followed by Shuang River (0.09%–0.44%) and Ao River (0.09%–0.20%). Jiao, Ximen and Feiyun Rivers had a low TN content of 0.06%–0.14%. The overall TOC/TN molar ratios varied at 5.0–11 in all the rivers.
Total lignin (Λ, mg/100 mg TOC) ranged from 0.075 to 4.236. Locations along Qiantang River had the lowest Λ values of 0.075–0.186. Ao and Shuang Rivers had Λ values of 0.244–1.706 and 0.329–1.909, respectively. Jiao, Ximen and Feiyun River had higher Λ values of 0.325–4.236. Similar to Λ and TOC, the S/V ratios (0.72–12.33, excluding the highest values of 21 and 37) and C/V ratios (0.486–8.000) in Qiantang River were higher than the S/V (0.250–3.500) and C/V ratios (0.02–0.692) in other five rivers. The rivers in this study had a wide range of (Ad/Al)v values of 0.045–1.842 and (Ad/Al)s values of 0.088–2.540. The extremely high S/V, C/V, TOC, but rather low Λ, in Qiantang River compared to the other five rivers is further illustrated in Figure 2. Correlation results among lignin parameters and bulk elemental composition showed no relationship, except for the significant positive correlation between TOC and TN (Appendix A, Table A3).

3.2. Sedimentary P Species

The results of sedimentary P fractions are given in Appendix A (Table A4). Percentages of each P fraction and bioavailable P to TP, and OC/OP molar ratios are then calculated. Table 1 shows the ranges and mean values of these parameters. The mean TP concentrations for these rivers are in the following order: Shuang (645 ± 29 mg P/kg) > Ao (124 ± 45 mg P/kg) > Jiao (81 ± 16 mg P/kg) > Feiyun (79 ± 7 mg P/kg) > Ximen (34 ± 5 mg P/kg) > Qiantang (13 ± 4 mg P/kg). Similar to TP, all P fractions were highest at Shuang River and lowest at Qiantang River. The extremely high concentrations of all P fractions of Shuang River sediments compared to the other five rivers are further illustrated in Figure 3. Bioavailable P (BAP) is the sum of NaOH-P and OP. The mean concentrations of bioavailable P are in this order: Shuang (559 mg P/kg) > Ao (89 mg P/kg) > Jiao (42 mg P/kg) > Feiyun (39 mg P/kg) > Ximen (29 mg P/kg) > Qiantang (5 mg P/kg). The percentages of bioavailable P to TP are in the following order: Shuang (87%) > Ximen (84%) > Ao (69%) > Qiantang (53%) > Jiao (50%) > Feiyun (49%). The Shuang River has the highest concentration of BAP, which was about 6 to more than 100 times higher than the other five rivers.
The mean OC/OP molar ratios are in the following order: Qiantang (18,754) > Jiao (917) > Ximen (729) > Feiyun (635) > Ao (397) > Shuang (90). Very high OC/OP ratio at Qiantang River was attributable to the highest TOC (ranged between 1.05% and 6.46%) and lowest OP (ranged from 3 to 7 mg/kg) in the Qiantang River compared to the other five rivers (TOC ranged from 0.29% to 2.77%; OP ranged from 26 to 687 mg/kg). As OP is preferentially utilized relative to OC during aerobic organic matter decomposition, higher TOC and higher OC/OP ratios indicate the presence of labile materials where the P was easily degradable [33]. Most of the sedimentary P species have significant positive correlation among one another (Appendix A, Table A5).

4. Discussion

4.1. Sources of Sedimentary Organic Matter

As angiosperms are composed of syringyl (S) and vanillyl (V) phenols, and gymnosperms contain vanillyl phenol, higher S/V ratios indicate the presence of more angiosperm compared to gymnosperm tissues. Higher C/V ratios indicate non-woody tissues as cinnamyl (C) phenols are found in non-woody tissues but not in woody tissues. Studies have demonstrated that S/V > 0.4 indicates the presence of angiosperm tissues and C/V > 0.2 indicates non-woody tissues [34,35]. The S/V and C/V ratios in the Shuang, Jiao, Ximen, Feiyun and Ao Rivers ranged from 0.250 to 3.500 and from 0.020 to 0.692, respectively, which showed predominance of non-woody angiosperms in these rivers, except for a few locations in Shuang and Jiao Rivers which have demonstrated the presence of some woody signal as represented by some rather low C/V ratios. The S/V and C/V compositional plot showed that most ratios fall within the range for non-woody angiosperm tissues (Figure 4). These results are inconsistent with other locations in this region such as Changjiang Estuary [10] and salt marsh at the southwest of Hangzhou Bay [36] which had shown predominance of non-woody angiosperm tissues.
Higher TOC/TN ratios could be due to preferential loss of N components that are protein-rich, lower TOC/TN could be due to conversion of plant materials to microbial biomass [37]. Low C/N ratios have also been demonstrated for organic matter from meta-sedimentary rocks [18]. Thus, the rather low TOC/TN molar ratios (which ranged from 5 to 11) in the rivers in this study (including Qiantang River) indicate decomposed organic matter, as also supported by the elevated (Ad/Al)v and (Ad/Al)s values in these rivers, which indicate more degraded lignin materials.

4.2. P Pollution

The Shuang River TP was slightly higher than the other rivers. The high NaOH-P, as well as all P contents, at the Shuang River most likely indicates P pollution from anthropogenic activities, as higher content of loosely bound-P has been associated with wastewater discharge [38]. The TP levels in rivers investigated in this study were slightly lower compared to some other locations in China such as the Min River Estuary marsh sediments which have TP ranging from 338 mg P/kg to 932 mg P/kg [39]; rivers discharging into the Bohai Sea such as Liao and Yongdingxin have TP of 219 mg P/kg and 913 mg P/kg [24]; TP in the Yellow River delta sediments was 542 mg P/kg [40]; and studies of ten major basins in China found that the average TP in sediments was around 733 mg P/kg [41].
The rivers in this study have high proportion of BAP in their sediments because of their high OP contents which constitute of 34% to 69% of TP. The percentage of NaOH-P to TP ranged from 11% to 44%, indicating that a portion of this fraction, which includes the loosely bound P and Fe-P, can be released to the aquatic environments. The BAP in these rivers were higher in comparison to some locations such as the east coast of Hainan Island (20% to 54% of BAP) [42] and the Jiazhou Bay (40%–53% BAP) [38]; rivers discharging into the Bohai Sea that were polluted with fertilizer and sewage have high abundances of NaOH-P and OP of 223 mg/kg NaOH-P (24% of TP) and 125 mg/kg OP (14% of TP), respectively [24]. These results suggest that sediments in these rivers are prone to release P to the overlying water column.

4.3. Dynamics of Sedimentary Organic Matter and P

Our results revealed slight decrease of Λ values along the rivers, followed by drastic increases in Λ values at some locations, especially at the river mouths. There were mixed trends of (Ad/Al)v and (Ad/Al)s values, with the locations at the river mouths usually have higher ratios (Figure 5). TOC and TN showed slight increase along the rivers, then decrease at the river mouths, as supported by the significant negative correlation between Λ with TOC and TN (p < 0.05), indicative of contribution from anthropogenic carbon and nitrogen besides terrestrial materials farther downstream. The P forms gradually increased, followed by decreasing trend along Qiantang and Jiao Rivers; and gradual decrease along the rivers at Feiyun, Shuang and Ximen; but gradual increase along Ao Rivers (Figure 6).
Decreasing abundance of terrestrial organic matter and P was most probably attributed to decomposition of terrestrial organic matter along the rivers. There was increased accumulation and further decomposition of terrestrial organic matter at the river mouths. Both continuous decomposition of terrestrial organic matter along the rivers and at the river mouths also indicate that these rivers most probably serve as carbon source. This is consistent with other studies which have found that rivers are carbon sources due to decomposition of fresher [43] terrestrial organic matter [44].
Increasing trends of TOC/TN ratios along the Qiantang, Shuang, Jiao, Ximen and Feiyun Rivers further supported increased organic matter decomposition farther downstream. The gradual increases of TOC/OP along the rivers indicate accumulation of terrestrial organic matter farther downstream and increased decomposition downstream. There were drastic decreases of TOC/TN ratios at the Ximen and Feiyun river mouths, this could indicate more decomposed materials, as supported by the very high (Ad/Al)v and (Ad/Al)s values here. The Qiantang River is well-known for the occurrence of tidal bore [45]. Thus, the lowest Λ values and P in the Qiantang River could be attributable to the rapid organic matter decomposition due to physical disturbances of the tidal bore facilitated mixing and resuspension, thus, further facilitated decomposition of sedimentary organic matter.

5. Conclusions

The S/V and C/V ratios in sediments of small rivers along the Zhejiang Coast of SE China indicate predominance of non-woody angiosperm tissues and the large ranges of (Ad/Al)v and (Ad/Al)s values indicate the presence of fresh to degraded lignin materials. The ranges of TOC in Shuang, Jiao, Ximen, Feiyun and Ao Rivers were 0.29%–2.77%; Qiantang River has the highest TOC of 1.05%–6.46%. Total lignin, Λ, in Shuang, Jiao, Ximen, Feiyun and Ao Rivers ranged from 0.24 to 4.24; Qiantang River has the lowest Λ of 0.08 to 0.19. TP was the highest in Shuang (645 mg P/kg), followed by the other four rivers (34–124 mg P/kg) and the lowest in Qiantang River (13 mg P/kg). On the other hand, Qiantang River has the highest OC/OP molar ratio (18,753), followed by the other four rivers (397–917) and Shuang River (90). High TOC in Qiantang River could be due to anthropogenic input. High OC/OP but low TP and Λ in Qiantang River indicates rapid recycling of organic matter and P. The high TP and low OC/OP in Shuang River could be due to the relatively higher P pollution in this river in comparison to the other rivers. Our results indicate rapid cycling of sedimentary organic matter and P along these rivers, resulting in highly degraded materials at the river mouths and low P pollution in the sediments.

Author Contributions

Writing—P.S.L., S.K.; supervision, P.S.L.; investigation, L.-X.C., S.-Y.L.; funding acquisition, S.K. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by National Natural Science Foundation of China (41273083).

Acknowledgments

This study acknowledges the MEL Senior Visiting Fellowship by the State Key Laboratory of Marine Environmental Science, Xiamen University.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table A1. Locations information.
Table A1. Locations information.
DateStationLongitude (°)Latitude (°)DateStationLongitude (°)Latitude (°)
2014.10.16A1120.600927.58842014.10.18J1121.463228.6900
Ao RiverA2120.595227.5901Jiao RiverJ2121.451128.6930
A3120.582727.5873J3121.442128.6958
A4120.572527.5803J4121.426528.6992
A5120.562027.5793J5121.420628.6991
A6120.554627.5864J6121.411528.7001
A7120.556227.5879J7121.390528.7028
2014.10.17F1120.645627.7355J8121.392828.7014
Feiyun RiverF2120.637127.7426J9121.367528.7036
F4120.624227.7604J10121.352228.7058
F5120.620027.76642014.10.19S1121.557229.2164
F6120.617027.7734Shuang RiverS2121.570229.1933
F7120.619327.7807S3121.590529.1744
F8120.617027.7877S4121.608529.1631
F9120.613027.7924S5121.623829.1669
F10120.628227.7703S6121.625229.1808
F11120.645527.7341S7121.625329.1883
F12120.652627.7275S8121.607329.1961
2014.10.18X1121.207828.3264S9121.621729.1997
Ximen IslandX2121.212728.33062014.10.20Q4120.442130.3903
X3121.216628.3261Qiantang RiverQ5120.453330.3921
X4121.214428.3194Q7120.422430.3635
X5121.212128.3118Q8120.417630.3520
X6121.208528.3193Q9120.412830.3405
X7121.210328.3082Q10120.406730.3266
X8121.211228.3035Q11120.401930.3133
Q12120.418530.3074
Q13120.424430.3185
Q14120.429230.3308
Table A2. Lignin parameters, TOC, TN and C/N ratios along (a) Qiantang River (Q), (b) Shuang River (S), (c) Jiao River (J), (d) Ximen Island (X), (e) Feiyun River (F), (f) Ao River (A).
Table A2. Lignin parameters, TOC, TN and C/N ratios along (a) Qiantang River (Q), (b) Shuang River (S), (c) Jiao River (J), (d) Ximen Island (X), (e) Feiyun River (F), (f) Ao River (A).
(a) Qiantang River (Q)
QiantangS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
Q110.0070.0040.0090.0201.7502.2500.1880.7572.660.535.90.075
Q120.0060.0020.0050.0133.0002.5001.0600.4031.740.355.80.075
Q100.0420.0020.0050.04921.0002.5000.3430.2062.630.525.90.186
Q130.0050.0040.0040.0131.2501.0000.4322.7091.050.215.80.124
Q90.0740.0020.0160.09237.0008.0000.6190.2836.461.365.50.142
Q140.0220.0020.0030.02711.0001.5000.2350.0881.810.336.30.149
Q80.0370.0030.0020.04212.3330.6670.4140.2094.060.835.70.103
Q70.0370.0040.0020.0439.2500.5000.0910.2163.490.4010.30.123
Q40.0470.0370.0180.1021.2700.4860.9550.765
Q50.0060.0080.0110.0250.7501.3750.1781.0162.040.386.30.123
Mean0.0280.0070.0080.0439.8602.0780.4510.6652.880.556.40.122
(b) Shuang River (S)
ShuangS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
S80.0180.0330.0060.0570.5450.1820.1640.5040.970.205.60.588
S90.0430.0420.0120.0971.0080.2840.3750.3570.670.145.61.454
S70.0370.0520.0060.0950.7120.1150.3770.5031.170.149.50.812
S60.0270.0480.0090.0840.5630.1880.1470.4590.440.105.31.909
S50.0180.0350.0030.0560.5140.0860.2420.4850.460.096.01.217
S40.0190.0380.0040.0610.5000.1050.3780.6680.840.195.00.726
S30.0240.0350.0040.0630.6860.1140.3190.5940.900.147.50.700
S20.0430.0490.0010.0930.8780.0201.3441.0700.900.0911.01.033
S10.0430.0420.0060.0911.0240.1430.2750.5702.770.447.30.329
Mean0.0300.0420.0060.0770.7140.1370.4020.5791.010.177.00.974
(c) Jiao River (J)
JiaoS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
J100.0080.0180.0060.0320.4440.3330.8420.6160.620.107.10.516
J90.0260.0190.0040.0491.3680.2111.2170.1360.650.117.10.754
J70.0190.0300.0050.0540.6330.1670.0580.5470.630.117.00.857
J80.0280.0080.0030.0393.5000.3750.1100.1430.670.117.30.582
J60.0800.0900.0080.1780.8890.0890.3530.4910.650.117.22.738
J40.0900.1410.0370.2680.6380.2621.8370.1580.680.117.43.941
J30.0520.0500.0110.1131.0400.2200.3420.3190.580.088.01.948
J20.0550.0660.0090.130.8330.1360.1010.1610.640.098.12.031
J10.0210.0190.0080.0481.1050.4210.0450.3460.620.098.00.774
Mean0.0420.0490.0100.1011.1610.2460.5450.3240.640.107.51.571
(d) Ximen Island (X)
XimenS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
X20.0410.0510.0070.0990.8040.1370.2490.2490.550.116.01.800
X10.0360.0380.0150.0890.9470.3950.1700.3160.480.096.01.854
X30.0430.0620.0210.1260.6940.3390.3910.8920.740.146.31.703
X60.0110.0130.0050.0290.8460.3850.7062.5400.810.146.90.358
X40.0330.0430.0080.0840.7670.1860.4780.7220.640.116.71.313
X50.0330.0560.0160.1050.5890.2860.2820.6030.770.136.81.364
X70.0320.0360.0080.0760.8890.2220.4811.2030.630.107.21.206
X80.0400.0410.0090.0900.9760.2200.2750.9730.290.065.43.103
Mean0.0340.0430.0110.0870.8140.2710.3790.9370.610.116.41.588
(e) Feiyun River (F)
FeiyunS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
F90.053 ± 0.00650.067 ± 0.01130.016 ± 0.00620.1370.798 ± 0.04970.244 ± 0.07490.269 ± 0.14850.232 ± 0.08420.600.098.12.294
F80.0130.0280.0080.0490.4640.2860.3480.5530.640.098.70.766
F70.0310.0340.0110.0760.9120.3240.0880.1690.650.098.61.169
F60.0530.0610.0090.1230.8690.1480.5300.8880.680.098.81.809
F50.0100.0080.0080.0261.2501.0000.0610.5970.800.109.50.325
F100.0300.0540.0060.0900.5560.1110.6020.6520.670.108.11.343
F40.0160.0270.0040.0470.5930.1480.1210.4170.670.098.70.701
F20.0300.0430.0080.0810.6980.1860.2690.3310.710.108.61.141
F10.0670.0670.0240.1581.0000.3580.0760.1130.760.109.32.079
F110.1080.1090.0160.2330.9910.1470.2950.2390.550.087.74.236
F120.0070.0280.0030.0380.2500.1070.9811.1070.680.107.80.559
Mean0.0380.0480.0100.0960.7620.2780.3310.4820.670.098.51.493
(f) Ao River (A)
AoS
(mg/g)
V
(mg/g)
C
(mg/g)
Total
(mg/g)
S/VC/V(Ad/Al)v(Ad/Al)sTOC
(%)
TN
(%)
C/NΛ
(mg/100 mg TOC)
A60.0420.0540.0200.1160.7780.3700.1600.1430.680.098.61.706
A70.0360.0350.0080.0791.0290.2290.2850.4600.600.098.01.317
A50.0390.0450.0110.0950.8670.2440.2740.2250.680.098.71.397
A40.0450.0670.0150.1270.6720.2240.2670.1651.030.157.81.233
A30.0110.0130.0090.0330.8460.6920.1520.2011.350.208.00.244
A20.0180.0130.0090.0401.3850.6920.3210.2400.980.196.00.408
A10.0410.0500.0100.1010.8200.2000.3770.2580.640.098.11.578
Mean0.0330.0400.0120.0840.9140.3790.2620.2420.850.137.91.126
Table A3. Correlation among the lignin parameters. (a) Qiantang River (Q): N = 10, (b) Shuang River (S): N = 9, (c) Jiao River (J): N = 9, (d) Ximen Island (X): N = 8, (e) Feiyun River (F): N = 11, (f) Ao River (A): N = 7.
Table A3. Correlation among the lignin parameters. (a) Qiantang River (Q): N = 10, (b) Shuang River (S): N = 9, (c) Jiao River (J): N = 9, (d) Ximen Island (X): N = 8, (e) Feiyun River (F): N = 11, (f) Ao River (A): N = 7.
(a) Qiantang River (Q): N = 10
QS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V10.692 *−0.031−0.669 *0.5010.861 **0.871 **0.124
C/V 10.261−0.1710.0090.6610.764 *−0.393
(Ad/Al)V 10.344−0.3870.0580.199−0.468
(Ad/Al)S 1−0.490−0.545−0.439−0.287
Λ 10.1270.1120.054
TOC 10.954 **0.037
TN 1−0.262
C/N 1
(b) Shuang River (S): N = 9
SS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V1−0.2090.4640.446−0.3960.779 *0.5720.664
C/V 1−0.723 *−0.6560.1440.0060.227−0.683 *
(Ad/Al)V 10.967 **−0.026−0.024−0.2250.778 *
(Ad/Al)S 1−0.1120.020−0.1520.646
Λ 1−0.704 *−0.681 *−0.212
TOC 10.939 *0.243
TN 1−0.094
C/N 1
(c) Jiao River (J): N = 9
JS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V10.265−0.203−0.367−0.2600.4540.351−0.166
C/V 10.0400.312−0.460−0.024−0.1270.108
(Ad/Al)V 10.1100.5140.4290.374−0.336
(Ad/Al)S 1−0.362−0.306−0.106−0.255
Λ 10.3820.1400.110
TOC 10.796 *−0.423
TN 1−0.865 **
C/N 1
(d) Ximen Island (X): N = 8
XS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V1−0.0560.4570.5440.263−0.347−0.462−0.031
C/V 10.0760.394−0.2410.2880.2990.070
(Ad/Al)V 10.843 **−0.6550.6020.5050.662
(Ad/Al)S 1−0.5190.3880.3210.391
Λ 1−0.845 **−0.766 *−0.831 *
TOC 10.961 **0.800 **
TN 10.618
C/N 1
(e) Feiyun River (F): N = 11
FS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V10.590−0.490−0.3760.3960.207−0.2580.433
C/V 1−0.523−0.158−0.3350.639 *0.2900.710 *
(Ad/Al)V 10.798 **−0.070−0.1830.204−0.603 *
(Ad/Al)S 1−0.4970.2200.416−0.168
Λ 1−0.632 *−0.655 *−0.455
TOC 10.810 **0.806 **
TN 10.378
C/N 1
(f) Ao River (A): N = 7
AS/VC/V(Ad/Al)V(Ad/Al)SΛTOCTNC/N
S/V1−0.2210.5600.1930.157−0.628−0.341−0.364
C/V 1−0.3970.485−0.888 **0.7420.844 *−0.574
(Ad/Al)V 1−0.0010.176−0.449−0.242−0.365
(Ad/Al)S 1−0.6360.2260.377−0.376
Λ 1−0.825 *−0.931 **−0.666
TOC 10.931 **−0.360
TN 1−0.688
C/N 1
* represents significance to 0.05; ** represents significance to 0.01.
Table A4. Sedimentary P fractions in the rivers. (a) Qiantang River (Q), (b) Shuang Creek (S), (c) Jiao River (J), (d) Ximen Island, (e) Feiyun River (F), (f) Ao River (A).
Table A4. Sedimentary P fractions in the rivers. (a) Qiantang River (Q), (b) Shuang Creek (S), (c) Jiao River (J), (d) Ximen Island, (e) Feiyun River (F), (f) Ao River (A).
(a) Qiantang River (Q)
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratio
NaOH-PHCl-PIPOPTPBAP
Q112.552.859.373.4812.856.032.6619741
Q124.301.549.283.4412.727.741.7413050
Q101.122.216.774.0110.785.132.6316921
Q132.532.1510.715.4116.127.941.055005
Q91.732.149.263.7012.965.436.4645130
Q142.035.4111.796.6318.428.661.817050
Q81.081.907.933.6611.594.744.0628621
Q71.78 ± 0.24 2.74 ± 1.29 8.35 ± 0.14 4.42 ± 0.59 12.776.203.4920410
Q47.1615.148014.455.5319.9812.69
Q51.405.54492.394.106.495.502.0412853
Mean2.574.169.034.4413.477.012.8818753
stdev± 1.87± 4.11± 3.18± 1.07± 3.87± 2.39± 1.63± 12214
(b) Shuang Creek (S)
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratio
NaOH-PHCl-PIPOPTPBAP
S8379.14315.42375.00311.60686.60690.740.9780
S9442.12 ± 17.41 303.34 ± 2.39 338.37 ± 2.80 261.85 ± 8.87 600.22703.970.6766
S7349.51313.79354.98275.26630.24624.770.7166
S6288.74378.91339.34278.53617.87567.270.4441
S5175.60352.34395.93270.21666.14445.810.4644
S4231.12339.26370.65303.27673.92534.390.8472
S3229.94373.42395.53271.49667.02501.430.7370
S2213.81374.51393.66244.55638.21458.360.9095
S1243.64358.08368.59259.95628.54503.592.77275
Mean283.74345.45370.23275.19645.42558.930.9490
Stdev± 88.31± 28.87± 22.57± 20.95± 29.10± 95.33± 0.71± 71
(c) Jiao River (J)
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratio
NaOH-PHCl-PIPOPTPBAP
J104.4824.1266.509.8776.3714.350.621629
J98.1123.0745.836.6852.5114.790.652507
J88.1143.4849.5412.2561.7920.360.671406
J78.0639.9750.4228.0678.4836.120.63579
J635.22 ± 10.85 34.43 ± 5.74 43.56 ± 6.54 40.87 ± 5.06 84.4376.090.65411
J49.0538.5639.0941.3780.4650.420.68422
J317.8138.5050.7355.81106.5473.620.58268
J213.7942.8548.5945.8394.4259.620.64360
J110.6234.3866.3523.9890.3334.60.62672
Mean12.8135.4851.1829.4180.5942.220.64917
stdev± 9.24± 7.44± 9.41± 17.55± 16.35± 23.99± 0.03± 765
(d) Ximen Island
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratio
NaOH-PHCl-PIPOPTPBAP
X24.4013.347.0731.0438.1135.440.55453
X110.0315.779.7830.1339.9140.160.48412
X33.1217.416.8528.7635.6131.880.75651
X62.2910.405.2620.9426.223.230.81997
X43.7613.488.8430.6539.4934.410.64537
X54.49 ± 0.45 15.69 ± 0.59 11.32 ± 0.41 20.43 ± 1.13 31.7524.920.77969
X72.4315.1818.4712.2030.6714.630.631337
X89.7513.7812.6515.5728.2225.320.29475
Mean5.0314.3810.0323.7233.7528.750.62729
stdev± 3.11± 2.12± 4.19± 7.42± 5.27± 8.22± 0.17± 335
(e) Feiyun River (F)
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratios
NaOH-PHCl-PIPOPTPBAP
F912.0134.4048.4335.8184.2447.820.60430
F85.5721.5160.3817.5277.923.090.64943
F713.20 ± 0.25 24.09 ± 0.67 51.47 ± 0.47 23.80 ± 2.82 75.27370.65707
F66.0521.8349.8924.5974.4830.640.68716
F54.1627.4958.8023.6182.4127.770.80870
F108.7528.2234.4747.4381.956.180.67365
F46.4128.0145.2836.1981.4742.60.67475
F211.8934.3062.9530.0092.9541.890.71607
F19.8432.8649.5221.4470.9631.280.76914
F119.7227.9727.6650.4078.0660.120.55284
F124.3426.1143.1325.9069.0330.240.68679
Mean8.3627.8948.3630.6178.9738.970.67635
Stdev± 3.23± 4.51± 10.67± 10.69± 6.70± 11.96± 0.07± 225
(f) Ao River (A)
LocsConcentration of P fraction (mg/kg)OC (%)OC/OP molar ratio
NaOH-PHCl-PIPOPTPBAP
A614.6040.7954.7952.08106.8766.680.68338
A710.6238.7449.2735.6484.9146.260.60435
A548.7749.0561.3162.68123.99111.450.68279
A418.7350.6848.3857.13105.5175.861.03465
A37.87 ± 0.84 51.42 ± 1.83 54.91 ± 6.17 40.99 ± 2.62 95.948.861.35851
A25.9552.8749.5179.79129.385.740.98317
A118.6426.5552.12168.97221.09187.610.6497
Mean17.8844.3052.9071.04123.9488.920.85397
stdev± 14.50± 9.54± 4.55± 45.54± 45.47± 48.90± 0.28± 233
Table A5. Correlation analyses among the P species and some lignin and elemental parameters.
Table A5. Correlation analyses among the P species and some lignin and elemental parameters.
HCl-PIPOPTPBAPOCTOC/OP
NaOH-P0.9190.9230.9250.9320.983−0.0964−0.208
1.232E-0222.977E-0231.895E-0231.270E-0243.586E-0400.4920.135
54545454545353
HCl-P 0.9920.9630.9890.958−0.122−0.258
1.765E-0482.291E-0311.522E-0448.198E-0300.3850.0618
545454545353
IP 0.9630.9930.960−0.133−0.266
2.722E-0313.153E-0501.951E-0300.3420.0543
5454545353
OP 0.9880.978−0.160−0.293
9.743E-0442.619E-0370.2540.0335
54545353
TP 0.977−0.146−0.280
1.698E-0360.2980.0424
545353
BAP −0.128−0.252
0.3600.0683
5353
OC 0.945
2.270E-026
53
LIGNINTNTOC/TN(Ad/Al)v(Ad/Al)s
NaOH-P−0.0422−0.0665−0.127−0.0376−0.0152
0.7640.6360.3660.7870.913
5353535454
HCl-P−0.0435−0.105−0.0565−0.00136−0.00302
0.7570.4550.6880.9920.983
5353535454
IP−0.0691−0.117−0.0172−0.00292−0.0157
0.6230.4050.9030.9830.910
5353535454
OP0.00593−0.135−0.0818−0.0404−0.0384
0.9660.3360.5600.7720.783
5353535454
TP−0.0373−0.126−0.0453−0.0192−0.0257
0.7910.3700.7470.8910.854
5353535454
BAP−0.0201−0.100−0.108−0.0397−0.0266
0.8870.4750.4430.7760.849
5353535454
OC−0.4730.977−0.2040.0123−0.0990
0.0003521.103E-0350.1420.9300.481
5353535353
TOC/OP−0.4210.950−0.2680.0472−0.0729
0.001701.752E-0270.05280.7370.604
5353535353
LIGNIN −0.4500.09340.126−0.207
0.0007170.5060.3670.138
53535353
TN −0.3450.0338−0.0762
0.01140.8100.587
535353
TOC/TN 0.0185−0.142
0.8950.310
5353
(Ad/Al)v 0.198
0.151
54
(Ad/Al)s
The pair(s) of variables with positive correlation coefficients and p values below 0.050 tend to increase together. For the pairs with negative correlation coefficients and p values below 0.050, one variable tends to decrease while the other increases. For pairs with p values greater than 0.050, there is no significant relationship between the two variables. Pearson Product Moment Correlation; Data source: Data 13 in Notebook1; Cell Contents: Correlation Coefficient; p Value; Number of Samples.

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Figure 1. Map showing the sampling locations: Qiantang River (Q), Shang River (S), Jiao River (J), Ximen Island (X), Feiyun River (F), Ao River (A); Maps showing the sampling locations along each river magnified: Qiantang River, Shuang River, Jiao River, Ximen Island, Feiyun River and Ao River.
Figure 1. Map showing the sampling locations: Qiantang River (Q), Shang River (S), Jiao River (J), Ximen Island (X), Feiyun River (F), Ao River (A); Maps showing the sampling locations along each river magnified: Qiantang River, Shuang River, Jiao River, Ximen Island, Feiyun River and Ao River.
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Figure 2. Mean values of lignin parameters in the study areas. The study locations include Qiantang (Q), Jiao (J), Feiyun (F), Shuang (S), Ximen (X) and Ao (A) Rivers.
Figure 2. Mean values of lignin parameters in the study areas. The study locations include Qiantang (Q), Jiao (J), Feiyun (F), Shuang (S), Ximen (X) and Ao (A) Rivers.
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Figure 3. Concentrations of all P fractions among the rivers.
Figure 3. Concentrations of all P fractions among the rivers.
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Figure 4. Plots of S/V and C/V ratio in sediments from sampling areas (a) including Q region, and (b) without Q region.
Figure 4. Plots of S/V and C/V ratio in sediments from sampling areas (a) including Q region, and (b) without Q region.
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Figure 5. Spatial distribution of (a) Λ, (b) TOC, TN, (c) TOC/TN molar ratio, (d) (Ad/Al)v and (Ad/Al)s ratios.
Figure 5. Spatial distribution of (a) Λ, (b) TOC, TN, (c) TOC/TN molar ratio, (d) (Ad/Al)v and (Ad/Al)s ratios.
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Figure 6. Spatial distribution of (a) sedimentary P species and (b) TOC/OP molar ratios along the Qiantang (Q), Shuang (S), Jiao (J), Ximen (X), Feiyun (F) and Ao (A) Rivers.
Figure 6. Spatial distribution of (a) sedimentary P species and (b) TOC/OP molar ratios along the Qiantang (Q), Shuang (S), Jiao (J), Ximen (X), Feiyun (F) and Ao (A) Rivers.
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Table 1. Ranges, mean and percentages P fractions.
Table 1. Ranges, mean and percentages P fractions.
LocsConcentration Ranges and Mean (in Brackets) (mg P/kg)Percentages to TP (%)
NaOH-PAPIPOPTPBAPNaOH-PAPIPOPBAP
Q1.08–7.161.54–15.152.39–14.453.44–6.636.49–19.984.74–12.69
(2.57)(4.16)(9.03)(4.44)(13.47)(7.01)19.0830.8867.0432.9652.04
S175.60–442.12303.34–378.91338.37–395.93244.55–311.60600.23–686.60445.81–703.97
(283.74)(345.45)(370.23)(275.19)(645.42)(558.93)43.9653.5257.3642.6486.60
J4.48–35.2323.07–43.4839.09–66.506.68–55.8152.51–106.5414.35–76.10
(12.81)(35.48)(51.18)(29.41)(80.59)(42.22)15.9044.0363.5136.4952.39
X2.29–10.0310.40–17.415.26–18.4712.20–31.0426.20–39.9114.63–40.16
(5.03)(14.38)(10.03)(23.72)(33.75)(28.75)14.9042.6129.7270.2885.19
F4.16–13.2021.51–34.4027.66–62.9517.52–50.4070.96–92.9523.09–60.12
(8.36)(27.89)(48.36)(30.61)(78.97)(38.97)10.5935.3261.2438.7649.35
A5.95–48.7726.55–52.8748.38–61.3135.64–168.9784.91–221.0946.26–187.61
(17.88)(44.30)(52.90)(71.04)(123.94)(88.92)14.4335.7442.6857.3271.74

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Loh, P.S.; Cheng, L.-X.; Lin, S.-Y.; Kandasamy, S. Characteristics of Sedimentary Organic Matter and Phosphorus in Minor Rivers Discharging into Zhejiang Coast, China. Geosciences 2020, 10, 357. https://doi.org/10.3390/geosciences10090357

AMA Style

Loh PS, Cheng L-X, Lin S-Y, Kandasamy S. Characteristics of Sedimentary Organic Matter and Phosphorus in Minor Rivers Discharging into Zhejiang Coast, China. Geosciences. 2020; 10(9):357. https://doi.org/10.3390/geosciences10090357

Chicago/Turabian Style

Loh, Pei Sun, Long-Xiu Cheng, Shi-Yuan Lin, and Selvaraj Kandasamy. 2020. "Characteristics of Sedimentary Organic Matter and Phosphorus in Minor Rivers Discharging into Zhejiang Coast, China" Geosciences 10, no. 9: 357. https://doi.org/10.3390/geosciences10090357

APA Style

Loh, P. S., Cheng, L. -X., Lin, S. -Y., & Kandasamy, S. (2020). Characteristics of Sedimentary Organic Matter and Phosphorus in Minor Rivers Discharging into Zhejiang Coast, China. Geosciences, 10(9), 357. https://doi.org/10.3390/geosciences10090357

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