Spatial variation of soil phosphorus in the water level fluctuation zone of the Three Gorges Reservoir: Coupling effects of elevation and artificial restoration.

The water level fluctuation zone (WLFZ) is a distinctive and important component of the reservoir ecosystem. Due to periodic inundation, the fraction, spatial distribution, and chemical reactivity of soil phosphorus (P) within the WLFZ can potentially impact the loading of P into reservoir waters. However, a detailed study of this subject is lacking. In this study, the soil P in the WLFZ of the Three Gorges Reservoir, China, was examined using a combination of chemical sequential extraction, 31P NMR, and adsorption experiments. The results of chemical sequential extraction showed that HCl-Pi constituted the largest P pool among all P forms, with a mean concentration of 338 mg/kg. The content of HCl-Pi decreased significantly toward the dam, while the content of Res-P decreased in the opposite direction. The highest contents of most P forms and total P were observed at an elevation of 160 m. 31P NMR measurements showed that NaOH-EDTA Pi detectable in WLFZ soils at 145 m, 160 m, and 175 m elevation consisted mainly of orthophosphate and pyrophosphate, while NaOH-EDTA Po contained phosphate monoesters and phosphate diesters, accounting for 1.4 % to 46.2 % of NaOH-EDTA TP. Adsorption experiments showed that soil P in the WLFZ was a potential P source for reservoir waters, with chemisorption being the dominant mechanism of P sequestration. The adsorption equilibrium concentration of WLFZ soil was lower at higher elevations (>170 m) compared to lower elevations (<150 m), exhibiting a decrease in the average maximum adsorption from 271 mg/kg to 192 mg/kg. Statistical analysis suggested that Ca and Fe content, particle size, elevation, and artificial restoration were key factors affecting the fraction and content of soil P in the WLFZ. Our findings contribute to an improved understanding of the behavior of soil P in the WLFZ of large reservoirs and its potential contribution to the reservoir waters.

Suspended phosphorus sustains algal blooms in a dissolved phosphorus-depleted lake.

The expansion of algal bloom in surface waters is a global problem in the freshwater ecosystem. Differential reactivity of organic phosphorus (Po) compounds from organic debris, suspended particulate matter (SPM), and sediment towards hydrolysis can dictate the extent of supply often limited inorganic P (Pi) for algal growth, thereby controlling the extent of bloom. Here, we combined solution P-31 nuclear magnetic resonance (31P NMR), sequential extraction, enzymatic hydrolysis, and 16S rRNA measurements to characterize speciation and biogeochemical cycling of P in Lake Erhai, China. Lower ratios of diester-P/monoester-P in SPM in January (mean 0.09) and July (0.14) than that in April (0.29) reflected the higher degree of diester-P remineralization in cold and warm months. Both H2O-Pi and Po were significantly higher in SPM (mean 1580 mg ·kg-1 and 1618 mg ·kg-1) than those in sediment (mean 8 mg ·kg-1 and 387 mg ·kg-1). In addition, results from enzymatic hydrolysis experiments demonstrated that 61% Po in SPM and 58% in sediment in the H2O, NaHCO3, and NaOH extracts could be hydrolyzed. These results suggested that H2O-Pi and Po from SPM were the primarily bioavailable P sources for algae. Changes of Pi contents (particularly H2O-Pi) in algae and alkaline phosphatase activity (APA) during the observation periods were likely to be controlled by the strategies of P uptake and utilization of algae. P remobilization/remineralization from SPM likely resulted from algae and bacteria (e.g., Pseudomonas). Collectively, these results provide important insights that SPM P could sustain the algal blooms even if the dissolved P was depleted in the water column.

Fuel from within: Can suspended phosphorus maintain algal blooms in Lake Dianchi.

Extensive algal bloom in the surface water is a pressing issue in Lake Dianchi that causes lake restoration to be difficult owing to complex and variable phosphorus (P) sources in the water column. P released from algae, suspended particles (SS), and sediment can provide sustainable P sources for algal blooms. However, little is known regarding the dynamic of P speciation in these substances from different sources. In this study, solution 31P nuclear magnetic resonance (31P NMR) and chemical sequential extraction were employed to identify P speciation in algae, SS, and sediment during different periods. Results showed that dissolved inorganic P (Pi) directly accumulated in algae in the form of orthophosphate (ortho-P) and pyrophosphate (pyro-P). Algae preferentially utilized Pi, followed by organic P (Po) in the water column when the Pi was insufficient during growth and reproduction. The 31P NMR spectra demonstrated that ortho-P, orthophosphate monoesters (mono-P), orthophosphate diesters (diester-P), and pyro-P dominated the P compounds across the samples tested. Increasing remineralization of SS mono-P driven by intense alkaline phosphatase activities was caused by increasing P needs of algae and pressure of P supply in the water column. The higher ratios of diester-P to mono-P in sediment (mean 0.55) than those in algae (mean 0.07) and SS (mean 0.11 in surface water, 0.14 in bottom water) suggested that the degradation and regeneration occurred within these P compounds during or after sedimentation. Pi content in algae during growth and reproduction was controlled by its P absorption and utilization strategies. Results of this study provide insights into the dynamic cycling of P in algae, SS, and sediment, explaining the reason for algal blooms in the surface water with low concentrations of dissolved P.

Effects of cascade dam on the distribution of heavy metals and biogenic elements in sediments at the watershed scale, Southwest China.

Cascade dam has important effects on the magnitude and dynamics of sediment particles, heavy metals, and biogenic elements in reservoirs. However, systematic studies on the interception effect of cascade dam on the various elements that occur in rivers at the watershed scale are lacking. The aims of this study were to (1) assess the interception effect of a cascade dam on heavy metals and biogenic elements and (2) investigate the key factors of these effects of the cascade dam. Surface sediments were collected from 29 sites distributed in the Wujiang River Basin (WRB, a watershed scale in Southwest China), including from tributaries (7 sites), the main stream (13 sites), and cascade reservoirs (9 sites). In addition, the particle sizes, heavy metals (Fe, Mn, Zn, Cr, Cu, As, Pb, and Cd), and biogenic elements (TOC, TN, and TP) of sediments were analyzed. Compared with the tributaries, D50 (median particle size) was significantly reduced by 56.8% of cascade reservoirs. The proportion of 63-2,000 µm decreased from 13.78 to 1.34%, indicating that more coarse particles were intercepted in the cascade reservoirs. The contents of heavy metals (Fe, Zn, Cu, As, and Cd) declined significantly along the way. On the whole, the contents of TOC, TN, and TP were highest in the midstream and lower in the upstream and downstream. The hydrological condition (reservoir age, HRT, and flow) and the basin area and internal and external inputs of cascade reservoirs are important factors. The findings deepen the current understanding of the mechanisms by which cascade dam affects the river transport of heavy metals and biogenic elements at the watershed scale and provide an important reference for establishing hydropower developments along rivers and developing aquatic environment management strategies.

Method for phosphate oxygen isotopes analysis in water based on in situ enrichment, elution, and purification.

The phosphate oxygen isotope (δ18OP) ratio has been proven to be an effective tool to trace the sources and biogeochemical cycles of phosphorus (P) in aquatic ecosystems. However, the enrichment of phosphate (PO4) and the removal of impurities are quite complex and easy to cause PO4 loss in current δ18OP analytical methods. Moreover, the δ18OP value obtained by the commonly-used instantaneous sampling method is more of the instantaneous information of P, which is accidental or uncertain for accurate identification of the P source. In this study, a new method of in situ enrichment, elution, and purification of PO4 (ISEEP) was developed for δ18OP analysis in waters. This method utilized a PO4 binding phase (Zr-Oxide gel) to selectively in situ adsorb PO4 in water and exhibited an adsorption capacity per unit area of up to 789.3 µg P/cm2. The PO4 on the gel was eluted easily with a 1 M NaOH solution. More than 99.7% of the common anions, cations, and dissolved organic matter (DOM), as well as more than 90% of the trace elements were removed synchronously after adsorption and elution of PO4. The recovery rate of PO4 in the whole procedure was as high as 92.8%. The XRD and SEM examinations showed that the ISEEP can obtain high-purity Ag3PO4 solid for the δ18OP measurement. The reliability of the ISEEP method is confirmed by the measured δ18OP value and standard deviation of parallel samples from different types of natural waters obtained by both the ISEEP and the current popular McLaughlin (2004) method. It provides a good prospect of this new method for tracing the P sources and their biogeochemical cycling in aquatic ecosystems.

Removal of phosphate by aluminum-modified clay in a heavily polluted lake, Southwest China: Effectiveness and ecological risks.

Lake eutrophication is a main water environmental problem. When the extraneous nutrients are effectively controlled, nutrients in water mainly source from endogenous release from the sediment. In situ passivation is an important pollution control technique for endogenous pollution in lakes or reservoirs. This study focused on Qianling Lake, a cascade-channel lake in Southwest China polluted by phosphorus (P), which was selected for an in situ passivation project using a novel Al-based passivator on the polluted water area. Accordingly, the release of endogenous nutrients from the sediment can be controlled to remediate the polluted water, and the remediation effect and ecological risk of the passivation were evaluated. The results showed that after 12 months of passivation, the release of P from the sediments can be effectively inhibited. Concentrations of total P (TP) and Chl-a within water of the passivation area were reduced by approximately 80% and 70%. Meanwhile, water transparency and the content of dissolved oxygen were remarkably enhanced. The application of the passivator remarkably improved the water quality. P in water and at the sediment-water interface was fixed on the surface of sediment in the form of Al-combined state. This passivator exhibits favorable P-controlling performance in the restoration of lakes and reservoirs polluted by endogenous P. This aluminum-modified clay is an effective passivator for remediation of internal P pollution in potentially similar lakes and reservoirs.

Pretreatment method for the analysis of phosphate oxygen isotope (δ18OP) of different phosphorus fractions in freshwater sediments.

Accurate measurement of the oxygen isotopic composition of dissolved phosphate (δ18OP) of different phosphorus (P) fractions in lacustrine sediments is very difficult because of the influence of large amounts of impurities. In this study, we developed a five-step method for obtaining high purity Ag3PO4 sample for the analysis of δ18OP of different P fractions in freshwater sediments. Sedimentary P was divided into NaHCO3-P, NaOH-P and HCl-P by chemical sequential extraction. Pretreatment procedures for different sedimentary P fractions were improved in the following respects: 1) abandonment of the magnesium-induced coprecipitation method to avoid the introduction of impurity ions, such as Mg2+ and Cl-, and reduce the loss of P; 2) use of a small amount of non-phosphate activated carbon powder to efficiently remove organic matter in extracts of NaHCO3-P and NaOH-P, and reduce the loss of P; 3) adjustment of the HCl-P extract pH to 4 in order to form Fe(OH)3-PO43- coprecipitate, thereby removing most of metals and Cl-. This method reduces the pretreatment steps, simplifies the operation and increases the recovery of phosphate (90.98%-96.69%). The high purity Ag3PO4 sample can be obtained and the repeatability and accuracy of measured δ18OP is better than 0.3‰, demonstrating high reliability and accuracy. This new method was used to analyze the δ18OP of different P fractions in sediments of a eutrophic lake in southwestern China. The preliminary results indicated that the δ18OP in the sediments can be used to identify different P sources, and provide new insights into sedimentary P cycling. The method established in this study provides a powerful tool for investigating the sources and biogeochemical cycle of P in freshwater sediments.

In situ, high-resolution evidence of phosphorus release from sediments controlled by the reductive dissolution of iron-bound phosphorus in a deep reservoir, southwestern China.

Reservoirs in southwestern China are encountering the challenge of eutrophication, in which internal phosphorus (P) release from sediments plays an important role. Studies on the high-resolution profile variations and release mechanisms of P at the sediment-water interface (SWI) are rare in these reservoirs until now. In this study, monthly monitoring (Nov 2017 to Oct 2018) using a composite diffusive gradient in thin films (DGT) technique was taken to determine the temporal and vertical profile variations of the DGT-labile P (Fe) at the SWI in Hongfeng Reservoir. The results showed that the average concentrations of the DGT-labile P (Fe) in surface sediments were 0.63 ±â€¯0.24 mg·L-1 and 4.61 ±â€¯1.12 mg·L-1, respectively, with significantly higher concentrations during the summer anoxic period than that during the winter aerobic period. The DGT-labile P (Fe) concentrations in sediments presented a significant positive correlation (r2 > 0.70, p < 0.001), supporting the simultaneous release of reactive P and reactive Fe from the sediments and indicating that the reductive dissolution of iron-bound P dominates the P release from sediments. The release rates of P ranged from 0.01 mg·m-2·d-1 to 0.83 mg·m-2·d-1 (mean: 0.22 mg·m-2·d-1) in Hongfeng Reservoir, which are higher than that in heavily eutrophic shallow lakes in eastern China, such as Lake Taihu. There is a higher P loading, stronger P reactivity, faster P release rates, and higher pollution potential in deep reservoirs of southwestern China than that in natural shallow lakes of eastern China, highlighting the importance and urgency of treating internal P pollution in deep reservoirs. Further studies on the mechanisms and controlling factors of the coupled Fe-P-S cycle in deep reservoirs are desirable in the future, so as to provide a scientific foundation for exploring effective internal P treatment techniques adaptive to deep reservoirs in southwestern China.

Assessment on the effects of aluminum-modified clay in inactivating internal phosphorus in deep eutrophic reservoirs.

Aluminum-salt inactivating agents are extensively applied to the restoration of lakes polluted by internal phosphorus (hereinafter referred to as "P"). However, there is a lack of micromechanism information regarding the sediment P cycle and its interactions with aluminum salts, which has restricted the engineering applications of aluminum salts. In this study, a sediment core incubation system was used to simulate the influence of aerobic and anaerobic conditions on the effectiveness and stability of aluminum-modified clay (AMC). This study also investigated the millimeter-scale dynamics of P across the sediment-water interface (SWI) using the HR-Peeper and DGT techniques. According to the results, sediment P release mainly occurred under anaerobic conditions. When the incubation system was in an anaerobic state, AMC effectively reduced the internal-P loading. In pore water, there was a positive correlation between soluble Fe and SRP, suggesting that the reductive dissolution of Fe-P constituted the main mechanism of sediment P release. After with dosing AMC, the concentrations of SRP and labile P in the capping layer both dropped abruptly to low levels and the content of Al-P in surface sediments rose, suggesting that AMC had strongly adsorbed phosphates, formed inert Al-P and blocked the phosphate exchange between pore water and overlying water. This study elaborated on the micromechanism of the control of sediment internal P input by AMC and revealed that Al-P precipitation constituted the main mechanism of the inhibition of sediment P release by aluminum-salt inactivating agents. The research findings have a great significance for guiding field applications of aluminum-salt inactivating agents.