The evolution of a typical plateau lake from macrophyte to algae leads to the imbalance of nutrient retention.

Long-term anthropogenic nitrogen (N) and phosphorus (P) inputs have led to lake eutrophication and decreased environmental quality. However, the imbalance in nutrient cycling caused by ecosystem transformation during lake eutrophication is still unclear. The N, P, organic matter (OM) and their extractable forms in the sediment core of Dianchi Lake were investigated. Combining ecological data and geochronological techniques, a coupling relationship between the evolution of lake ecosystems and nutrient retention was established. The results show that the evolution of lake ecosystems promotes the accumulation and mobilization of N and P in sediments, leading to an imbalance in nutrient cycling in the lake system. From the "macrophyte-dominated" period to the "algae-dominated" period, the accumulation rates of potential mobile N and P (PMN, PMP) in sediments have significantly increased, and the retention efficiency of total N and P (TN, TP) has decreased. The increased TN/TP ratio (5.38 ± 1.52 ‒ 10.19 ± 2.94) and PMN/PMP ratio (4.34 ± 0.41 ‒ 8.85 ± 4.16), as well as the reduced humic-like/protein-like ratio (H/P, 11.18 ± 4.43 ‒ 5.97 ± 3.67), indicated an imbalance in nutrient retention during sedimentary diagenesis. Our results show that eutrophication has resulted in the potential mobilization of N in sediments exceeding P, providing new insights for further understanding the nutrient cycle in the lake system and strengthening lake management.

Simultaneous immobilization of ammonia and phosphorous by thermally treated sediment co-modified with hydrophilic organic matter and zeolite.

The use of calcined sediments (CS) for thin-layer capping is an environment-friendly technology for controlling nitrogen (N) or phosphorus (P) release. However, the effects of CS derived materials and efficiency in controlling the sedimentary N/P ratio have not been thoroughly investigated. While zeolite-based materials have been proven efficient to remove ammonia, it is limited by the low adsorption capacity of PO43-. Herein, CS co-modified with zeolite and hydrophilic organic matter (HIM) was synthesized to simultaneously immobilize ammonium-N (NH4+-N) and remove P, due to the superior ecological security of natural HIM. Studies on the influences of calcination temperature and composition ratio indicated that 600 °C and 40% zeolite were the optimal parameters leading to the highest adsorption capacity and lowest equilibrium concentration. Compared with doping with polyaluminum chloride, doping with HIM not only enhanced P removal but also achieved higher NH4+-N immobilization efficacy. The efficiency of zeolite/CS/HIM capping and amendment in prohibiting the discharge of N/P from sediments was assessed via simulation experiments, and the relevant control mechanism was studied at the molecular level. The results indicated that zeolite/CS/HIM can reduce 49.98% and 72.27% of the N flux and 32.10% and 76.47% of the P flux in slightly and highly polluted sediments, respectively. Capping and incubation with zeolite/CS/HIM simultaneously resulted in substantial reductions in NH4+-N and dissolved total P in overlying water and pore water. Chemical state analysis indicated that HIM enhanced the NH4+-N adsorption ability of CS owing to its abundant carbonyl groups and indirectly increased P adsorption by protonating mineral surface groups. This research provides a novel strategy to control sedimentary nutrient release by adopting an efficient and ecologically secure remediation method to rehabilitate eutrophic lake systems.

Effects of calcination on the environmental behavior of sediments by phosphorus speciation and interface characterization.

Dredged sediments derived from eutrophicated lakes poses hardness of sludge disposal and ecological risks. The proper pretreatment and utilization of dredged sediments presented a challenge. In this study, Dianchi Lake sediments were dredged, thermally treated and utilized as particle capping material in batch experiments. The effects of calcination on phosphorus speciation and sediment-water interface environment as well as P immobility mechanism were predominantly explored. The microstructures and chemical compositions of calcined sediments were investigated, indicating the porosity and mineralization components were greatly enhanced. The fractional analysis of phosphorus revealed that the calcination process reduced the percentage of unsteady phosphorus, transforming into stable inert phosphorus fractions (Al-P, Ca-P and Res-P), respectively, thereby minimized its mobility and eutrophication risk. Interestingly, calcination temperatures of 700 °C and 800 °C resulted in smaller releasing potentials and equilibrium phosphorus concentrations, despite having lower adsorption capacities than 550 °C. Furthermore, the results of redox potential monitoring showed that the thermally treated Dianchi Lake sediments could enhance the redox potential and dissolved oxygen in the surface sediment, indicating the amelioration of interfacial environment. The practical monitoring experiments confirmed the capping depressed the DTP to 0.031 mg L-1. The investigation of this study provided explicit evidence of Ca coupled P and aerobic Fe bound P strengthened the immobilization effects, and the development of sediment calcination demonstrates a promising strategy for alleviating the burden of endogenous pollution and improving aerobic environment, which are of great significance for lake ecological remediation.

Biogeochemical dynamics of particulate organic phosphorus and its potential environmental implication in a typical "algae-type" eutrophic lake.

Organic phosphorus (Po) plays a very important role in the process of lake eutrophication, but there is still a lack of knowledge about the internal cycle of Po in suspended particulate matter (SPM) dominated by algal debris. In this study, the characterization of bioavailable Po by sequential extraction and enzymatic hydrolysis showed that 45% of extracted TP was Po in SPM of Lake Dianchi, and 43-98% of total Po in H2O, NaHCO3 and NaOH fractions was enzymatically hydrolyzable Po (EHP, H2O-EHP: 31-53%). Importantly, labile monoester P was the main organic form (68%) of EHP, and its potential bioavailability was higher than that of diester P and phytate-like P. According to the estimation of P pools in SPM of the whole lake, the total load of Pi plus EHP in the H2O extract of SPM was 74.9 t and had great potential risk to enhance eutrophication in the lake water environment. Accordingly, reducing the amount of SPM in the water during the algal blooming period is likely to be a necessary measure that can successfully interfere with or block the continuous stress of unhealthy levels of P on the aquatic ecosystem.

The adsorption-release behavior of sediment phosphorus in a typical "grass-algae" coexisting lake and its influence mechanism during the transition sensitive period.

In the early stage of eutrophication, the coexistence of "grass and algae" in lakes is obvious. Understanding the P sorption-desorption behavior in natural sediments during the ecologically sensitive transition period has important scientific value for predicting the deterioration of lake ecosystems and formulating restoration measures, but the related mechanisms are still unclear. In this study, the analysis results of sedimentary dissolved organic matter (DOM) fractions, extractable Fe (hydr)oxide fractions and P adsorption experiments showed that sedimentary DOM fractions, especially the tyrosine-like protein fractions and microbial humic-like fractions, played a part in determining the EPC0 and Kd values of sediments in the plateau lake environment. The compound effect of amorphous Fe (hydr)oxides and sedimentary OM affected the increase of sedimentary P adsorption. Interestingly, these phenomena were strongly correlated with water depth. Furthermore, the distribution of water depth to aquatic plants indirectly regulated the values of sedimentary EPC0 and Kd. Meanwhile, the ability of submerged plants to control the sedimentary EPC0andKd values will be forced to shift shallowly, thereby forcing a significant reduction of areas with low EPC0 and high Kd values. This not only enhanced the risk of endogenous P release in lakes, but also accelerated the further deterioration of aquatic ecosystems. Therefore, studying the long-term scale changes of sedimentary EPC0 and Kd values can help to understand the duration of the lake ecological transition period and prevent the transitional deterioration of ecosystem.

Water depth determines spatial and temporal phosphorus retention by controlling ecosystem transition and P-binding metal elements.

Shallow lakes are more susceptible to eutrophication than deep lakes. The geochemical and biogeochemical mechanisms controlling the vulnerability to eutrophication for deep lakes and shallow lakes remain unknown. Therefore, we investigated the combined Phosphorus (P) retention mechanism with P fractions, water depth, distribution of P-binding metal elements, and macrophytes coverage in a degrading ecosystem of Erhai Lake. We concluded that different mechanisms control the P retention in deep-water areas and shallow-water areas. In shallow areas covered by macrophytes, the biogeochemical process manipulates the P retention by changing the total organic carbon (TOC), calcium (Ca) distributions and turbulence. In deep areas without macrophyte coverage, the aluminum (Al) and iron (Fe) distributions control the P retention by a physicochemical process. Manganese (Mn) was found to be a potential proxy in tracking the kinetic release and readsorb of redox-sensitive P (BD-P) in deep areas. The historical record and core sample indicate that the hydrological engineering induced water depth variation is a vital factor changing the ecosystem of Erhai Lake by forming a large area of intermediate area where macrophytes could only survive at low water level. The uplift of water level in the 1990s gradually changed the ecosystem of Erhai Lake from macrophyte-dominated to algal-macrophyte concomitant that reduced the accumulation of stable P fractions and their binding metals. Macrophytes were capable to preserve P in biomass in the macrophyte-dominated ecosystem, which released 150% and 72% of more labile organic P (NaOH25-nrP) and BD-P in the sediment after the deterioration than before, respectively. Therefore, water depth is a prerequisite to restoring the P preservation capacity of sediment and the macrophyte ecosystem. Further hydraulic engineering projects should consider the effect of water-level-variation-induced ecosystem transition.

Importance of ammonia nitrogen potentially released from sediments to the development of eutrophication in a plateau lake.

Sedimentary nitrogen (N) in lakes significantly influenced by eutrophication plays a detrimental role on the ecological sustainability of aquatic ecosystems. Here, we conducted a thorough analysis of the importance of N potentially released from sediments during the shift of "grass-algae" ecosystem in plateau lakes. From 1964 to 2013, the average total amount of sedimentary potential mineralizable organic nitrogen (PMON) and exchangeable N in whole Lake Dianchi were 5.50 × 103 t and 3.44 × 103 t, respectively. NH4+-N was the main product (>90%) of sedimentary PMON mineralization. The PMON in sediments had great release potential, which tended to regulate the distribution of aquatic plants and phytoplankton in Lake Dianchi and facilitated the replacement of dominant populations. Moreover, NH4+-N produced by sedimentary PMON mineralization and exchangeable NH4+-N have increased the difficulty and complexity of ecological restoration in Lake Dianchi to a certain extent. This study highlights the importance of sedimentary N in lake ecosystem degradation, showing the urgent need to reduce the continuous eutrophication of lakes and restore the water ecology.

Historical changes of sedimentary P-binding forms and their ecological driving mechanism in a typical "grass-algae" eutrophic lake.

With the transformation of lake ecosystem from "clear water" to "turbid water", the residual phosphorus (P) accumulated in sediments may slow down the process of aquatic ecological restoration, and the related mechanisms are complex and need to be better understood. In this study, high-resolution systematic investigation and analysis of P-binding forms in the sediments showed that Lake Dianchi, the largest plateau lake in Southwest China, was enriched with NaOH-rP, HCl-P and Res-P, but depleted in NH4Cl-P, BD-P and NaOH-nrP. The BD-P, NaOH-nrP and NaOH-rP were the main contributors to potential P release from sediments, while the release potential of NH4Cl-P was relatively weak (<1%). When the external P loading gradually decreased, the internal P loading of Lake Dianchi was estimated to be 522 mg P/(m2•a) in the past 30 years. The succession of "grass-algae" type in Lake Dianchi coincided with reduced absorption and transformation of potential mobile P and decreased accumulation of stable P, especially the Res-P. Meanwhile, the temporal variation of potential mobile P was a good predictor of ecological degradation and reduced ecosystem sustainability in Lake Dianchi.

Features and influencing factors of nitrogen and phosphorus diffusive fluxes at the sediment-water interface of Erhai Lake.

Nitrogen and phosphorus diffusion at the sediment-water interface is vital to the water quality of lakes. In this paper, N and P diffusive fluxes at the sediment-water interface in Erhai Lake were studied using the sediment-pore water diffusive flux method. Characteristics of temporal and spatial variation of N and P diffusive fluxes were analyzed. Effects of the physicochemical properties of sediments and overlying water were discussed. Results showed that (1) the total N and P diffusive fluxes at the sediment-water interface of Erhai Lake are relatively low. The diffusive flux of ammonia nitrogen is 8.97~74.84 mgd-1 m-2, higher in the middle of the lake, followed by the northern and southern regions successively. The P diffusive flux is -0.007~0.050 mgd-1 m-2, higher in northern region of the lake, followed by middle and southern regions successively. The annual N diffusive flux has two peaks, and the higher peak is in September. The annual P diffusive flux shows a "V-shaped" variation, reaching the valley in July. N and P diffusive fluxes decrease with an increase of sediment depth. Overall, N and P diffusive fluxes at the sediment-water interface in Erhai Lake show different temporal and spatial variation. (2) Aquatic plants promote N and P diffusion at the sediment-water interface in Erhai Lake. The pH, DO, and SD of the overlying water are important influencing factors for the P diffusive flux. P diffusive flux is inversely proportional to the total phosphorous (TP) concentration of the overlying water. The physicochemical environment of overlying water slightly influences the N diffusive flux. The activity of sediments and the organic content are two main influencing factors of N diffusive flux, while P content and morphology of sediments are the main influencing factors of P diffusive flux. Iron and manganese ions are important elements that influence N and P diffusive fluxes at the sediment-water interface. (3) The P diffusive flux at the sediment-water interface in Erhai Lake is mainly affected by the physical and chemical properties of water, whereas the N diffusive flux is mainly influenced by the mineralization of organic matter in sediments. The P diffusive flux at the sediment-water interface is sensitive to the overlying water quality. Sediment transformation from "source" to "sink" was observed in 1 year. On the contrary, N diffusive flux is less sensitive to lake water quality. Endogenetic pollutant control in Erhai Lake should focus on P control.

DGT induced fluxes in sediments model for the simulation of phosphorus process and the assessment of phosphorus release risk.

Diffusive gradients in thin films (DGT)-induced flux in sediments (DIFS) (DGT-DIFS) model for phosphorus (P) has been investigated to provide a numerical simulation of a dynamic system of the DGT-pore water-sediment in Dianchi Lake (China). Kinetic parameter-T C (33-56,060 s), distribution coefficient-K d (134.7-1536 cm(3)g(-1)), and resupply parameter-R (0.189-0.743) are derived by DGT measurement, the sediment/pore water test, and the DIFS model. The changes of dissolved concentration in DGT diffusive layer and pore water and sorbed concentration in sediment, as well as the ratio of C DGT and the initial concentration in pore water (R) and mass accumulated by DGT resin (M) at the DGT-pore water-sediment interface (distance) of nine sampling sites during DGT deployment time (t) are derived through the DIFS simulation. Based on parameter and curves derived by the DIFS model, the P release-transfer character and mechanism in sediment microzone were revealed. Moreover, the DGT-DIFS parameters (R, T C , K -1 , C DGT ), sediment P pool, sediment properties (Al and Ca), and soluble reactive P (SRP) in overlying water can be used to assess "P eutrophication level" at different sampling sites with different types of "external P loading." The DGT-DIFS model is a reliable tool to reveal the dynamic P release in sediment microzone and assess "internal P loading" in the plateau lake Dianchi.

[Concentration of Phosphorus in Sediments Interstitial Water as Affected by Distribution of Aquatic Plants in Dianchi Lake].

In order to reveal the effect of aquatic plants distribution on the mass concentration of phosphorus in sediment interstitial water, the mass concentrations of Dissolved Total Phosphorus (DTP), Soluble Reactive Phosphorus (SRP) and Dissolved Organic Phosphorus (DOP) in the sediment interstitial water and overlying water from areas with or without plants in the same site of Dianchi were studied. The vertical variation characteristics of phosphorus forms in sediment interstitial water were analyzed to explore the effect of aquatic plants on the phosphorus forms in sediment interstitial water. The results showed: ①Aquatic plants had an significant effect on the phosphorus mass concentration of the sediment interstitial water in different Dianchi lakes. However, they varied with different distribution sites and depth. ②Aquatic plants significantly decreased the percentage of DOP contribution in the sediment interstitial water. The average contribution of DOP with aquatic plants was 32.87%, while that without plants reached 57.68%; ③Aquatic plants significantly inhibited the release of inorganic phosphorus in sediments and promoted the transformation of DOP. The SRP diffusion flux at sediment-water interface with aquatic plants was increased by 39.99% as compared with that without plants; ④The growth of aquatic plants significantly reduced the concentration of phosphorus in sediment interstitial water, especially DOP, and the reduction rate of the sediment interstitial water DOP was from 38.02% to 85.49%. Therefore, the analysis of the contribution and reduction rate of aquatic plants on the sediment interstitial water DOP was of great importance in understanding the relationship between aquatic plants and DOP, as well as the mineralization of organic phosphorus in sediments.

Element remobilization, "internal P-loading," and sediment-P reactivity researched by DGT (diffusive gradients in thin films) technique.

Labile P, Fe, and sulfide with the high spatial resolution in sediment porewater of five sites (A-E) of Dianchi Lake (China) were measured at same locations using AgI/Chelex-100, Chelex-100, and ferrihydrite DGT (diffusive gradients in thin films) probes. DGT derived P/Fe/S concentrations in sediment porewater on millimeter or sub-millimeter scale in order to reveal the element remobilization process and the mechanism of "internal P-loading" of sediments in Dianchi Lake. Decomposition of alga biomass in the uppermost sediment layer and the reductive dissolution of Fe-bound P in the anoxic sediment were the two main processes causing P release. A dynamic numerical model-DIFS (DGT-induced flux in sediments) was used to assess sediment-P reactivity (capacity of solid pool and rate of transfer) and P release risk by kinetic parameter-T C (1089∼20,450 s), distribution coefficient-K d (167.09∼502.0 cm(3) g(-1)), resupply parameter-R (from 0.242 to 0.518), and changes of dissolved/sorbed concentration, R and M at the microzone of DGT/porewater/sediment.

[Relationship between the DO and the environmental factors of the water body in Lake Erhai].

The contents of DO and nitrogen (N), phosphorus (P), chlorophyll a in water from Lake Erhai were analysed by combining the nitrogen and phosphorus forms in sediment. The results indicated that the DO contents of the water from Lake Erhai varied from 6.61 to 7.42 mg/L from 1992 to 2009, which is generally decreased. The minimum mean value was 6.42 mg/L in September. The trend of the DO contents from north to south was decreasing, and also decreased with the increasing of the water depth in Lake Erhai, the DO content was 5.15 mg/L at the water bottom. The relationship between the contents of DO and N, P was negative, and the relativity of different months was greater than that of different years. The relationship between the contents of DO and the contents of labile-P, organic-P, NH4(+) -N in sediment was negative, which was positive with the contents of Fe/Al-P, inorganic P and NO3(-) -N. The relationship between the contents of DO and chlorophyll a in water was negative, which indicated that Lake Erhai is aerobic, and is approaching anaerobic gradually. With the increasing of released content of N and P, the increasing of alga biomass was accelerated and the worsening of water body eutrophication also can be promoted by the decreased DO content in water from Lake Erhai.