[Spectroscopic and Molecular Characterization of Water Soluble Organic Matter from Sediments in the Macrophyte-dominated and Algae-dominated Zones of Taihu Lake].

Macrophyte- and algae-dominated lakes (zones) are the two typical states of shallow lakes, where the source and composition of organic matter are distinct. The burial of organic matter (OM) in the sediment supports the role of lakes as carbon sinks. However, organic matter in the sediments could be further processed, influencing the carbon cycle. The post-burial metabolism of the sedimentary OM relates closely to its composition. However, information on the differences in composition remains limited, especially the molecular composition of organic matter from sediments in the macrophyte-dominated and algae-dominated lakes. In this study, sediments were collected from the macrophyte-dominated and algae-dominated zones of Taihu Lake (East Taihu Lake and Meiliang Bay, respectively), and the active pool of sedimentary OM (water soluble organic matter, WSOM) was extracted and purified. The composition of the WSOM was characterized in detail via absorption spectroscopy, fluorescent spectroscopy, infrared spectroscopy, and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). The optical index of E2:E3 showed that the molecular size of WSOM in the macrophyte-dominated zone (M-WSOM) was slightly larger than that in the algae-dominated zone (A-WSOM). Consistently, the intensity-weighted molecular weights were identified as 388.9 and 379.9, respectively, via FT-ICR MS analysis. M-WSOM was more humified than A-WSOM, as evidenced by the SUVA254 and HIX values. The FT-ICR MS results showed that the relative abundance of the condensed aromatic substance and the aromatics were 6.3% (intensity-weighted) and 7.7% for M-WSOM and 1.1% and 4.4% for A-WSOM, respectively. The excitation-emission matrix fluorescence-parallel factor analysis (EEM-PARAFAC) suggested that the protein-like component was more in A-WSOM than that in M-WSOM, and the FT-ICR MS results showed that the intensity-weighted relative abundances of peptides were 35.6% and 15.6% for A-WSOM and M-WSOM, respectively. The FT-ICR MS results further showed that the heteroatom-containing molecules were abundant in the sedimentary WSOM, i.e., 82.9% and 91.7% for M-WSOM and A-WSOM, respectively. The nitrogen-containing molecules dominated, contributing to 53.5% and 78.5% of M-WSOM and A-WSOM, respectively. There were 30.4% and 41.4% phosphorus-containing molecules in M-WSOM and A-WSOM, respectively. The phosphorus-containing molecules in M-WSOM were mainly aliphatics and highly unsaturated structures with low oxygen, whereas those in A-WSOM were mainly peptides. This study elucidated the detailed molecular composition of WSOM in the macrophyte-dominated and algae-dominated zones of Taihu Lake, which aids understanding of the carbon, nitrogen, and phosphorus biogeochemical cycles in lakes.

Adsorption of humic acids to lake sediments: Compositional fractionation, inhibitory effect of phosphate, and implications for lake eutrophication.

Humic acid (HA) and phosphate interactions play a vital role in the biogeochemical cycle of carbon and nutrients and thus the trophic state of a lake. The adsorption behavior of HAs to sediments in the absence and presence of phosphate was investigated in this study. Three types of HAs were used, AHA from algae-dominated lake sediments, MHA from macrophyte-dominated lake sediments, and a reference HA (RHA) with terrestrial sources. The adsorption capacity of lake sediments was highest for AHA, which can be explained by that AHA contained more carboxyl-containing molecules, proteinaceous compounds and polysaccharides that were preferentially adsorbed by minerals. Phosphate showed a stronger inhibitory effect on MHA adsorption than on AHA adsorption, suggesting that AHA can more effectively replace phosphate adsorbed to sediments. Our findings show that the functional groups of organic compounds control not only their fractionation and burial but also their ability to replace phosphate in sediments. We propose a novel mechanism to explain the legacy effect of lake eutrophication. That is, as lakes shift from a macrophyte-dominated state to more eutrophic, algae-dominated state, increasing algae-derived organic compounds can promote the release of phosphate from sediments, forming a positive feedback loop that sustains internal phosphorus loading and hence lake eutrophication.

The Light-to-Nutrient Ratio in Alpine Lakes: Different Scenarios of Bacterial Nutrient Limitation and Community Structure in Lakes Above and Below the Treeline.

The light-to-nutrient hypothesis proposes that under high light-to-nutrient conditions, bacteria tend to be limited by phosphorus (P), while under relatively low light-to-nutrient conditions, bacteria are likely driven towards carbon (C) limitation. Exploring whether this light-to-nutrient hypothesis is fitting for alpine lakes has profound implications for predicting the impacts of climatic and environmental changes on the structures and processes of aquatic ecosystems in climate-sensitive regions. We investigated the environmental conditions and bacterioplankton community compositions of 15 high-elevation lakes (7 above and 8 below treeline). High light-to-nutrient conditions (denoted by the reciprocal value of the attenuation coefficient (1/K) to total phosphorus (TP)), high chlorophyll a (Chl a) concentrations, low TP concentrations and low ratios of the dissolved organic carbon concentration to the dissolved total nitrogen concentration (DOC:DTN) were detected in above-treeline lakes. Significant positive correlations between the bacterioplankton community compositions with 1/K:TP ratios and Chl a concentrations indicated that not only high light energy but also nutrient competition between phytoplankton and bacteria could induce P limitation for bacteria. In contrast, low light-to-nutrient conditions and high allochthonous DOC input in below-treeline lakes lessen P limitation and C limitation. The most abundant genus, Polynucleobacter, was significantly enriched, and more diverse oligotypes of Polynucleobacter operational taxonomic units were identified in the below-treeline lakes, indicating the divergence of niche adaptations among Polynucleobacter oligotypes. The discrepancies in the light-to-P ratio and the components of organic matter between the above-treeline and below-treeline lakes have important implications for the nutrient limitation of bacterioplankton and their community compositions.

Long-term changes of water quality in aquaculture-dominated lakes as revealed by sediment geochemical records in Lake Taibai (Eastern China).

The rapid development and exploitation of the Yangtze River basin in order to ensure human food security and increase living space in recent decades has resulted in significant potential for degradation of water quality in the river and in hundreds of lakes. Understanding how lake environments have evolved to their present state under a variety of external influences is crucial for evaluating their current status and anticipating future scenarios of environmental changes. However, the lakes along the middle reaches of the Yangtze River (MRY) are as yet little studied. Here, we described the long-term anthropogenic environmental transformations of a small lake (Lake Taibai) in the MRY area, based on a detailed quantitative geochemical analysis of the aliphatic hydrocarbons, nutrients (N and P), biogenic silica (BSi), and major and trace elements present in a dated sediment core retrieved from the lake. Our data revealed that levels of short-chain n-alkanes, αß-hopanes and the trace elements arsenic (As) and cadmium (Cd) were all low for the entire record in sediments prior to ca. 1970, reflecting unpolluted natural state of the lake. Pronounced anthropogenic effects began to appear in sediments deposited in the subsequent years ca. 1970-1990, during which the levels of all these components were elevated, most likely driven by input of nitrogen (N) and phosphorus (P) containing chemical fertilizers, pesticides and diesel oil respectively. Since ca. 1990, changes of short-chain n-alkane levels in the sediment suggested the lake had undergone dramatic eutrophication in which existing anthropogenic stressors were exacerbated by technological advances that extended the use of chemical fertilizer into aquaculture. This pattern contrasted with an otherwise comparable lake in the lower Yangtze River basin, Lake Changdang, in which trace element and petroleum pollution were much more prominent due to dramatic urbanization and industrialization of the catchment.

Anthropogenically driven differences in n-alkane distributions of surface sediments from 19 lakes along the middle Yangtze River, Eastern China.

During the past few decades, the Yangtze River basin has undergone massive anthropogenic change. In order to evaluate the impacts of human interventions on sediment n-alkanes of lakes across this region, the aliphatic hydrocarbon fractions of 19 surface sediment samples collected from lakes along the middle reaches of the Yangtze River (MYR) were analyzed using gas chromatography-mass spectrometry. The n-alkanes extracted from the sediments contained a homologous series from C15 to C34, with a notable predominance of odd carbon compounds except for sediments from the more intensively industrialized Lake Daye, in which > C21 n-alkanes showed no odd/even predominance, and carbon preference index (CPI) approached unity. Abundance values of middle-chain (C21, C23, and C25) and long-chain (C27, C29, C31, and C33) n-alkanes in Lake Daye were approximately 4 to 3 times greater than the average for other lakes, reaching 272.4 and 486.3 µg/g TOC, respectively, in the study. Short-chain n-alkanes (C15, C17, and C19) in the sediments varied in abundance from 10.0 to 76.2 µg/g TOC across the study and showed a moderate correlation with total phosphorus (TP) concentrations in the overlying water. The results indicated anthropogenic eutrophication enhanced the accumulation of short-chain n-alkanes in sediments because the primary producers in which they are synthesized are highly susceptible to nutrient forcing. Middle-chain n-alkane abundances were less affected by eutrophication and generally enriched in macrophyte lakes, while long-chain n-alkanes tend to be low in sediments from more eutrophic water. In the case of Lake Daye, direct discharges of petroleum products from heavy industry have introduced quantities of petroleum n-alkanes (> C21), far exceeding the amounts of biogenic input, and the sediment > C21 n-alkanes detected in this study showed typical characteristics of petroleum source. In other lakes, inputs of petroleum products from surface runoff of vehicle/traffic emissions associated with urbanization and economic growth contributed comparatively few n-alkanes to sediments, resulting in declines in CPI for > C21 n-alkanes, most obviously in Lakes Huanggai, Donghu, and Futou. Calculated CPI values suggest that a major proportion of the n-alkanes present in these lakes are derived from biogenic input. The results of this study provided evidences that n-alkane profiles of lake sediments respond sensitively to human-induced eutrophication and different sources of petroleum pollution.

Composition of dissolved organic matter controls interactions with La and Al ions: Implications for phosphorus immobilization in eutrophic lakes.

Applications of aluminium (Al) salt or lanthanum (La) modified bentonite (LMB) have become popular methodologies for immobilizing phosphorus (P) in eutrophic lakes. The presence of humic substances, has been shown to inhibit this form of treatment due to the complexation with La/Al. However, the effects of other dissolved organic matter (DOM), especially that derived from phytoplankton (the dominant source in eutrophic lakes) are unknown. In this study, the interaction with La/Al of Suwannee River Standard Humic Acid Standard II (SRHA) and algae-derived DOM (ADOM) were investigated and compared. Differed to SRHA which was dominated by polyphenol-like component (76.8%, C1-SRHA), majority in ADOM were protein-like substance, including 41.9% tryptophan-like component (C2-ADOM) and 21.0% tyrosine-like component (C3-ADOM). Two reactions of complexation and coprecipitation were observed between SRHA/ADOM and La/Al. Complexation dominated at low metal inputs less than 10 µM and coprecipitation was the main reaction at higher metal inputs. For ADOM, the tryptophan-like component (C2-ADOM) was the important component to react with metal. The reaction rate for C2-ADOM with La were about two-third of that for C1-SRHA, indicating that the influence of C2-ADOM was significant during the P immobilization by La/Al-based treatment in eutrophic lakes. The P removal data in the presence of ADOM confirmed the significant inhibition of ADOM. In addition, based on the composition of coprecipitates and relatively biodegradable character of tryptophan-like substances (C2-ADOM), the coprecipitation of ADOM was assumed to reduce the stability of precipitated P in eutrophic lakes. The release of P from the potential biodegradation of the coprecipitates and thus the possible decline of the performance of P immobilization by La/Al-based treatments is an important work in the future.