Applying fluorescence spectroscopy coupled with Gaussian band fitting to reveal dynamic variation process of humus fractions from riparian soils along an urbanized river.

Humus, an important fraction of soil organic matter, play an environmental role on nutrients, organic and inorganic pollutants in riparian zones of urbanized rivers. In this study, dynamic variation process of humus fractions from riparian soils was revealed along Puhe River. Composite soil samples of four depths were collected from four land-uses, i.e., eco-conservation area (ECA), industrial area (INA), urban/town area (UTA), rural/agricultural area (RAA). Based on synchronous fluorescence spectra coupled with Gaussian band fitting, fulvic/humic acid predominantly contained tyrosine-like (TYLF), tryptophan-like (TRLF), microbial-like (MLF), fulvic-like (FLF) and humic-like (HLF) substances within each soil profile. TRLF, MLF and FLF (89.43-90.30 %) are the representative components in fulvic-acid, while MLF and HLF (52.81-59.97 %) in humic-acid. Phenolic, carboxylic and humified materials were present in both humus. According to 2-dimensitonal correlation spectroscopy and canonical correlation analysis, fulvic/humic acid within the ECA soil profile could be mainly derived from the degradations of terrestrial plant metabolites and residuals. Within the INA, fulvic-acid could be associated with treated/untreated wastewater, which entered the river and flew into the riparian during high flow period; whereas humic-acid could be relative to the terrestrials. Fulvic-acid had the same source as humic-acid in the UTA, which might be concerned with scattered domestic sewage and livestock wastewater, rather than the fluvial water. Furthermore, the source of fulvic/humic acid in the RAA was the crop metabolites and residuals, apart from the livestock wastewater. Noticeably, the variations of humus fractions in the ECA and RAA roughly occurred in 0-60 cm, while approximately in 20-80 cm in the INA and UTA. This proved that humus fractions in the former were referred to the plant/crop residuals, whereas humus fractions in the latter were those the terrestrials and fluvial water. This study could provide a key support for the construction and restoration of the urbanized riparian zone.

Applying fluorescence spectroscopy and DNA pyrosequencing with 2D-COS and co-occurrence network to deconstruct dynamical DOM degradation of air-land-water sources in an urban river.

In an urban river, comprehending the interplay between dissolved organic matter (DOM) and atmospheric, terrestrial, and aquatic sources is crucial. This encompassed investigating temporal variations in DOM and its association with the bacterioplankton community to gain profound insights into the biogeochemical dynamics and biodegradability of DOM. DOM was extracted from PM2.5, soil, sediment, bait, and terrestrial/aquatic plant residuals collected along the Wenyuhe River in Beijing, China - a region predominantly supplied with reclaimed water. Subsequently, mixed microbial communities from the river were introduced into DOM samples originating from each source and incubated for 10 days. Principal component analysis (PCA) applied to reassembled excitation-emission matrix (EEM) data revealed two distinct clusters: cluster 1 comprising soil, sediment, and PM2.5 samples; and cluster 2 consisting of bait as well as terrestrial/aquatic plant residuals. According to parallel factor analysis, C1 (microbial humic-like) and C2-C3 (fulvic-like) dominated the DOM from soil, sediment, and PM2.5. These components were continuously degraded during incubation, except for PM2.5. DOM from bait and terrestrial/aquatic plants contained representative components of C6 (phenolic-like) and C7 (tryptophan-like), which underwent extensive decomposition. Interestingly, DOM in PM2.5 contained aliphatic compounds and polycyclic aromatic hydrocarbons (PAHs) but exhibited weak degradation with the complete disappearance of C6 and C7. Rhodococcus was a unique species capable of degrading PAHs, which might be particularly important considering the specificity of PM2.5 pollution. Based on two-dimensional correlation spectroscopy (2D-COS), variations in DOM components such as C6, and C7 were significantly larger compared to those of C1, C2, C3, and C5 (terrestrial humic-like) from bait samples, sediments, and residual terrestrial plants. MW-2D-COS analysis revealed that DOM from bait samples and terrestrial/aquatic plants experienced substantial degradation by the second day while DOM from soil or sediment decomposed mainly on the fourth day. Notably, the decomposition of DOM fractions in PM2.5 occurred throughout the entire four-day period. Co-occurrence network analysis classified sources of DOM into two clusters similar to PCA results: cluster 1 showed significant microbial degradation of fulvic-like compounds while cluster 2 demonstrated deep microbial decomposition of tyrosine-like and phenolic compounds. Therefore, the artificial loading of DOM into rivers not only expands the chemical diversity within DOM but also perturbs bacterioplankton diversities.

Molecular-level composition of dissolved organic matter in distinct trophic states in Chinese lakes: Implications for eutrophic lake management and the global carbon cycle.

Dissolved organic matter (DOM) is an abundant and mobile part of the aquatic environment and plays important roles in aquatic biogeochemical cycles and the global carbon cycle. Recently, eutrophication has become an important environmental issue in global lakes, but how eutrophication drives changes in the molecular composition of DOM along trophic gradients remains poorly understood. We thus characterized 67 DOM isolates from 11 lakes along a trophic gradient in China by using a combined approach including absorption spectroscopy, excitation-emission matrix fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our results indicated that dissolved organic carbon and absorption coefficients at 350 nm increased with increasing trophic status index. The ultraviolet absorbance at 254 nm and fluorescence intensity of all fluorescent components were higher in eutrophic lakes than in oligotrophic lakes. DOM in high trophic state lakes tended to be dominated by higher molecular weight, unsaturation degree, greater abundance of S-containing compounds, and condensed or polycyclic aromatic compounds than oligotrophic lakes. Additionally, autochthonous DOM characterized by more aliphatic compounds increased with the increasing trophic state. We concluded that nutrient input along with allochthonous DOM favors the lake eutrophication and subsequently increases the release and accumulation of autochthonous DOM. Consequently, eutrophication modifies the structure of the organic matter into more complex materials with increased input of allochthonous DOM and increased release of autochthonous DOM, which could accelerate global carbon cycle processes. Our results here have potential to contribute significantly to future studies of DOM dynamics in eutrophic lakes.

Linking the molecular composition of autochthonous dissolved organic matter to source identification for freshwater lake ecosystems by combination of optical spectroscopy and FT-ICR-MS analysis.

Autochthonous dissolved organic matter (DOM) is increasingly released in lakes due to eutrophication, and thus affects the composition and environmental behaviors of DOM in eutrophic lakes. However, there are only limited studies on the molecular characteristics of autochthonous DOM and its influencing mechanisms. Herein, end-member DOM samples of macrophytes, algae, sediments and freshwater DOM samples in eutrophic lakes (Ch:Taihu and Dianchi) were collected and characterized by optical spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The results revealed the chemical structures of autochthonous DOM were more aliphatic and less oxidized, which was marked by increases in lipid compounds and decreases in the lignin components as compared to the allochthonous DOM-dominated freshwaters. More specially, algae-derived DOM contains more lipid compounds, while macrophyte-derived DOM was dominated by lignin and tannin compounds according to Van Krevelen plots. Sediment-derived DOM contained more N-containing compounds. The traditional optical indices indicated the relative aromaticity covaried with polyphenolic and polycyclic aromatics, whereas those reflecting autochthonous DOM covaried with more aliphatic compounds. Multivariate analysis of FT-ICR-MS data of end-members and freshwaters revealed the predominant terrestrial input to Lake Taihu and greater contribution of algae released DOM to Dianchi. This study provides critical information about the characteristics of autochthonous DOM at a molecular level and confirmed autochthonous DOM was compositionally distinct from allochthonous DOM. Overall autochthonous DOM should be gained more attention in the eutrophic lakes.

Novel reversibly switchable wettability of superhydrophobic-superhydrophilic surfaces induced by charge injection and heating.

Reversibly switching wettability between superhydrophobicity and superhydrophilicity has attracted widespread interest because of its important applications. In this work, we propose a reversible superhydrophobic-superhydrophilic conversion induced by charge injection and heating. Different from the conventional electrowetting phenomenon caused by the accumulation of solid-liquid interfacial charges, we discovered a phenomenon where charge injection and accumulation at the solid surface results in a sharp increase in wettability. The wettability of a sprayed SiO2 nanoparticle coating on a glass slide was shown to change from superhydrophobic to superhydrophilic by charge injection and heating, and the superhydrophobicity was restored by heating, verifying a reversible superhydrophobic-superhydrophilic conversion. The influence of voltage, temperature, and time on the coating wettability and its durability under reversible conversion have been studied.