Ceramsite production using water treatment residue as main ingredient: The key affecting factors identification.

As an inevitable by-product of potable water production, drinking water treatment residue (DWTR) recycling to make ceramsite can provide both environmental and economic benefits in constructing filtration treatment system for water environment remediation. Given the varied properties of DWTR from different waterworks, this study aims to identify the key factors affecting ceramsite production from DWTR as main ingredient based on five different DWTR with using clay as the auxiliary material. The results showed that of sintering temperature (500-1000 °C), DWTR:clay ratio (5:5 to 9:1), sintering time (5-60 min), and granule diameter (5-15 mm), the sintering temperature was the key parameter. Increasing temperatures from 500 to 1000 °C gradually promoted DWTR sintering by enhancing Si and Al crystallization, which typically increased the formation of SiO2 and CaAl2Si2O8 crystals in ceramsite. Ceramsites made from different DWTR tended to have different properties, mainly resulting from varied contents of Si (20.2%-48.6%), K (0.0894%-2.39%), Fe (4.56%-14.3%), and loss on ignition (11.7%-39.5%). During ingredients preparation to produce up-to-standard ceramsite, supplying additional Si and diluting loss on ignition were necessary for all DWTR, while supplying K and diluting Fe may be required for specific DWTR, due to the potential varied DWTR compositions caused by different water production processes applied (e.g., type of flocculants). Further toxicity characteristic leaching procedure analysis indicated the increased leaching of Cu. However, DWTR based ceramsite was identified as non-hazardous material; even, sintering treatment reduced the leachability of Ba, Be, Cd, and Cr. DWTR based ceramsite also had relatively high specific surface area (22.1-50.5 m2/g) and could adsorb Cd, Cu, and Pb from solution. Overall, based on appropriate management, DWTR can be recycled as the main ingredient in the production of ceramsite for water environment remediation.

Resuspension and settlement characteristics of lake sediments amended by phosphorus inactivating materials: Implications for environmental remediation.

The classical lake internal phosphorus (P) pollution control using P-inactivating materials is typically carried out by reducing the release of soluble P from sediments to overlying water; however, particulate P loading through sediment resuspension could also cause internal P pollution for algae breeding. Therefore, based on lanthanum modified bentonite clay (Phoslock®) and drinking water treatment residues (DWTR), the effect of P inactivating materials on sediment resuspension and settlement were comprehensively investigated to assess the variations in particulate P pollution from sediment. Results showed that both materials could effectively control soluble P pollution from sediment, while both had limited effect on the supplement of particulate P to overlying water. The reason may be that hydrodynamic disturbance was the key factor regulating sediment resuspension and settlement. The disturbance induced the resuspension of different sized sediments, especially <8 µm fractions, while increasing disturbing intensities promoted resuspension of relatively larger sized sediments (e.g., <63 µm). Further analysis suggested that after resuspension and settlement, the efficiencies of reducing bioavailable P by Phoslock® in relatively large sized sediment fraction (e.g., <63 µm) were substantially less than those in relatively small sized sediment (<8 µm). Although the reducing efficacies of DWTR had limited changes in different sized sediments, the remaining bioavailable P were clearly higher in smaller sized sediments with DWTR. The different performances on bioavailable P reduction mainly resulted from the distributions of materials and original P in different sized sediments. These findings indicated the potential supplement of particulate P for algal growth during resuspension and settlement of sediments amended by P inactivating materials. Overall, understanding the sediment P bioavailability and hydraulic properties at different sizes and the lake hydrodynamic conditions is essential to develop appropriate methods to control lake internal P pollution.

The release inhibition of organic substances from microplastics in the presence of algal derived organic matters: Influence of the molecular weight-dependent inhibition heterogeneities.

As the emerging contaminants, the behavior and fate of microplastics (MPs) were highly related to the interactions with surrounding organic matters. However, information on the effects of molecular sizes of organic matters on the interaction is still lacking. In this study, the bulk algal-derived organic matter (AOM) samples were obtained and further fractionated into high molecular weight (HMW-, 1kDa-0.45 µm) and low molecular weight (LMW-, < 1 kDa) fractions. The interaction between MPs [polyethylene (PE) and polystyrene (PS)] and these MW-fractionated AOMs were characterized by dissolved organic carbon, fluorescence and absorbance spectroscopy, and fourier transform infrared (FTIR) analysis. Results showed that presence of AOM could effectively inhibit the release of additives from MPs. Further analysis found that the inhibition extents decreased in the order of HMW- > bulk > LMW-AOM. The absorbance and fluorescence spectroscopy showed that aromatic protein-like substances in HMW fraction exhibited higher adsorption affinity to MPs than the bulk and LMW counterparts. The strong sorption of aromatic substances may offer more binding sites for additives to inhibit the release of organic substances. Moreover, two dimensional FTIR correlation spectroscopy revealed that the HMW non-aromatic substances were preferentially adsorbed onto PS, which led to an enhanced adsorption capacity to additives by forming H-bonding. Therefore, the MW- and component-dependent heterogeneities of AOM samples must be fully considered in evaluating the environmental behavior of MPs.

Flavobacterium aurantiibacter sp. nov., an orange-pigmented bacterium isolated from cyanobacterial aggregates in a eutrophic lake.

A bacterial strain, designated TH167T, was isolated from cyanobacterial aggregates in eutrophic Lake Taihu in China. Cells were observed to be slightly curved rod-shaped, motile by gliding, aerobic, Gram-stain-negative, proteorhodopsin-containing. Optimal growth was obtained at pH 7.0 (range: 6.0-9.0), 28 °C (range: 4-32 °C) and 0 % (w/v) NaCl (range: 0-2.0 %) in Reasoner's 2A broth. No growth was observed at 37 °C. The cells were found to be positive for catalase and oxidase activities. The major fatty acids (>10 %) were identified as iso-C15 : 0, iso-C15 : 1 G and anteiso-C15 : 0. The major polar lipids of the isolate comprised phosphatidylethanolamine, one unidentified phospholipid and two unidentified aminolipids. The major respiratory quinone was menaquinone-6. The genomic G+C content of strain TH167T was 40.4 mol% based on total genome calculations. Based on similarities of 16S rRNA gene sequences, strain TH167T was affiliated with the genus Flavobacterium, exhibiting the highest sequence similarities to Flavobacterium eburneum SA31T (94.16 %), Flavobacterium yanchengensehgT (94.09 %) and Flavobacterium lacus NP180T (93.95 %). The phenotypic, chemotaxonomic and phylogenetic properties, and genome analysis suggested that strain TH167T represented a novel species within the genus Flavobacterium, for which the name Flavobacterium aurantiibacter sp. nov. is proposed. The type strain is TH167T (=CGMCC 1.15805T=LMG 29719T).

Selective Aza Diels-Alder and Domino [4+2]/[2+2] Cycloaddition Reactions of Arynes with N-Sulfonyl Ketimines.

Transition-metal-free inverse electron-demand aza Diels-Alder and domino [4+2]/[2+2] cycloaddition reaction of arynes and N-sulfonyl ketimines has been demonstrated. This novel, mild, and efficient protocol allows rapid access to isothiazole dioxide-fused dihydroquinoline or dihydrocyclobutaquinoline derivatives selectively by simply varying the equivalents of aryne precursors. The application of this method has been amply illustrated in the synthesis of 2,4-diarylquinolines.

Toward Quantitative Understanding of the Bioavailability of Dissolved Organic Matter in Freshwater Lake during Cyanobacteria Blooming.

Occurrence of cyanobacterial harmful algal blooms (CyanoHAB) can induce considerable patchiness in the concentration and bioavailability of dissolved organic matter (DOM), which could influence biogeochemical processes and fuel microbial metabolism. In the present study, a laboratory 4-stage plug-flow bioreactor was used to successfully separate the CyanoHAB-derived DOM isolated from the eutrophic Lake Taihu (China) into continuum classes of bioavailable compounds. A combination of new state-of-the-art tools borrowed from analytical chemistry and microbial ecology were used to characterize quantitatively the temporary evolution of DOM and to get deeper insights into its bioavailability. The results showed a total 79% dissolved organic carbon loss over time accompanied by depletion of protein-like fluorescent components, especially the relatively hydrophilic ones. However, hydrophilic humic-like fluorescent components exhibited bioresistant behavior. Consistently, ultrahigh resolution mass spectrometry (FTICR-MS) revealed that smaller, less aromatic, more oxygenated, and nitrogen-rich molecules were preferentially consumed by microorganisms with the production of lipid-like species, whereas recalcitrant molecules were primarily composed of carboxylic-rich alicyclic compounds. Moreover, the bioavailability of DOM was negatively correlated with microbial community diversity in the bioreactor. Results from this study provide deeper insights into the fate of DOM and relevant biogeochemical processes in eutrophic lakes.

Efficient Synthesis of Dimeric Oxazoles, Piperidines and Tetrahydroisoquinolines from N-Substituted 2-Oxazolones.

A mild and practical method for the construction of heterocycles from N-substituted 2-oxazolones through cascade, BF3 ⋅Et2 O/H2 O-catalyzed reactions involving iminium ion generation and trapping by external or internal olefinic and aryl moieties is described. Mechanistic and computational studies revealed the strong protic acid HBF4 as the initiating catalyst for these cascade reactions. Providing access to novel molecular diversity, these processes may facilitate chemical biology studies, drug discovery efforts and natural products synthesis.

Electrolyte Cations Binding with Extracellular Polymeric Substances Enhanced Microcystis Aggregation: Implication for Microcystis Bloom Formation in Eutrophic Freshwater Lakes.

The hydrodynamic and structural properties of Microcystis extracellular polymeric substances (EPS) in electrolytes with different valences and ionic strengths were investigated via using dynamic light scattering, the fluorescence excitation emission matrix coupled with parallel factor (EEM-PARAFAC) analysis, two-dimensional correlation spectroscopy (2D-COS), and cryogenic transmission electron microscopy (Cryo-TEM). The hydrodynamic diameters of EPS colloids exhibited no variation for monovalent NaCl but a substantial increase for divalent CaCl2 and MgCl2. However, the negative electrophoretic mobilities for all complexes indicated that charge neutralization would not be the main mechanism for EPS aggregation. Application of EEM-PARAFAC and 2D-Fourier transform infrared (FTIR)-COS revealed obvious electrolyte binding potential with both fluorescent phenolic and aromatic compounds and nonfluorescent polysaccharides. The complexation model showed that divalent Ca(2+) and Mg(2+) exhibited a strong binding capability with phenolic -OH, aromatic C═C, and polysaccharide C-O groups, while the monovalent electrolyte exhibited negligible association with these groups. Such a strong complexation can bridge each individual biomolecule together to form EPS aggregates and Microcystis colonies, as supported by in situ Cryo-TEM and light microscope observation, respectively. Given the increased concentration in natural ecosystems, electrolyte cations, especially divalent cations, would play increased roles in Microcystis bloom formation and thus should be considered.

Niveispirillum cyanobacteriorum sp. nov., a nitrogen-fixing bacterium isolated from cyanobacterial aggregates in a eutrophic lake.

A Gram-stain-negative, slightly curved rod-shaped, non-spore-forming diazotrophic bacterium, designated strain TH16T, was isolated from cyanobacterial aggregates taken from eutrophic Lake Taihu, Jiangsu Province, China. The pH range for growth was 5-9 (optimum at pH 7.0), salinity range was 0-2% (w/v) NaCl (optimum 0%) and temperature range was 20-37 °C (optimum 30 °C) in nutrient broth. Phylogenetic analysis indicated that strain TH16T clusters near and is closely related to the genus Niveispirillum within the family Rhodospirillaceae of the class Alphaproteobacteria. Within the genus Niveispirillum, strain TH16T was related most closely to Niveispirillum irakense KBC1T (98.1% 16S rRNA gene sequence similarity) and Niveispirillum fermenti CC-LY736T (97.0 %). The DNA G+C content of strain TH16T was 64 mol%. DNA-DNA relatedness between strain TH16T and the type strains of N. irakense and N. fermenti was 39.6 and 30.1%, respectively. The major respiratory quinone was ubiquinone Q-10.The major fatty acids (>10%) were C18  :  1ω6c/C18  :  1ω7c, C18  :  1 2-OH and C16  :  0 3-OH. Genes in the puf operon, encoding proteins of the photosynthetic reaction centre and core light-harvesting complexes, were also present. Based on morphological, chemotaxonomic and phylogenetic data, strain TH16T represents a novel species within the genus Niveispirillum, for which the name Niveispirillum cyanobacteriorum sp. nov. is proposed. The type strain is TH16T ( = CGMCC 1.12958T = LMG 28334T).

Novel precipitated zirconia-based DGT technique for high-resolution imaging of oxyanions in waters and sediments.

Water-sediment exchange is a fundamental component of oxyanion cycling in the environment. Yet, many of the (im)mobilization processes overlay complex spatial and temporal redox regimes that occur within millimeters of the interface. Only a few methods exist that can reliably capture these porewater fluxes, with the most popular being high-resolution diffusive gradients in thin films (HR-DGT). However, functionality of HR-DGT is restricted by the availability of suitable analyte binding agents within the sampler, which must be simple to cast and homogeneously distributed in the binding layer, exhibit adequate sorption capacities, be resistive to chemical change, and possess a very fine particle size (≤10 µm). A novel binding layer was synthesized to meet these requirements by in situ precipitation of zirconia into a precast hydrogel. The particle diameter≤0.2 µm of zirconia in this precipitated gel was uniform and at least 50-times smaller than the conventional molding approach. Further, this gel had superior binding and stability characteristics compared with the commonly used ferrihydrite HR-DGT technique and could be easily fabricated as an ultrathin gel (60 µm) for simultaneous oxygen imaging in conjunction with planar-optodes. Chemical imaging of anion and oxygen fluxes using the new sampler were evaluated on Lake Taihu sediments.

Synthesis of indazoles and azaindazoles by intramolecular aerobic oxidative C-N coupling under transition-metal-free conditions.

A transition-metal-free oxidative C-N coupling method has been developed for the synthesis of 1H-azaindazoles and 1H-indazoles from easily accessible hydrazones. The procedure uses TEMPO, a basic additive, and dioxygen gas as the terminal oxidant. This reaction demonstrates better reactivity, functional group tolerance, and broader scope than comparable metal catalyzed reactions.

Influences of dissolved organic matters on the adsorption and bioavailability of sulfadiazine: Molecular weight- and type-dependent heterogeneities.

The bioavailability of contaminants in aquatic environments was highly related with the existing forms (soluble or adsorbed) and properties of dissolved organic matters (DOMs). In this study, the molecular weight (MWs)-dependent effects of DOMs on the adsorption and bioavailability of sulfadiazine were explored. Colloid ZnO and Al2O3 were employed as the representative colloidal particles, and algae-derived organic matter (AOM) and humic acid (HA) were selected as typical autochthonous and allochthonous DOMs. The ultrafiltration procedure was applied to divide the bulk DOMs into high MW (HMW-, 1 kDã0.45 µm) and low MW (LMW-, <1 kDa) fractions. Results showed that HMW-DOM contained more aromatic and protein-like substances as compared to the LMW counterparts. In addition, presence of AOM promoted sulfadiazine adsorption capabilities by 1.19-4.54 folds and mitigated the inhibition ratio by 0.56-0.78 folds, whereas those of HA inhibited sulfadiazine adsorption by 0.27-0.84 folds and enhanced the biotoxicity by 1.21-1.45 folds. Regardless of different DOM types, HMW-fraction exhibited highest effects on sulfadiazine adsorption and bioavailability, followed by the bulk- and LMW-fractions. Two-dimensional correlation spectroscopy showed that sulfadiazine was adsorbed on colloidal surfaces prior to AOM, and the subsequent adsorption of AOM can provide additional sites for sulfadiazine adsorption, which decreased the concentrations of aqueous sulfadiazine as well as the biotoxicity to Microcystis aeruginosa (M. aeruginosa). The HA, however, was preferentially adsorbed on colloidal surfaces, which hindered the subsequent sulfadiazine adsorption and resulted in a high sulfadiazine abundance in aqueous solution as well as the enhanced biotoxicity to M. aeruginosa. This study highlighted the importance of the types and MWs of DOMs in influencing the behaviors and ecological effects of aquatic contaminants.

Humic substance mitigated the microplastic-induced inhibition of hydroxyl radical production in riparian sediment.

Hydroxyl radicals (·OH) generated during the flooding-drought transformation process play a vital role in affecting nutrient cycles at riparian zone. However, information on the processes and mechanisms for ·OH formation under the influence of microplastics (MPs) remains unclear. In this study, the effects of MPs on ·OH production from riparian sediments with different biomass [e.g., vegetation lush (VL) and vegetation barren (VB)] were studied. The results showed that presence of MPs inhibited the production of ·OH by 27 % and 7.5 % for VB and VL sediments, respectively. The inhibition was mainly resulted from the MP-induced reduction of the biotic and abiotic mediated Fe redox processes. Spectral analysis revealed that VL sediments contained more high-molecular-weight humic-like substances. Presence of MPs increased the abundances and activities of Proteobacteria, Acidobacteria and Actinobacteria, which were conducive to the changes in humification and polar properties of organic matters. The reduced humic- and fulvic-like substances were accumulated in the flooding period and substantially oxidized during flooding/drought transformation due to the enhanced MP-mediated electron transfer abilities, thus mitigated the MP-induced inhibition effects. Therefore, in order to better understanding the biogeochemical cycling of contaminants as influenced by ·OH and MPs in river ecosystems, humic substances should be considered systematically.

Photo-methanification of aquatic dissolved organic matters with different origins under aerobic conditions: Non-negligible role of hydroxyl radicals.

Lingering inconsistencies in the global methane (CH4) budget and ambiguity in CH4 sources and sinks triggered efforts to identify new CH4 formation pathways in natural ecosystems. Herein, we reported a novel mechanism of light-induced generation of hydroxyl radicals (•OH) that drove the production of CH4 from aquatic dissolved organic matters (DOMs) under ambient conditions. A total of five DOM samples with different origins were applied to examine their potential in photo-methanification production under aerobic conditions, presenting a wide range of CH4 production rates from 3.57 × 10-3 to 5.90 × 10-2 nmol CH4 mg-C-1 h-1. Experiments of •OH generator and scavenger indicated that the contribution of •OH to photo-methanificaiton among different DOM samples reached about 4∼42 %. In addition, Fourier transform infrared spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry showed that the carbohydrate- and lipid-like substances containing nitrogen-bonded methyl groups, methyl ester, acetyl groups, and ketones, were the potential precursors for light-induced CH4 production. Based on the experimental results and simulated calculations, the contribution of photo-methanification of aquatic DOMs to the diffusive CH4 flux across the water-air interface in a typical eutrophic shallow lake (e.g., Lake Chaohu) ranged from 0.1 % to 18.3 %. This study provides a new perspective on the pathways of CH4 formation in aquatic ecosystems and a deeper understanding on the sources and sinks of global CH4.

Molecular weight-dependent differences in spectral properties and metal-binding behaviors of dissolved organic matter from different lakes.

Dissolved organic matter (DOM) plays an important role in governing metal speciation and migration in aquatic systems. In this study, various DOM samples were collected from Lakes Erhai, Kokonor, and Chaka, and size-fractionated into high molecular weight (HMW, 1 kDa-0.7 µm) and low molecular weight (LMW, <1 kDa) fractions for measurements of dissolved organic carbon (DOC), spectral properties, and metal binding behaviors. Our results demonstrated that samples from Lake Chaka exhibited the highest DOC concentration and fluorescence indices but the lowest percentage of carbohydrates. Regardless of sampling locations, the HMW-DOM fractions contained higher abundances of aromatic DOM, carbohydrates and protein-like substances, but lower abundance of fulvic acid-like substances compared to those in the LMW fractions. Metal titration experiments coupled with the excitation-emission matrix (EEM)-parallel factor (PARAFAC) modeling revealed that the quenching of the PARAFAC-derived fluorescent components was more pronounced in the presence of Cu(II) compared to Pb(II). Humic-like components emerged as a superior model, exhibiting higher binding affinities for Cu(II) than protein-like substances, while the opposite trend was observed for Pb(II). In samples obtained from Lakes Erhai and Kokonor, the condition stability constants (Log KM) for the binding of both Cu(II) and Pb(II) with the HMW-DOM fraction were higher than those with the LMW-DOM fraction. Conversely, a contrasting trend was observed for Lake Chaka. This study highlighted the heterogeneity in spectral properties and metal-binding behaviors of natural DOMs, contributing to an improved understanding of the molecular interactions between DOM components and metal ions and their environmental fate in aquatic ecosystems.

Climate warming promotes collateral antibiotic resistance development in cyanobacteria.

Both cyanobacterial blooms and antibiotic resistance have aggravated worldwide and posed a great threat to public health in recent years. As a significant source and reservoir of water environmental resistome, cyanobacteria exhibit confusing discrepancy between their reduced susceptibility and their chronic exposure to antibiotic mixtures at sub-inhibitory concentrations. How the increasing temperature affects the adaptive evolution of cyanobacteria-associated antibiotic resistance in response to low-level antibiotic combinations under climate change remains unclear. Here we profiled the antibiotic interaction and collateral susceptibility networks among 33 commonly detected antibiotics in 600 cyanobacterial strains isolated from 50 sites across four eutrophicated lakes in China. Cyanobacteria-associated antibiotic resistance level was found positively correlated to antibiotic heterogeneity across all sites. Among 528 antibiotic combinations, antagonism was observed for 62 % interactions and highly conserved within cyanobacterial species. Collateral resistance was detected in 78.5 % of pairwise antibiotic interaction, leading to a widened or shifted upwards mutant selection window for increased opportunity of acquiring second-step mutations. We quantified the interactive promoting effect of collateral resistance and increasing temperature on the evolution of both phenotypic and genotypic cyanobacteria-associated resistance under chronic exposure to environmental level of antibiotic combinations. With temperature increasing from 16 °C to 36 °C, the evolvability index and genotypic resistance level increased by 1.25 - 2.5 folds and 3 - 295 folds in the collateral-resistance-informed lineages, respectively. Emergence of resistance mutation pioneered by tolerance, which was jointly driven by mutation rate and persister fraction, was found to be accelerated by increased temperature and antibiotic switching rate. Our findings provided mechanic insights into the boosting effect of climate warming on the emergence and development of cyanobacteria-associated resistance against collateral antibiotic phenotypes.

Dissolved organic matter promoted hydroxyl radical formation and phenanthrene attenuation during oxygenation of iron-pillared montmorillonites.

The oxygenation of Fe(II)-bearing minerals for hydroxyl radicals (HO•) formation and contaminant attenuation receives increasing attentions. However, information on dissolved organic matter (DOM) with different types, concentrations, and molecular weights (MWs) in manipulating HO• formation and contaminant attenuation during mineral oxygenation remain unclear. In this study, four iron-pillared montmorillonites (IPMs) and two DOM samples [e.g., humic acids (HA) and fulvic acids (FA)] were prepared to explore the HO• formation and phenanthrene attenuation during the oxygenation of IPMs in the presence or absence of DOMs. Results showed that iron-pillared and high-temperature calcination procedures extended the interlayer domain of IPMs, which provided favorable conditions for a high HO• production from 1293 to 14537 µmol kg-1. The surface-absorbed/low crystalline Fe(Ⅱ) was the predominant Fe(Ⅱ) fractionations for HO• production, and presence of DOMs significantly enhanced the HO• production and phenanthrene attenuation. Moreover, regardless of the types and concentrations, the low MW (LMW, <1 kDa) fraction within DOM pool contributed highest to HO• production and phenanthrene attenuation, followed by the bulk and high MW (HMW-, 1 kDa∼0.45 µm) fractions, and FA exhibited more efficient effects in promoting HO• production and phenanthrene attenuation than HA. The fluorescent spectral analysis further revealed that phenolic-like fluorophores in LMW-fraction were the main substances responsible for the enhanced HO• production and phenanthrene attenuation. The results deepen our understandings toward the behaviors and fate of aquatic HO• and contaminants, and also provide technical guidance for the remediation of contaminated environments.

Heterogeneity in metal binding by individual fluorescent components in a eutrophic algae-rich lake.

Dissolved organic matter (DOM) affects the toxicity, mobility and bioavailability of metals in aquatic environment. In this study, the interactions between two metals of environmental concern [Cu(II) and Fe(III)] with DOM in a euthrophic algae-rich lake (Lake Taihu, China), including dissolved natural organic matter (NOM) and algal extracellular polymeric substance (EPS), were studied using fluorescence excitation-emission matrix (EEM) quenching titration combined with parallel factor (PARAFAC) analysis. Obvious protein-like peaks were detected in algal EPS matrix, while both protein- and humic-like peaks can be found in NOM. PARAFAC analysis identified four fluorescent components, including one humic-, one tryptophan- and two tyrosine-like components, from 114 EEM samples. It was shown that fluorescent tyrosine- (log K(M) > 5.21) and humic-like substances (log K(M) > 4.84) in NOM fraction exhibited higher metal binding capacities than those in EPS matrix, while algal EPS was characterized with a high metal-tryptophan-like substances affinity (log K(M) > 5.08). Moreover, for the eutrophic algae-rich lakes, fluorescent tryptophan- and humic-like substances were responsible for Cu transportation, whereas the mobility of Fe would be related with the tyrosine-like substances. The results facilitate a further insight into the biogeochemical behaviors of metals in eutrophic algae-rich ecosystems as well as other related aquatic environments.

Investigation of cytotoxic cadmium in aquatic green algae by synchrotron radiation-based Fourier transform infrared spectroscopy: Role of dissolved organic matter.

The heavy metal Cd can cause severe toxicity on aquatic algae, but there are few studies on the cytotoxicity of heavy metal on algae based on synchrotron radiation technology. In this study, synchrotron radiation-based Fourier transform infrared spectromicroscopy (SR-FTIR) was used to characterize in vivo the toxic effects of Cd on Cosmarium sp. cells, emphasizing the influence of dissolved organic matter (DOM) on Cd toxicity. Results showed that, in the absence of DOM, obvious growth inhibition, cell volume reduction, and photosynthesis disruption could be observed with increasing Cd concentrations (0-500 µg/L). Based on the SR-FTIR imaging and functional group quantification, it was shown that the biosynthesis of biomolecules such as proteins, lipids, and carbohydrates was inhibited in algal cells. However, the addition of DOM caused significant heterogeneities in biomacromolecule biosynthesis that an increased biosynthesis of carbohydrates and structural lipids but an inhibited biosynthesis of proteins and storage lipids were observed. Furthermore, the correlation analysis and principal component analysis showed a good correlation between v(C-OH)/Amide II and biochemical parameters, indicating that changes of carbohydrates could be used as the biomarker to indicate the cytotoxicity of heavy metals to algal cells. These findings provide insight into the mechanisms of heavy metal cytotoxicity to aquatic algae and systematic cytotoxicity assessment under various aquatic conditions.

Carbonized bacterial cellulose/FeMn composite as efficient catalyst toward contaminant degradation: The crucial role of hydrogen reduction.

The structure especially the active site manipulation of Fenton-like catalysts was essential for the efficient removal of organic contaminants in the aquatic environment. In this study, the carbonized bacterial cellulose/FeMn oxide composite (CBC@FeMnOx) were synthetized and modified by hydrogen (H2) reduction to obtain the carbonized bacterial cellulose/FeMn composite (CBC@FeMn), with emphasis on the processes and mechanisms for atrazine (ATZ) attenuation. The results showed that H2 reduction did not change the microscopic morphology of the composites but destroy the Fe-O and Mn-O structures. Compared with the CBC@FeMnOx composite, the H2 reduction could promote the removal efficiency from 62% to 100% for CBC@FeMn, as well as the enhancement of degradation rate from 0.021 min-1 to 0.085 min-1. The quenching experiments and electron paramagnetic resonance (EPR) displayed that the hydroxyl radicals (•OH) was the major contributor for ATZ degradation. The investigation for Fe and Mn species indicated that H2 reduction could increase the content of Fe(II) and Mn(III) in the catalyst, thus improving the generation of •OH and accelerating the cycle process between Fe(III)/Fe(II). Owing to the excellent reusability and stability, it was indicated that the H2 reduction can be considered as an efficient way to regulate the chemical valence of the catalyst, thus enhancing the removal efficiency of aquatic contaminants.