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.

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.

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.

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.

Investigation and prediction of the biotoxicity of Cu2+ to Chlorella vulgaris: modification of the biotic ligand model.

The increased copper ion (Cu2+) concentrations in aquatic ecosystem significantly influence the environmental quality and ecosystem safety, while information on the Cu2+ biotoxicity to aquatic microorganisms and the models for biotoxicity prediction are still unclear. In this study, the toxicities of Cu2+ to Chlorella vulgaris under different environmental conditions (e.g., Na+, K+, Ca2+, Mg2+, pH, and dissolved organic matter) were explored, with the experimental results in comparison with those predicted by the biotic ligand model (BLM). Results showed that increased Cu2+ concentration caused obvious toxicities to C. vulgaris, whereas the commonly occurring cations and dissolved organic matters can protect the metabolism system of C. vulgaris. The presence of extracellular polymeric substances (EPS) matrix can alleviate the biotoxicity via increasing the surface biosorption but decreasing cell internalization of Cu2+ in C. vulgaris. Due to the presence of EPS matrix, the experimental biotoxicity results under each condition were significantly lower than those predicted by the BLM model, which was thus modified via taking the EPS matrix as the supplement of allochthonous organic matters. After that, the modified BLM was characterized with a higher degree of precision and can be used in natural waters for biotoxicity prediction. Results obtained can enhance our insights into the ecological effects and biotoxicity prediction of heavy metals in natural aquatic ecosystems.

Sediment resuspension causes horizontal variations in the distributions of phosphorus (P) and P-inactivating materials with differing P immobilization in different sediment planes.

The importance of controlling internal phosphorus (P) pollution in lakes has been recognized by scientists, and the application of P-inactivating materials to immobilize sediment P is often considered. However, sediment resuspension, a typical physical process occurring in lakes, has been demonstrated to increase the uncertainty of immobilization. In this study, we explored the characteristics of P immobilization in the horizontal direction under the effects of resuspension using annular flume tests based on drinking water treatment residuals (DWTR). The results showed that resuspension caused the mobile P and bioavailable P to be heterogeneously distributed in sediment planes after DWTR addition, resulting in varying P immobilization efficiencies at different depths. In particular, the coefficient of variation was 14.2-24.5% for mobile P horizontally distributed in the planes, resulting in a range of mobile P decreasing efficiencies at 24.0-47.8%. Further analysis indicated that variations in horizontal distribution were typically due to the varied migration of particles of different sizes. Specifically, P immobilization in sediment planes at different depths was regulated by promoting the migration of <8 µm DWTR after relatively low-intensity disturbance (in surface 0-1 cm sediment). After relatively high-intensity disturbance (in the whole 0-3 cm sediment), immobilization in the horizontal direction was regulated by coupling the migration of >63 µm DWTR (to the bottom) with the mixing of <8 µm DWTR in the sediment plane at different depths. The varying horizontal distributions of total P, resulting from the migration of 16-32 µm sediment, could enhance the heterogeneities of the P immobilization. Thus, the particle size of materials and lake background conditions, for example, the hydrodynamic characteristics and P distributions in differently sized sediments, should be used as key bases to select or develop P-inactivating materials to design proper remediation strategies for controlling internal P pollution in lakes.

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.

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.

Biochar as additive for improved building performances and heavy metals solidification of sediment-based lightweight concrete.

The sustainable disposal of large volumes of contaminated dredged river sediment has become a challenge for municipal management. In this study, a cutting-edge biochar application method was innovated, which converted the polluted dredged sediment into a low-carbon and environmentally friendly building material through an autoclave-free method. As the amount of biochar addition increased from 0 to 2% (w/w), the compressive strength of the dredged sediment-based lightweight concrete (DS-LC) increased from 3.92 to 4.61 MPa. Accordingly, the thermal conductivity decreased from 0.237 to 0.222 W/(m K), the water absorption decreased by 6%, and the water resistance coefficient increased by 33%. Results of X-ray diffraction (XRD) and thermogravimetric (TG) analysis showed that biochar promoted the hydration reaction and the carbonation process. Scanning electron microscopy (SEM) attached with energy-dispersive X-ray spectroscopy (EDX) showed that biochar addition changed the microstructure of the DS-LCs, which made the pore distribution more uniform and densified. Biochar addition also strengthened the immobilization of heavy metals (Cu, Zn, Cr, and As) by approximately 18-27% and combination of biochar and silica fume could increase the heavy metal immobilization by 28-44%. Compared with the traditional concrete material, the DS-LC with biochar addition could not only reduce the carbon emission but also has potential economic benefit for the treatment and utilization of dredged sediment.

High Flux Nanofiltration Membranes with Double-Walled Carbon Nanotube (DWCNT) as the Interlayer.

Nanofiltration (NF) membranes with a high permeability and rejection are of great interest in desalination, separation and purification. However, how to improve the permeation and separation performance still poses a great challenge in the preparation of NF membranes. Herein, the novel composite NF membrane was prepared through the interfacial polymerization of M-phenylenediamine (MPD) and trimesoyl chloride (TMC) on a double-walled carbon nanotube (DWCNT) interlayer supported by PES substrate. The DWCNT interlayer had a great impact on the polyamide layer formation. With the increase of the DWCNT dosage, the XPS results revealed an increase in the number of carboxyl groups, which decreased the crosslinking degree of the polyamide layer. Additionally, the AFM results showed that the surface roughness and specific surface area increased gradually. The water flux of the prepared membrane increased from 25.4 L/(m2·h) and 26.6 L/(m2·h) to 109 L/(m2·h) and 104.3 L/(m2·h) with 2000 ppm Na2SO4 and NaCl solution, respectively, under 0.5 MPa. Meanwhile, the rejection of Na2SO4 and NaCl decreased from 99.88% and 99.38% to 96.48% and 60.47%. The proposed method provides a novel insight into the rational design of the multifunctional interlayer, which shows great potential in the preparation of high-performance membranes.

Changes of the physicochemical properties of extracellular polymeric substances (EPS) from Microcystis aeruginosa in response to microplastics.

Microplastics (MPs) are ubiquitous in aquatic ecosystems and can significantly influence the growth, aggregation and functions of phytoplankton biomass. However, variations in the extracellular polymeric substances (EPS) of phytoplankton in terms of compositions and structures in response to MPs were still not reported. In this study, EPS matrix of Microsystis aeruginosa was applied and fractionated into loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) fractions, with the time-dependent changes in response to different concentrations (10, 100 and 500 mg/L) of MPs being explored via using the fluorescence excitation emission matrix coupled with parallel factor (EEM-PARAFAC) and two-dimensional Fourier transform infrared correlation spectroscopy (2D-FTIR-COS) analysis. Results showed that 500 mg/L of MP concentration significantly inhibited Microcystis growth by 30.5% but enhanced EPS secretion. In addition, organic composition in LB-EPS and TB-EPS varied differently in response to increased MP exposure, as the ratio of polysaccharide/protein increased in the TB-EPS but decreased in LB-EPS. Further analysis revealed obvious heterogeneities in organic component variations in response to MPs, as the C-O functional groups and glycosidic bonds in the TB-EPS preferentially responded, which lead to the domination of polysaccharides and humus substances; while the carbonyl, carboxyl and amino functional groups in the LB-EPS exhibited a preferential response, which caused the enhanced percentage of the tryptophan-like proteins. In addition to organic compositions, the aromaticity, hydrophobicity and humification in the LB-EPS fraction increased with enhanced MP exposure, which, as a result, may influence the ecotoxicological risk of MPs. Therefore, Microcystis can dynamically adjust not only the EPS contents but also the compositions in response to MPs exposure. The results can improve our understanding on the eco-physiological impact of phytoplankton-MP interaction in aquatic environment, and indicate that the dose-dependent and long-term effects of MPs on phytoplankton should be considered in future study.

Integrated evaluation of the reactive oxygen species (ROS) production characteristics in one large lake under alternating flood and drought conditions.

Reactive oxygen species (ROS) are omnipresent in natural aquatic environments, and play an important role in biogeochemical cycles. One of the dominant sources of ROS in surface waters was thought to be from dissolved organic matter (DOM) interacting with photochemical process. The properties of DOM were different between the flood and drought periods in lakes; yet, information on how these variations influence ROS photoproduction is unknown. Through a three-year study, the photochemical properties of DOM and the resultant ROS photoproduction between the flood and drought period were determined in the largest freshwater lake in China (Lake Poyang). Results found that quantum yield coefficients of excited triplets (3CDOM*), apparent quantum yields of singlet oxygen (1O2) and hydroxyl radicals (•OH) were holistically higher in the flood period than those in the drought period. The optical properties of DOM showed that DOM in the flood period featured an allochthonous input, accompanied by higher molecular size (E2/E3), aromatic content (SUVA254), humification degree (HIX), while DOM in the drought period was mainly internal input. Fourier transform ion cyclotron resonance mass spectrometry (FI-ICR MS) further revealed that some refractory components, such as lignin-like and carboxyl-rich alicyclic molecules (CRAM) presented higher abundance in the flood period, and played the positive impacts on ROS production. Orthogonal partial least squares (OPLS) were used to build novel multivariate predictive models for indicating the spatio-temporal ROS production. Also, the relatively higher steady-state concentrations of 3CDOM* and 1O2 in the flood period could significantly diminish the half-lives of acetochlor. Considering the photochemical activity of DOM varied considerably at different periods, this study provided a new method to predict ROS production and contributed to a new insight into stage-specific emerging contaminants removing in natural aquatic environments.

Preparation of Porous Silicate Cement Membranes via a One-Step Water-Based Hot-Dry Casting Method.

A commercial interest in the improvement in the separation performance and permeability of porous materials is driving efforts to deeply explore new preparation methods. In this study, the porous silicate cement membranes (PSCMs) were successfully prepared through an adjustable combination of hot-dry casting and a cement hydration process. The obtained membrane channel was unidirectional, and the surface layer was dense. The physical characteristics of the PSCMs including their pore morphology, porosity, and compressive strength, were diversified by adjusting the solid content and hot-dry temperature. The results indicated that with the solid content increasing from 40 wt. % to 60 wt. %, the porosity decreased by 8.07%, while the compressive strength improved by 12.46%. As the hot-dry temperature increased from 40 °C to 100 °C, the porosity improved by 23.04% and the BET specific surface area and total pore volume enlarged significantly, while the compressive strength decreased by 27.03%. The pore size distribution of the PSCMs exhibited a layered structure of macropores and mesopores, and the pore size increased with the hot-dry temperature. Overall, the PSCMs, which had typical structures and adjustable physical characteristics, exhibited excellent permeability and separation performance.

Insights into phenanthrene attenuation by hydroxyl radicals from reduced iron-bearing mineral oxygenation.

The oxygenation of Fe(II)-bearing minerals for hydroxyl radicals (HO•) formation and contaminant attenuation receive increasing attention, while the mechanisms for specific Fe(II) species in manipulating HO• formation and contaminant attenuation are unclear. Herein, a total of four Fe(III)-bearing minerals were applied in the reduction-oxygenation processes to produce HO•. Results showed that the total HO• generated from the Fe-(oxyhydr)oxides were significantly higher than those from the Fe-silicates, with the order of goethite and hematite (~1500 µmol kg-1) > Fe-montmorillonite (~550 µmol kg-1) > chlorite (~120 µmol kg-1). The HO• formation was largely hinged on the reactive Fe(II) species, i.e., the surface-adsorbed/low-crystalline Fe(II) in the Fe-bearing minerals. For the co-incubation of minerals and phenanthrene, the concentrations of phenanthrene decreased from the initial 3.0 mg L-1 to 0.7 mg L-1 and 1.9 mg L-1 for Fe-montmorillonite and goethite, respectively, suggesting the HO• mediated by the Fe-montmorillonite was more conducive for phenanthrene attenuation. The goethite tended to promote the formation of free HO•, while the Fe-montmorillonite with interlayer structure can provide attachment sites for the surface-adsorbed/low-crystalline Fe(II), resulting in high potential for surface-bound HO• formation and phenanthrene attenuation. This study highlights the importance of Fe-bearing minerals in manipulating HO• formation, providing new insight into the removal of contaminants in ecosystems.

Dissolved organic matters with low molecular weight fractions exhibit high photochemical potential for reactive oxygen formation.

The photochemical properties of dissolved organic matter (DOM) were highly related to the molecular weight (MW) and organic compositions. In this study, the bulk algae- and macrophyte-derived DOM (ADOM and MDOM, respectively) and Suwannee River humic acid (SRHA) were applied and fractionated into low MW- (LMW, <1 kDa) and high MW-(HMW-, 1 kDã0.45 µm) fractions. The formation and mechanisms of photochemically produced reactive intermediates (e.g., HO•, 1O2, and 3CDOM*) for these bulk and MW-fractionated samples were compared via the irradiation experiment, fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Results showed that humic-/fulvic-like substances were mainly distributed in the LMW fraction which occupied about 44-60% of total organic carbon for ADOM and MDOM and 13% for SRHA. Photochemical experiments showed that the autochthonous DOMs (e.g., ADOM and MDOM) were characterized with comparable formation rates and quantum yields of reactive oxygens with the allochthonous SRHA, suggesting the high photochemical formation potential. Further analysis showed obvious MW-dependent heterogeneities that, irrespective of DOM types, the LMW-fraction exhibited higher formation rates and quantum yields, followed by the bulk- and then the HMW-fractions. The fluorescence and FT-ICR-MS results indicated that the unique biochemical classes, i.e., humic-/fulvic-like moieties and protein-/lipid-derived compounds in the LMW fractions may be responsible for the high apparent quantum yields. This study highlighted the importance of simultaneous characterization of MW and organic compositions for evaluating the photochemical potential and other behaviors and effects of aquatic DOMs.

Quantifying the bioaccumulation of Pb to Chlorella vulgaris in the presence of dissolved organic matters with different molecular weights.

Dissolved organic matter (DOM) is ubiquitous in natural waters which exhibits obvious effects on the toxicity of heavy metals. However, information on the toxicity of heavy metals in the presence of DOMs with different molecular weights (MWs) was still unclear. In this study, Suwannee river humic acid (SRHA) and algae-derived organic matter (ADOM) were selected as typical terrestrial and microbial DOMs, with the bulk DOMs fractionating into high MW (HMW-, 1 kDa ~ 0.45 µm) and low MW (LMW-, < 1 kDa) fractions to explore the MW-dependent heterogeneities in the bioaccumulation of Pb to Chlorella vulgaris. Results showed that, regardless of DOM types, the LMW fraction exhibited more acidic groups and humic-like substances than the HMW counterparts. Presence of bulk DOM can decrease the bioaccumulation of Pb, while the specific effects were MW- and type-dependent. The LMW-SRHA enhanced the bioaccumulation of Pb while the HMW counterpart alleviated the effects. However, both the HMW- and LMW-ADOM can reduce the bioaccumulation of Pb to C. vulgaris. Moreover, the correlation analysis showed a significant positive correlation between the content of phenolic-OH and the adsorbed/internalized amounts of Pb, demonstrating that the phenolic-OH played a critical role in altering the bioaccumulation of Pb. The results obtained in this study suggest that distribution of MWs, number of acidic functional groups, and metal complexation capacity within DOM pool should be considered for the eco-environmental risk assessment of heavy metals in aquatic environments.

Assessing the enhanced reduction effect with the addition of sulfate based P inactivating material during algal bloom sedimentation.

The typical harm effect of algal bloom sedimentation is to increase sulfides level in surroundings, threatening aquatic organisms and human health; whereas, P inactivating materials containing sulfate are commonly attempted to be used to immobilize reactive P or to flocculate excessive algae in water columns for eutrophication control. In this study, variations in sulfate reduction during algal bloom sedimentation with the addition of sulfate based inactivating materials was comprehensively assessed based on using Al2(SO4)3 with comparison to AlCl3. The results showed that addition of Al2(SO4)3 had more substantial effect on overlying water and sediment properties compared to those of ACl3. Al2(SO4)3 can enhance sulfate reduction, resulting in temporary increase of sulfides (p < 0.01) and quick decrease of various Fe (p < 0.01) in overlying water and then promoting the formation of FeS and FeS2 (determined by EXAFS analysis) in sediments. Most importantly, the increased sulfides, as well as the physical barrier on sediment formed due to Al2(SO4)3 addition, enhanced the transformation of sulfides to odorous contaminants, increasing odorous contaminants (especially methyl thiols) production by approximately one order of magnitude in overlying water. Furthermore, the increased sulfides facilitated to the enrichment of microorganisms related to S cycles (Thiobacillu with relative abundance of 23.8%) and even promoted to enrich bacterial genus potentially with pathogenicity (Treponema) in sediments. The impacts of sulfate tended to be regulated by algae concentration; however, careful management was recommended for sulfate based inactivating materials application to control eutrophication with algal blooms.

Development of phosphorus composite biochar for simultaneous enhanced carbon sink and heavy metal immobilization in soil.

As a porous and carbon material, biochar is focused on respectively in sequestrating carbon and stabilizing metals in soil, while few studies attempted to design biochar for simultaneously achieving these two targets. This study proposed to produce phosphorus-composite biochar for synchronously enhancing carbon sequestration and heavy metals immobilization. Two phosphorus materials from tailings, Ca(H2PO4)2 and Ca5(PO4)3(OH), were selected as modifier to load into biomass prior to pyrolysis. Results showed that incorporating P not only increased pyrolytic C retention in biochar by 36.1-50.1%, but also obtained biochar with higher stability by chemically formation of COP, C-PO3 and C2-PO2. After 90-day incubation with soil, more C was sequestrated in the P-biochar amended soil (59.6-67.0%) than those pristine biochar (43.2-46.6%). Highly soluble Ca(H2PO4)2 was more efficient than Ca5(PO4)3(OH) in this regard. Meanwhile, these P-composite biochar exhibited more Pb/Cd immobilization (31.3-92.3%) compared with the pristine biochar (9.5-47.2%), which was mainly due to the formation of stable precipitates Pb5(PO4)3Cl and Cd3(PO4)2, especially for Ca5(PO4)3(OH) modification. Additionally, P-composite biochar "intelligently" altered soil microbial community, i.e., they suppressed Actinobacteria proliferation, which is correlated to carbon degradation, while promoted Proteobacteria growth, facilitating phosphate dissolution for ready reaction with heavy metals to form precipitate, benefiting the Pb and Cd immobilization. A dual functions biochar was engineered via simply loading phosphorous prior to pyrolysis and simultaneously enhanced carbon sequestration and heavy metal immobilization.

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.