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Heavy metals were typical contaminants in aquatic ecosystems, while their effects on the biotoxicity and metabolism of algal cells in the presence of organic ligands were still unclear. In this study, the contrasting effects of Cu and humic acids (HA) on the growth inhibition, oxidative stress and extracellular secretion of microalga Chlorella vulgaris were studied at environmentally relevant concentrations of Cu (0~2 mg/L) and HA (0~20 mg/L). Results showed that, with increased Cu addition, the algal growth rate decreased while concentrations of superoxide dismutase and malondialdehyde increased showing evident growth inhibition and oxidative damage in the sole presence of Cu. However, the presence of HA could significantly alleviate the Cu-induced toxicity damage, and higher concentrations of HA exhibited greater alleviation efficiencies. Fluorescence spectroscopy combined with flow field flow fractionation revealed that secretion of 50 kDa~0.45 μm of extracellular protein-like substances was the critical fractions responsible for the biotoxicity alleviation. Analysis of Cu contents within extracellular polymeric substance (EPS) matrix showed that not only the secretion amounts but also the acquisition capacities of EPS matrix decreased due to the addition of HA. This study benefited an in-depth understanding toward the toxicity of heavy metals to aquatic microorganisms in natural waters that contained abundant organic ligands.

Nitrogen (N) is one of the nutrients embedded in biowastes and its speciation in solid–liquid–gas pyrolysis products is closely related to environmental issues such as the greenhouse effect, acid r...

N,O-Bis(tert-butoxycarbonyl)hydroxylamines are readily accessible as imine surrogates, which are bench stable and could quantitatively generate the corresponding imines for in situ applications. An unpresented catalytic asymmetric method for the synthesis of α-amino esters and ketones from novel imine surrogates, N,O-bis(tert-butoxycarbonyl)hydroxylamines, as well as its preliminary mechanistic studies are reported. A variety of optically enriched products were obtained in excellent yields and enantioselectivities (up to 99% yield and >99% ee).

Colloidal particles in lake waters interact inevitably with cyanobacterial extracellular polymeric substance (EPS), which will change their behavior and fate. Quantitative prediction of the effects of cyanobacterial EPS on colloidal behavior is difficult due to its variability and heterogeneity. To explore the effects of molecular weight (MW) fractions and chemical properties of cyanobacterial EPS on aggregation kinetics of colloidal particles, time-series cyanobacterial samples were collected in Lake Taihu, China, from April to November (during blooming and maintenance period), with the bulk EPS matrix fractionating into low MW (LMW-,1 nm) and high MW (HMW-, 1 nm-0.45 μm) fractions. HMW-EPS was generally characterized with higher absorbance and predominant distribution of protein-like substances, while LMW-EPS contained mainly the humic- and fulvic-like substances. The absorbance, molecular size, and humification degree for each MW fraction consistently increased from April to November, showing obvious temporal variations from blooming period to maintenance period. As for the MW-dependent aggregation behaviors, the HMW-EPS provided better stability against aggregation than the LMW-EPS, and the bulk EPS matrix that consisted of HMW- and LMW-fractions exhibited the effects intermediate between that of each fraction alone. Regardless of MW fractions, the effects of EPS-induced stability enhancement were more evident in maintenance period than in blooming period. Further analysis showed that the colloidal stability was correlated positively with SUVA

Lignocellulose is a promising sustainable alternative fuel and its decomposition is critical for the formation of sediment organic matter. The lignin of lignocellulose limits the access of enzymes to cellulose and slows down the decomposition. Therefore, the development of efficient microbial consortia to deconstruct lignin is of great interest. In this study, a 715-day in situ experiment was performed to investigate the degradation process of macrophyte Phragmites australis debris at different depths of sediments (up to 38 cm) in a eutrophic lake. Although litter mass degradation showed an obvious decreasing tendency as the depth increased, the efficiency of lignin degradation in subsurface sediments was significance higher than that in surface sediments (p

This study proposed a scheme for drinking water treatment residue (DWTR) pretreatment to eliminate concerns about potential unfavorable effects caused by excessive release of nutrients (typically N) during recycling in restoration of a water environment with relatively low pollution (e.g., eutrophic surface water). Inspired by soil washing, the pretreatment scheme was based on washing processes; correspondingly, the N desorption characteristics, possibility of recycling solutions for subsequent desorption, and variations in DWTR adsorption capabilities were investigated. The results showed that N, mainly as ammonia N (NH4+-N), was quickly desorbed from DWTR; the concentrations of desorbed NH4+-N were an order of magnitude higher than those of nitrate N (NO3−-N). After six rounds of desorption, most ion-exchangeable NH4+-N was desorbed, and NH4+-N released from the DWTR (after the desorption test) declined markedly from 11.1 to

The metal binding potential of dissolved organic matter (DOM) is highly related with its inherent properties such as molecular weight (MW). Here sediment DOMs with different origins, i.e., algae- and macrophyte-dominated sediment DOM (named as ASDOM and MSDOM, respectively), were size-fractionated into low MW (LMW-,1 kDa) and high MW (HMW-, 1 kDa~0.45 μm) fractions, with the spectral and metal binding properties in different MW fractions exploring via total organic carbon, absorption spectroscopy, fluorescence parallel factor (PARAFAC) analysis, and Cu(II) titration techniques. The MSDOM contained more organic carbon, lower specific UV absorbance, lower fluorescence index, higher humification index, and lower biological index compared to the ASDOM. As for the MW-fractionated samples, the humic- and fulvic-like fluorophores were mainly distributed in the LMW-DOM, while the protein-like ones were located richly in the HMW-DOM. Thus, obvious MW- and origin-dependent heterogeneities in abundance and spectral properties were observed for sediment DOMs. One humic-like, one fulvic-like, and two protein-like fluorescent components were identified by PARAFAC analysis, with different components exhibiting different variable patterns in response to Cu(II) addition. Irrespective of sample sources, humic- and fulvic-like components had higher condition stability constants (logK

Natural organic matter (NOM), a heterogeneous mixture with various organic components and continuous molecular weight (MW) distribution, is omnipresent in natural waters. To date, understanding of the MW-dependent adsorption fractionation of NOM samples on colloids is limited due to the lack of NOM fractionation and characterization methods. In this study, the ultrafiltration technique was applied to fractionate the bulk NOM samples into low MW (LMW

Anaerobic ammonium oxidation coupled to ferric iron reduction (Feammox) has been assumed to play an important role in nitrogen removal from ecosystems. This study assessed the potential role of Feammox in nitrogen transformation in eutrophic lake sediment using an isotope tracing technique in sediment slurry incubation experiments. Feammox was discovered in eutrophic lake sediment. A significant correlation was found between Feammox rates and iron-reducing rates. Furthermore, the positive correlations between the abundance of iron-reducing bacteria (FeRB), such as Geobacteraceae spp. and Shewanella spp., and Feammox rates indicate that Feammox was mediated by FeRB. The potential rate of Feammox in the isotopic tracer incubation treatment was 0.23-0.43 mg N kg-1 day-1. The estimated nitrogen loss caused by Feammox accounts for 5.0-9.2% of the human-induced N input annually into the eutrophic lake. Feammox alone or coupled with anaerobic ammonium oxidation (anammox) and/or denitrification may have an essential role in the nitrogen cycle within eutrophic lake sediment.

Colloidal particles are omnipresent in lake sediments and substantially influence the retention, transportation, and fate of contaminants in lake ecosystems. In this study, the abundance, chemical composition and adsorption behavior of sedimentary colloids (including total and inorganic colloids) from different ecological regions, were for the first time investigated via ultrasonic extraction, spectral analysis and batch absorption experiments. Results showed that the extraction efficiencies of sedimentary colloids showed an ultrasonic energy-dependent enhancement, and the algae-dominated area contained comparable colloidal abundance with the macrophyte-dominated area (i.e., 198.5 vs. 183.3 mg/g). Despite the different ecosystems, these sedimentary colloids usually had a wide size distribution of 30-200 nm, and were characterized with montmorillonite-, kaolin-, volkonskoite-, and quartz-rich chemical compositions. Batch experiment showed that the total pristine colloids exhibited higher adsorption capacity for Pb(II) than the inorganic colloids both for the macrophyte- and algae-dominated sediments, and the adsorption process followed pseudo-second-order kinetics and Langmuir isotherm, irrespective of different colloidal types. Thus, sedimentary colloids can immobilize the heavy metals in sediment and decrease their release into the water column, which can be considered as a sink for contaminants. This study highlighted the significance of sedimentary colloids in determining the physicochemical properties of lake sediments and in evaluating the environmental behavior and fate of contaminants in lake ecosystems.

Abstract: Rifamycins are considered a milestone for tuberculosis (TB) treatment because of their proficient sterilizing ability. Currently, available TB treatments are complicated and need a long duration, which ultimately leads to failure of patient compliance. Some new rifamycin derivatives, i.e., rifametane, TNP-2092 (rifamycin-quinolizinonehybrid), and TNP-2198 (rifamycin-nitromidazole hybrid) are under clinical trials, which are attempting to overcome the problems associated with TB treatment. The undertaken review is intended to compare the pharmacokinetics, pharmacodynamics and safety profiles of these rifamycins, including rifalazil, another derivative terminated in phase II trials, and already approved rifamycins. The emerging resistance of microbes is an imperative consideration associated with antibiotics. Resistance development potential of microbial strains against rifamycins and an overview of chemistry, as well as structure-activity relationship (SAR) of rifamycins, are briefly described. Moreover, issues associated with rifamycins are discussed as well. We expect that newly emerging rifamycins shall appear as potential tools for TB treatment in the near future.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments, whose behaviors and fate are highly related to the chemical compositions and size distribution. In this study, the UV-induced photodegradation properties of DOMs with different origins (i.e., macrophyte- and algae-derived) were investigated using absorption and fluorescence spectroscopy as well as flow field-flow fractionation (FlFFF). Results showed that, irrespective of DOM origins, the chromophoric components could be more effectively photo-degraded than the non-chromophoric ones. Though the two DOMs were characterized with similar fluorophores, the photodegradation properties showed obvious heterogeneities in DOM origins and molecular weights (MWs). Compared to macrophyte-derived DOM (MDOM), the algae-derived DOM (ADOM) exhibited a higher degradation rate and efficiency due to the abundance of labile components like newborn protein-like substances. The FlFFF results revealed a high photo-preferability of 100 kDa-0.45 μm protein-like MDOM and same photo-sensitivity of the size-fractionated humic-like moieties, testifying the reduction of molecular sizes during the photodegradation. However, the increase in relative percentage for 100 kDa-0.45 μm protein-like components and 5–15 kDa humic-like moieties implied a possible enhancement of molecular sizes for ADOM during the early period (i.e., the first hour) of photodegradation. This study provides new insights into the origin-related heterogeneities in compositions and size distribution for DOM transformation.

Tetracycline (TC) adsorption capacity on pristine biochar was limited. Biochar modification can greatly improve its adsorption amount. In this study, rice straw was mixed with FeCl3·6H2O and urea to prepare a Fe–N modified biochar via a one-pot pyrolysis method at 700 °C. Meanwhile, pristine biochar (RSBC), urea modified biochar (N–RSBC), FeCl3·6H2O-modified biochar (Fe–RSBC) were produced as control. More functional groups, more graphited carbon structure, and magnetic components were observed in Fe–N–RSBC. Compared with RSBC, the surface area, total pore and micropore volume of Fe–N–RSBC increased 3.4-fold, 3.0-fold and 2.3-fold, respectively. The maximum capacity of TC adsorption on Fe-N-RSBC reached 156 mg·g−1, which was 5.4 − fold, 8.2 − fold and 1.9 − fold increase to that of RSBC, N-RSBC, Fe-RSBC, respectively. The mechanism of TC adsorption on Fe-N-RSBC involved pore filling, hydrogen-bond interaction, surface complexation, and π–π interaction. Therefore, Fe-N-RSBC can be used as an effective adsorbent for TC removal from aqueous solution.

Pyrolysis process significantly influences the physicochemical properties and potential application of magnetic porous biochars (MPBCs). However, the effects of pyrolysis temperature on the properties of MPBCs as well as substantial adsorption are still unclear. This study reported a facile method to obtain the MPBC from tea waste via pyrolysis of a mixture of hydrochar, KHCO3, and FeCl3·6H2O under different temperatures (500–800 °C), and explored further the adsorption toward tetracycline (TC). Results showed pyrolysis temperature obviously influenced the physicochemical properties of MPBCs, and MPBC pyrolyzed at 700 °C (MPBC-700) has a highest specific surface area (1066 m2 g−1) and pore volume (2.693 cm3 g−1). However, the adsorption potential increased consistently from 59.35 mg g−1 for MPBC-500 to 333.22 mg g−1 for MPBC-800, suggesting that the surface area and pore volume were not the only factors determining TC adsorption. Further analysis showed that the pore-filling, π-π interaction, complexation, and hydrogen bonding contributed together to TC adsorption. Moreover, all MPBCs possessed a high saturation magnetization, indicating the easy separation by an external magnet. Therefore, MPBCs (especially at 700 °C) can act as the excellent adsorbents for contaminant removal due to their high separation, adsorption, and reuse performance.

The properties of biochars and their adsorption performance are highly dependent on the carbonation methods. In this study, five carbonation methods, namely, hydrothermal treatment (HT), direct carbonization (BC), carbonization of hydrochar (HBC), KHCO3 activation carbonation (KBC), and KHCO3 activation carbonation of hydrochar (KHBC), were adopted to prepare tea waste biochars. Adsorption behaviors and mechanisms toward tetracycline (TC) by biochar in the aquatic environment were investigated. The results showed that carbonation methods significantly influence the morphology, carbon structure, chemical composition, and functional groups of the biochars based on the characterization of surface area and pore volume analysis, Fourier Transform Infrared Spectroscopy, Raman spectrum, Scanning Electron Microscope, Transmission Electron Microscope, X-ray photoelectron spectroscopy, X-Ray Diffraction, and elemental analysis. Combination of hydrothermal treatment with KHCO3 activation can significantly increase the surface area and enlarge the pore structure of biochar (KHBC and KBC). The BET of KHCO3-activated BCs nearly increased 280 times (KHBC: 1350.80 m2 g−1; KBC: 1405.06 m2 g−1). BET, total pore volume and micropores volume of biochar has a positive influence on TC adsorption capacity. In addition, all adsorption processes can be well fitted by Langmuir and pseudo-second-order kinetic models. The maximum adsorption capacity of KHCO3-activated BCs nearly increased approximately 40 times (KHBC: 451.45 mg g−1; KBC: 425.17 mg g−1). The dominant mechanisms of biochar-adsorbed TC were pore-filling effect and π–π interactions, followed by hydrogen bonds and electrostatic interactions. Therefore, KHBC has the potential to act as sorbents for TC removal from aquatic environment.

Eutrophication and metal pollution are global environmental problems. The risk of metal pollution is high in the eutrophic lakes because of high mobility of metal in sediments. However, the mechanism of cadmium (Cd) mobility in sediments is still unclear. Here we study the mobilization of Cd in sediments from the eutrophic Lake Taihu via monthly field monitoring of mobile Cd using diffusive gradient in thin films (DGT) and high resolution dialysis (HR-Peeper) techniques. We found a high mobility of Cd in sediments in February and March, resulting from reductive dissolution of Mn oxide mediation by high microbial activities, as shown by the similarities in distribution patterns of DGT-labile Cd and Mn. A two orders of magnitude increase in dissolved Cd concentrations (about 28 μg L−1) was observed in May and June, with dissolved Cd concentrations in overlying water about 110 times higher than the criteria continuous concentration set by Environmental Protection Agency. Hourly changes were found to coincide and correlate between dissolved Cd and dissolved organic matter (DOM) under simulated anaerobic conditions, strongly suggesting that the sudden outbreak of Cd pollution observed in the field resulted from the complexation of DOM with Cd in sediments. This was further supported by the NICA-Donnan model that more than 71% of dissolved Cd in the pore water in May and June was present as Cd-DOM complexes. Three components of DOM including humic-, tryptophan-, and tyrosine-like components in the sediments in June was identified using the fluorescence excitation emission matrix-parallel factor analysis. We found that Cd was stable complexed with tyrosine-like component. The Fourier transform infrared and two-dimensional correlation spectroscopy further revealed that Cd was bound to phenolic O H, alkene C C, alcoholic C O, aromatic C H, and alkene CH groups. Our study effectively promotes the understanding of Cd mobilization in sediments and highlights the risk of sudden Cd pollution events in the eutrophic lakes.

Fe-based materials used to adsorb P are commonly considered to be limited by the increased Fe lability, while Fe in drinking water treatment residue (DWTR) shows stable P adsorption abilities. Accordingly, this study aimed to gain insight into Fe lability in DWTR as compared to FeCl3 and Fe2(SO4)3 using Fe fractionation, EXAFS, and high-throughput sequencing technologies. The results showed that compared to Fe2(SO4)3 and FeCl3, Fe was relatively stable in the DWTR under the effects of organic matter, sulfides, and anaerobic conditions. Typically, the addition of FeCl3 and Fe2(SO4)3 enhanced Fe mobility in sediment and overlying water, promoting the formation of Fe-humin acid and ferrous sulfides (FeS and FeS2). However, the addition of DWTR, even at relatively high doses of Fe, has limited impact on Fe mobility. The addition remarkably increased oxidizable Fe in sediment (by approximately 63%), causing Fe to be dominated by oxidizable and residual fractions (like those in raw DWTR); EXAFS analysis also suggested that Fe-humin acid increased substantially with the addition of DWTR, becoming the main Fe species in sediment (with a relative abundance of 50.1%). Importantly, the Fe distributions were stable in sediment with DWTR added, which demonstrated that organic matter stabilized the Fe in the DWTR. Further analysis indicated that all materials promoted the enrichment of bacterial genera potentially related to Fe metabolism (e.g., Bacteroides, Dok59, and Methanosarcina). Fe2O3 in the FeCl3 and Fe2(SO4)3 groups and Fe-HA in the DWTR group were the key species affecting the microbial communities. Overall, the stabilizing effect of organic matter on Fe in DWTR could be used to develop Fe-based materials to enhance Fe stability for environmental remediation.

Dissolved organic matter (DOM) adsorption on colloid surface occurred ubiquitously in aquatic ecosystems, while variations in molecular weight (MW) distribution during adsorption remained poorly understood. In this study, the adsorption and MW fractionation of aquatic DOMs with different origins (e.g., macrophyte- and algae-derived, MDOM and ADOM, respectively) on colloid surface were examined using total organic carbon, absorption and fluorescence spectroscopy, and flow field flow fractionation (FlFFF) analysis. Both the total organic carbon and spectroscopic results showed the predominant adsorption of DOMs within the first 45 min, which behaved not synchronously with MW fractionation. Quantitative FlFFF analysis further indicated that the organic ligands with different MWs exhibited different adsorption affinities on colloid surface. It was found that 5–15 kDa and 50 kDa0.45 μm were preferential adsorption fraction for humic- and protein-like MDOM, respectively, while 0.3–2 kDa and 0.3–50 kDa were preferential adsorption fraction for humic- and protein-like ADOM, respectively. Therefore, the MW fractionation of DOMs upon adsorption was highly dependent on DOM origins as well as specific components. Results obtained herein can enlarge our insights into adsorption and the resultant behavior and fate of DOMs that were highly related with the MW fractionation in aquatic environments.

We report the synthesis of a series of graphene-induced self-assembly phase transformations of tetragonal β-In2S3 into cubic α-In2S3 at lower temperatures based on the principles of molecular and crystal engineering and a simple one-pot soft integration strategy based on wet chemistry. Controlled contact In2S3/G heterojunction hybrids with sizes ranging from 3D/2D to 2D/2D. In the process, the 3D petal-like In2S3 is transformed into 2D nanosheets grown on the 2D graphene "mat". Due to effective charge separation and close interfacial contact, the excellent visible catalytic purification performance for the degradation of organic pollutants, benzyl alcohol selective oxidation and reduction of Cr2O72- has been achieved. The significantly improved photocatalytic purification efficiency is mainly due to the graphene-induced phase transition which increases the number of active sites and strengthens the two-dimensional/two-dimensional contact of the interface, which promotes the effective transmission and separation of photo-excited carriers, thereby Effectively improve the photocatalytic purification ability. This research provides new insights for the preparation of high-efficiency graphene-based nano-hybrid photocatalysts with controllable structure through rational use of the structure-oriented and induced phase transition effects of graphene, and expands its visible light catalytic purification applications.

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

Knowledge of the dynamic changes in molecular size of natural colloidal organic matter (COM) along the aquatic continuum is of vital importance for a better understanding of the environmental fate and ecological role of dissolved organic matter and associated contaminants in aquatic systems. We report here the pH- and cation-dependent size variations of COMs with different sources (river and lake) quantified using flow field-flow fractionation (FIFFF), fluorescence spectroscopy and parallel factor analysis (PARAFAC), attenuated total reflectance Fourier transform infrared (ATR–FTIR) spectroscopy, and zeta potential analysis. Increasing pH caused a decline in molecular sizes and an obvious size transformation from the >10 kDa to 5–10 kDa and further to 1–5 kDa size fraction, whereas the opposite trend was observed for increasing cation (e.g., Ca2+ and Cu2+) abundance. Compared with lakewater COM, the riverwater COM exhibited a greater pH-dependent dispersion but less extent in cation-induced aggregation, demonstrating that the dispersion and aggregation dynamics were highly dependent on COM source and solution chemistry (e.g., pH and cations). Based on ATR–FTIR analysis, the extensive dissolution of C=O and C–O functional groups resulted in a greater pH-dependent dispersion for river COM. Fluorescence titration revealed that, despite their similar cation-induced aggregation behavior, the binding constants of all the PARAFAC-derived components for Cu2+ were 1–2 orders of magnitude higher than those for Ca2+ (logKM: 4.54–5.45 vs. 3.35–3.70), indicating a heterogeneous nature in cation-DOM interactions. The greater extent of decline in zeta potential for lake COM suggested a Ca-induced charge neutralization and aggregation mechanism. However, for Cu-induced aggregation, chemical complexation was the predominant pathway for the river COM, with higher binding constants, while charge neutralization and chemical complexation co-induced the aggregation of lake COM. Thus, natural COMs may have different environmental behavior along the aquatic continuum and further affect the fate and transport of contaminants in aquatic environments.

Dissolved organic matter (DOM) in aquatic environment significantly influences the behavior and fate of heavy metals via binding, complexation and thus changes the metal speciation; however detailed interfacial processes and mechanisms are still unclear. Here, differential absorbance and fluorescence spectra and two dimensional UV–FTIR heterospectral correlation analysis were applied to probe into the Pb(II)–DOM interaction at a wide range of pH and ionic strength (IS). The absorbance of DOM molecules under all conditions increased with metal addition, while the different extents of absorbance variations along the wavelength range in the differential zero-order and log-transformed absorbance spectra indicated the site heterogeneity within the DOM pool for metal binding. Spectral parameters, namely differential fluorescent components 1 and 2 (DFC1 and DFC2) and differential slopes of log-transformed absorbance in the range of wavelength 350–400 nm (DSlope350–400) were found to be highly correlated with the total amounts of DOM-bound Pb(II) predicted by the NICA-Donnan model, while the differential absorbance spectra at 235 nm (DA235) was related to the extent of Pb(II) bound by carboxylic groups. Thus, these parameters are an indicator or proxy for the in situ Pb(II)–DOM interaction extent. Aryl C–H gave the fastest response to Pb(II) binding at lower pH and IS (e.g., pH 4.7 and IS = 0.01 M), followed by carboxyl C=O and polysaccharide C–OH and then chromophoric groups at 265 nm (CDOM265). However, the CDOM265 bound to Pb(II) prior to aryl C–H and polysaccharide C–OH groups at higher pH and IS (6.0 and 0.1 M, respectively), showing that the binding sequences were highly dependent on solution chemistry. Differential spectra combined with two dimensional UV–FTIR heterospectral correlation analysis can be used as a promising approach to elucidate metal–DOM interaction processes, including site heterogeneity, binding sensitivity and sequence at the functional group level.

The separation and recovery of pollutant-loaded magnetic carbon materials from organic contaminated environment is recently concerned, but the change of sorption ability and mechanism of activated carbon and biochar caused by magnetic particles modification still need to be explored. Here, the magnetic modification of two coconut shell-, coal-derived activated carbon and one biochar, and its effect on the removal of phenol from water were investigated. Magnetic activated carbon (MAC) and magnetic biochar (MBC) were prepared by co-precipitation. The increase of mass magnetic susceptibilities and energy dispersive X-ray spectroscopy (EDX) analysis showed that magnetic particles were successfully coated on the surface of virgin carbonaceous materials (VCMs). Magnetic modification enhanced the surface area and pore volume of activated carbon, and preserved those structure properties of biochar. Magnetic activated carbon had lower adsorption rates (10.641 g mg−1·min−1) than virgin activated carbon (20.575 g mg−1·min−1) while magnetic biochar exhibited higher adsorption rate (0.618 g mg−1·min−1) compared with virgin biochar (0.040 g mg−1·min−1), which were related to mass transport process. Data from Langmuir model results suggested that maximum adsorption capacities of three carbon adsorbents were increased by magnetic modification. The enhanced removal of phenol after magnetizing process may attribute to the increase of specific surface area and pore volume. Among VCMs/MCCs, magnetic coconut shell-derived carbon material with 951.84 m2/g surface area exhibited the most organic contaminant sorption performance. This finding gives insight into the adsorption mechanism of magnetic AC/BC for phenol, and provides a guidance to choose the appropriate magnetic composites to remove the organic contaminant effectively.

Drinking water treatment residue (DWTR) often exhibits favorable microbial effect on nitrogen (N) removal during recycling as phosphorus (P) adsorbent in environmental remediation. Given the relatively high concentrations of iron (Fe) in DWTR and the importance of Fe-cycling microbial communities to regulate N cycles in nature, this study hypothesized that the favorable effect on N removal stemmed from the coupling of N to Fe cycle-related microbial communities in DWTR, which was then verified by microbial enrichment tests using metagenome technology and high-throughput sequencing analysis. The results suggested that DWTR seeded by activated sludge (0.05% in dry weight) acquired a strong and steady ability to convert different forms of N. After approximately 90 d of enrichment, the complete microbial N cycle, including 41 functional genes, was characterized in DWTR. The identified functional microbial communities showed relatively high similarity in DWTR enriched at different N levels, although the communities tended to be affected by N loading and initial N concentrations. Importantly, pairwise comparisons showed the close relations between N-cycling pathways (except N fixation) and various Fe-cycling genera, especially Ferrovum and Geobacter, which demonstrated the comprehensive functions of Fe and N cycling-related microbial communities. The P adsorption capability of DWTR was also maintained after enrichment. Overall, DWTR could be feasibly used to enhance microbial functions for simultaneous N and P pollution control.

Seasonal flooding-drought transformation process of lake sediments lead to changes of dissolved oxygen and redox conditions and the resultant generation of hydroxyl radical (HO•). To date, information on HO• formation and its regulators in seasonal lake sediments is largely unexplored. In this study, a total of nineteen sediments were collected from Lake Poyang, China, with the formation and mechanisms of HO• during the oxygenation process exploring via the incubation experiments, Fe K-edge X-ray adsorption spectroscopy, ultrafiltration, and fluorescent spectroscopy. Results showed that the concentrations of HO• generated ranged from 3.75 ± 1.13 to 271.8 ± 22.81 μmol kg−1, demonstrating high formation potential and obvious spatial heterogeneity. The yield of HO• formed was positively correlated with the contents of Fe(II), sedimentary organic carbon, and dissolved organic carbon, showing a general contribution of these reduced substances to HO• formation. Furthermore, application of Fe K-edge X-ray adsorption spectroscopy revealed the key species of sedimentary Fe-smectite for HO• formation due to its high peroxidase-like activity. Besides inorganic Fe(II), the sedimentary dissolved organic matters (DOMs) represented an important regulator for HO• formation, which contributed about 2–11% of the total HO• generation. Moreover, the DOM-induced formation potential was found to be highly related to the molecular weight distribution that the low molecular weight- (LMW

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.

A phosphine-catalyzed novel enantioselective [4 + 2]-annulation reaction between allene ketones and 1-azadienes has been developed, and tetrahydropyridines were obtained in good yields and with excellent enantioselectivities. Subsequent exposure of tetrahydropyridines to benzyne leads to a [2 + 2]-cyclization, creating optically enriched polycyclic piperidines with a quaternary stereogenic center and a cyclobutene moiety. The reported stepwise [4 + 2]/[2 + 2]-cycloadditions represent a new approach to access enantiomerically enriched nitrogen-containing six-membered ring systems.

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.

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.

The stability/aggregation propensity of inorganic colloids in eutrophic shallow lakes is of great essence in governing the water transparency and contaminant behavior. In this study, time-resolved dynamic light scattering was employed to investigate the aggregation kinetics of Al2O3 inorganic colloids over a wide range of cyanobacterial extracellular polymeric substance (EPS) concentrations in the absence and presence of electrolyte cations. The results showed that EPS adsorption alone greatly decreased the hydrodynamic diameters of colloidal particles, whose stability behavior followed closely the predictions of the classical DLVO theory. Electrolyte cations, however, can induce the aggregation of colloidal particles, and divalent Ca2+ were found to be more efficient in destabilizing the colloids than monovalent Na+, as indicated by the considerably lower critical coagulation concentrations (2.5 mM for Ca2+ vs. 170 mM for Na+). Further addition of Ca2+, i.e., >2.5 mM, caused an extremely high aggregation degree and rate. High resolution transmission electron microscopy revealed that this enhanced aggregation should be attributed to the gel-like bridging between colloidal particles, which were verified to be the amorphous EPS-Ca2+ complexes. Field-emission scanning electron microscopy coupled with elemental mapping provided additional evidence that the bridging interaction of EPS with Ca2+ was the predominant mechanism for the aggregation enhancement.

Microbial degradation is an elimination method for removal of organic contaminants from soil and water. However, the main factor limiting its practical application is high bacterial sensitivity to environmental factors such as pH, toxicity, and mass transfer. In this study, biochar was produced pyrolytically from peanut shells at 350 °C, 550 °C, and 750 °C (referred to as BC350, BC550, and BC750, respectively) and their promotion on phenol biodegradation in wastewater by the bacterium Pseudomonas citronellolis was investigated. Higher initial phenol concentration (>400 mg L−1) showed obvious inhibition on biodegradation with the removal efficiencies being less than 46%, and even the bacterium failed to survive at the phenol concentrations of higher than 1000 mg L−1. With biochar incorporated, the removal efficiencies of phenol increased from below 46% to up to 99% at the initial concentrations of 400–1200 mg L−1. Immobilization of strains in biochar by calcium alginate further increased the microbial tolerance to high concentrations of phenol (i.e., 63% removal at 1200 mg L−1). Scanning electron microscopy demonstrated that biochar acted as shelter to support the bacterium to struggle with extreme conditions. The initial adsorption of phenol by biochar alleviated the initial toxicity of phenol to bacterium and the subsequent gradual desorption controlled the bioavailability of phenol. In this regard, BC350 showed a comparable sorption capacity with BC550 and BC750, while a higher desorption potential than them, thus balanced better the toxicity and bioavailability of phenol to microbes. Alkalinity of BC550 and BC750 played important roles in rescuing the microbes from being damaged by pH shock via neutralizing the fast generation of acidic intermediates. The extractable organic substances in BC350 could be consumed by bacterium as substrates, which was confirmed by incubating the strains in water-extractable solution. Results of this study indicate that incorporation of microbes with biochar could promote the biodegradation of high concentration organic wastewater.

A novel multi-cathode, single-anode system integrating a sediment microbial fuel cell -based biosensor was developed for in-situ, continuous, and online monitoring of dissolved oxygen (DO) concentrations along various depths of lake water. The signal feedback mechanism was evaluated based on a relationship between voltage and DO concentration at corresponding depths. With an external resistance of 1000 Ω, a linear relationship was found (regression coefficient, R2 = 0.9576) between voltage and DO in the range of 0–9 mg L−1. The sensor performance was further optimized under various influence factors. The results of indoor experiments indicated that the optimal anode to single cathode area ratio was 11:1. The sensor signal could also be significantly influenced by organic matter content in sediment; thus, the addition of 5% organic matter could obtain a stable anode potential and a high voltage output. Furthermore, the sensor was operated in-situ for 67 days in a lake environment, which also led to a good correlation between the voltage and DO (R2 = 0.8897). Thus, this integrated system has great potential as an early-warning program to help identify environmental risks in aquatic environments.

Rhizosphere, formed via the input of root exudates, is one of the most dynamic biological interfaces on earth. Investigation of carbon dynamics in rhizosphere is thus crucial for the understanding of soil biogeochemical processes. Herein, synchrotron radiation-based Fourier transform infrared (SR-FTIR) combined with two dimensional correlation spectroscopy (2D-COS) was used to probe and identify the changes of chemical constituents and functional groups of organic carbon on the root/soil interface in rhizosphere of two plants [Leptochloa chinensis (L.) Nees and Cyperus rotundus L.]. The SR-FTIR results showed obviously heterogeneous distributions of functional groups in rhizosphere at microscale. Specifically, regardless of plant species, about 20–30 μm regions in rhizosphere can be affected by root activities. The peak area ratios of organic-OH and aliphatic-C to clay-OH on the root/soil interface in rhizosphere were 4.04–8.48 times higher than that in bulk soil, providing direct evidence of the organic carbon storage due to root activities. 2D-COS analysis suggested that the root activities induced the first adsorption or sequestration of newly organics (3350 cm−1) on the root/soil interface, followed by the destruction of clay-OH (3621 or 860 cm−1), leading to the release of mineral associated organics and nutrients (e.g., 1510 and 1150 cm−1) from the soil. These results can enlarge our knowledge on the concentration, distribution, and dynamics of organic carbon in rhizosphere at the microscale level and also the environmental behaviors and fate of other elements and contaminants that associated with organic carbon in rhizosphere. Capsule SR-FTIR combined with 2D-COS can explore the distribution and dynamics of organic carbon on the root/soil interface in rhizosphere.

Phytoplankton-derived extracellular polymeric substances (EPS) are of vital importance for the biogeochemical cycles of hydrophobic organic pollutants in lake ecosystems. In this study, roles of loosely-bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) in biosorption of phenanthrene (PHE) on a typical cyanobacteria Microcystis aeruginosa were investigated. The results showed that the biosorption of PHE on M. aeruginosa cell varied lasted 24 h, while the binding of PHE to LB-EPS and TB-EPS reached equilibrium within less than 2 h. The equilibrium biosorption capacities of M. aeruginosa cell, LB-EPS and TB-EPS were 6.78, 12.31, and 9.47 μg mg−1, respectively, indicating that the binding of PHE to EPS was a considerable process involved in biosorption. Fluorescence quenching titration revealed that increasing temperature induced more binding sites in EPS for PHE and the binding process was driven by electrostatic force and hydrophobic interactions. Interestingly, dynamic and static quenching processes occurred simultaneously for the binding of PHE to protein-like substances in EPS, whereas the binding of PHE to humic-like substances belonged to static quenching. The relatively higher contents of proteins in LB-EPS produced a stronger binding capacity of PHE. Overall, the interactions between hydrophobic organic pollutants and cyanobacterial EPS are favorable to the bioaccumulation of hydrophobic organic pollutants in cyanobacteria and facilitate the regulatory function of cyanobacterial biomass as a biological pump.

Nanoparticle binding with organic ligands in natural waters is important to understand their environmental behavior and fate. In this study, the interaction of two metal oxide nanoparticles (nano-CuO and nano-Fe3O4) with extracellular polymeric substances (EPS) from algal aggregates was studied through using fluorescence emission-excitation matrix (EEM) quenching titration combined with parallel factor (PARAFAC) analysis. Spectroscopy analysis detected two protein-like peaks in the loosely bound EPS (LB–EPS) fraction, while both protein-, fulvic- and humic-like peaks can be found in the tightly bound EPS (TB–EPS) fraction. PARAFAC analysis identified three independent fluorescence components, including one tryptophan-, one tyrosine- and one humic-like component, from 68 original EEM spectra. A quenching experiment showed that humic-like components in the TB–EPS fraction exhibited higher nanoparticle binding capacities (logKM > 6.23) than that in the LB–EPS fraction (logKM: 5.66), while the mobility of nano-Fe3O4 would be influenced by organic ligands in the TB–EPS fraction (logKM > 6.28). Based on the results, the toxicity of nanoparticles in the eutrophic waters would be higher than those in the oligotrophic ecosystems. This study facilitates a deeper understanding of the environmental behavior and fate of metal oxide nanoparticles in eutrophic aquatic ecosystems.

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.

Phosphatization of ZnO nanoparticles (ZNPs) at various pHs and its influence on subsequent lead sorption were investigated. Results showed that, in presence of phosphate, both the chemical speciation and crystalline phase of ZNPs were pH dependent that most of them were converted to crystalline Zn3(PO4)2 at acidic pHs, but only little amorphous hopeites can be formed under alkaline condition. Phosphatization process significantly enhanced subsequent lead sorption with the order of acidic process > alkaline > pristine ZNPs. Spectroscopic analysis including ATR-FTIR and XPS revealed main mechanisms of lead phosphate precipitation and inner-sphere complexes for lead sorption on acidic and alkaline treatment products, respectively. The potential toxicity of ZNPs and heavy metals in eutrophic aquatic ecosystems would thus be reduced due to the ubiquitous phosphatization process. This study highlights the importance of environmental variables in exploring the environmental behavior and fate of heavy metals as well as nanoparticles in natural waters.

Dissolved organic matter (DOM) is ubiquitous in aquatic ecosystem and characterized by a wide range of molecular weight (MW) distribution. In this study, a total of nine bulk DOM samples, including five International Humic Substances Society (IHSS) standards and four naturally collected samples, were fractionated into low MW (LMW-, ) was investigated. The formation rate of HO (RHO ) for the bulk samples were 4.60–7.27 × 10−12 M/s/mg-C/L for IHSS standards and 4.63–7.66 × 10−12 M/s/mg-C/L for naturally collected samples. Regardless of sample types, the LMW fraction was found to exhibit generally higher RHO values than the HMW counterparts. For IHSS standards, the RHO decreased from 4.68–8.46 × 10−12 M/s/mg-C/L for LMW fraction to 3.67–6.66 × 10−12 M/s/mg-C/L for HMW fraction, and for naturally collected samples, the value of RHO decreased from 5.21–12.04 × 10−12 M/s/mg-C/L for LMW fraction to 3.25–6.49 × 10−12 M/s/mg-C/L for HMW counterpart. A positive correlation between the net RHO and the normalized intensities of fluorescent peak [Em/Ex: (400–500)/(230–250) nm] was found, showing that the HO formation was strongly coupled to the abundance of humic-like substances. The results indicate that aquatic DOM is an important pool for HO formation, and characterization of MW distribution rather than average MW is thus required to explain the DOM-induced formation potential of HO .

Cyanobacterial extracellular polymeric substances (EPSs) in aquatic environments are easily adsorbed onto colloidal particles, whereas the adsorption behavior as affected by molecular weight (MW) properties remained unknown till now. Herein, the bulk cyanobacterial EPS matrix ( Bulk > LMW-EPS, demonstrating obvious MW-dependent adsorption heterogeneities. During adsorption, the values of SUVA254 in residual supernatants exhibited an initial decrease followed by gradual increase for all samples, suggesting that the preferentially adsorbed aromatic substances can be subsequently replaced by the non-aromatic moieties. 2D–FTIR–COS further revealed that the carboxylic groups of proteins were preferentially adsorbed onto colloidal surface, followed by the C C functional groups and then the C H groups of polysaccharides, which accounted for the variations of SUVA254 values in the supernatants. This study demonstrated that the adsorption behavior of EPS matrix was highly MW-dependent, and detailed characterization on size fractionation is thus needed in future studies.

The overgrowth of macrophytes has become serious due to increasing eutrophication in shallow lakes. The primary degradation processes of macrophytes litter, including photodegradation and biodegradation, induce considerable patchiness in the concentration and bioavailability of dissolved organic matter (DOM). In this study we investigated the composition evolution of DOM derived from emergent aquatic plant litter, Phragmites australis, in microbial degradation, photodegradation, and the combination of bio- and photo-degradation. Results revealed that the effects of photo- and biodegradation on the composition difference of macrophyte litter-derived DOM during short- and long-term degradation phase were different. Although large changes in DOM were observed after five days of incubation, the abundance and chemical composition were similar in the three treatments. However, more concentration of DOM was produced by combined photo- and biodegradation at the long-term degradation phase, and the composition of DOM showed less lignin-like formulae, as well as less condensed aromatic and aromatic compounds when compared to sole treatments. More reactive oxygen species (ROS) were found under the combined treatments, thus the contents of refractory components (condensed aromatic- and aromatic compound groups) were reduced. This study provide deeper insight into the fate of DOM and relevant biogeochemical processes in eutrophic lakes.

The loading of La can substantially enhance the adsorption capability of drinking water treatment residue (DWTR) for better recycling. Normally, the modification was based on incubation of DWTR and La solution at a certain ratio, following by solid-liquid separation and drying processes. This study attempted to simplify La loading procedures by adopting high ratio of DWTR and La solution to eliminate the solid-liquid separation, aiming to promote the potential actual production. According to the results of the short- (2 d) and long-term (30 d) P adsorption tests, the N2 gas sorption and desorption analysis, the X-ray photoelectron spectroscopy analysis, and the metal fractionation, the substantial enhanced adsorption capability of the modified DWTR was maintained and the La loading mechanisms to DWTR changed little after eliminating solid-liquid separation processes during modification; typically, La loading increased the initial P adsorption rates from 1.00 (raw DWTR) to 6.08 and 6.03 mg g−1 d−1 for the modified DWTR with and without the separation processes. Furthermore, the DWTR before and after modification had little unfavorable effect on the survival of snail Bellamya aeruginosa, while eliminating the separation processes tended to reduce the bioavailability of Al, Fe, and La in the modified DWTR. These results demonstrated that solid-liquid separation was not the key step for DWTR modification and that the developed simple modification method was feasible for La loading to DWTR, promoting the beneficial recycling in environmental remediation.

Stability of colloidal particles contributes to the turbidity in the water column, which significantly influences water quality and ecological functions in aquatic environments especially shallow lakes. Here we report characterization, origin and aggregation behavior of aquatic colloids, including natural colloidal particles (NCPs) and total inorganic colloidal particles (TICPs), in a highly turbid shallow lake, via field observations, simulation experiments, ultrafiltration, spectral and microscopic, and light scattering techniques. The colloidal particles were characterized with various shapes (spherical, polygonal and elliptical) and aluminum-, silicon-, and ferric-containing mineralogical structures, with a size range of 20–200 nm. The process of sediment re-suspension under environmentally relevant conditions contributed 78–80% of TICPs and 54–55% of NCPs in Lake Taihu, representing an important source of colloids in the water column. Both mono- and divalent electrolytes enhanced colloidal aggregation, while a reverse trend was observed in the presence of natural organic matter (NOM). The influence of NOM on colloidal stability was highly related to molecular weight (MW) properties with the high MW fraction exhibiting higher stability efficiency than the low MW counterparts. However, the MW-dependent aggregation behavior for NCPs was less significant than that for TICPs, implying that previous results on colloidal behavior using model inorganic colloids alone should be reevaluated. Further studies are needed to better understand the mobility/stability and transformation of aquatic colloids and their role in governing the fate and transport of pollutants in natural waters.

Cyanobacterial blooms as a global environmental issue are of public health concern. In this study, we investigated the spatial (10 sites) and temporal (June, August and October) variations in: 1) their biomass based on chlorophyll-a (chl-a) concentration, 2) their toxic genotype based on gene copy ratio of mcyJ to cpcBA, and 3) their cpcBA genotype composition of Microcystis during cyanobacterial bloom in Lake Taihu. While spatial-temporal variations were found in chl-a and mcyJ/cpcBA ratio, only spatial variation was observed in cpcBA genotype composition. Samples from northwestern part had a higher chl-a, but mcyJ/cpcBA ratio didn't vary among the sites. High chl-a was observed in August, while mcyJ/cpcBA ratio and genotypic richness increased with time. The spatial variations in chl-a and mcyJ/cpcBA ratio and temporal variation in cpcBA genotype were correlated negatively with dissolved N and positively with dissolved P. Spatial distribution of Microcystis biomass was positively correlated with nitrite and P excluding October, but no correlation was found for spatial distribution of mcyJ/cpcBA ratio and cpcBA genotype. Spatial distribution of toxic and cpcBA genotypes may result from horizontal transport of Microcystis colonies, while spatial variation in Microcystis biomass was probably controlled by both nutrient-mediated growth and horizontal transport of Microcystis. The temporal variation in Microcystis biomass, toxic genotype and cpcBA genotype composition were related to nutrient levels, but cause-and-effect relationships require further study.

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV-Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments.

Dissolved organic matter (DOM) is ubiquitous and plays an important role in regulating water quality, ecological function, and the fate and transport of trace elements and pollutants in aquatic environments. Both the colloidal precursors (i.e.1 kDa) and bulk DOM collected from a freshwater estuary were incubated in the dark for 21 days to examine dynamic changes in molecular size and composition induced by microbial degradation and self-assembly. Results showed that the concentrations of total organic carbon, carbohydrates, and protein-like substances decreased by 11-30% during incubation, while those of humic- and fulvic-like substances remained relatively constant, indicating humic substances are more resistant to microbial utilization compared to carbohydrates and protein-like DOM. Despite the different extents in decline, these DOM components had a similar transformation pathway from the1 kDa to colloids (1 kDa-0.45 μm) and further to microparticles (0.45 μm). Overall, carbohydrates and protein-like substances, especially the high molecular weight components, were preferentially decomposed by microorganisms whereas humic- and fulvic-like DOM components significantly coagulated through abiotic self-assembly. The contrasting degradation/transformation pathways between the humic-like and protein-like substances along the size continuum, as also characterized by flow field-flow fractionation analysis, demonstrated that the dynamic transformation and degradation of DOM is regulated by both molecular size and organic composition. This finding provides new insights into the biogeochemical cycling pathways of heterogeneous DOM and its environmental fate and ecological role in aquatic systems.

The use of phosphorus (P) inactivating agents to reduce internal P loading from sediment for lake restoration has attracted increasing attention. Reasonably, the physicochemical properties of P inactivating agents may vary with the interference of various environmental factors, leading to the change of control effectiveness and risks. In this study, the effect of fulvic acid (FA) adsorption on the properties of two agents, drinking water treatment residuals (DWTRs) and Phoslock®, was investigated. The results showed that after adsorption, there was little change for the main structures of DWTRs and Phoslock®, but the thermostability of Phoslock®, as well as the particle size and settleability of the two agents decreased. The specific surface area and pore volume of DWTRs also decreased, while those of Phoslock® increased. Further analysis indicated that aluminum and iron in DWTRs were stable during FA adsorption, but a substantial increase of lanthanum release from Phoslock® was observed, in particular at first (P

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.

Metal binding of organic ligands can definitely affect its environmental behavior in waters, while information on the binding heterogeneity with different organic ligands is still lacked till now. In this study, the binding of zinc with organic matters associated with cyanobacterial blooms, including dissolved organic matters (DOM) and attached organic matters (AOM), were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy (2D-COS). Metal-induced fluorescent quenching was obviously observed both for DOM and AOM, indicating the formation of metal–ligand complexes. Compared with the one-dimensional spectra, 2D-COS revealed the sequences of metal–ligand interaction with the following orders: 276 nm > 232 nm for DOM and 232 nm > 276 nm for AOM. Furthermore, the modified Stern–Volmer model showed that the binding constant (log K M ) of 276 nm in DOM was higher than that of 232 nm (4.93 vs . 4.51), while AOM was characterized with a high binding affinity for 232 nm (log K M : 4.83). The ranks of log K M values were consistent with the sequential orders derived from 2D-COS results both for the two samples. Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal–ligand interaction.

Extracellular polymeric substances (EPS) from bloom-forming cyanobacteria exist ubiquitously in eutrophic waters, while their effects on the aggregation/stabilization of nanoparticles remain unknown. In this study, the stability of ZnO nanoparticles (ZNPs) upon adsorption of cyanobacterial EPS was investigated by using two dimensional ATR-FTIR correlation spectroscopy, XPS and DLVO theory. Results showed that the adsorption process followed the Langmuir isotherm and pseudo-second-order kinetics both for the total organic contents as well as the individual parallel factor-derived components. The physicochemical and spectroscopic techniques revealed the mechanism of both electrostatic attraction and surface complexation in EPS adsorption. Further analysis showed increased absorbance and turbidity of ZNPs solutions with EPS addition, demonstrating the enhanced colloidal stability. The DLVO theory explained that the increased energy barriers and values of second energy maximum were responsible for the stability enhancement. This study facilitates a deeper insight into the environmental behavior of nanoparticles in eutrophic algae-rich waters.