Cotransport of nanoplastics and plastic additive bisphenol AF (BPAF) in unsaturated hyporheic zone: Coupling effects of surface functionalization and protein corona.

The ecological risk of combined pollution from microplastics (MPs) and associated contaminants usually depends on their interactions and environmental behavior, which was also disturbed by varying surface modifications of MPs. In this study, the significance of surface functionalization and protein-corona on the cotransport of nanoplastics (NPs; 100 nm) and the related additive bisphenol AF (BPAF) was examined in simulated unsaturated hyporheic zone (quartz sand; 250-425 µm). The electronegative bovine serum albumin (BSA) and electropositive trypsin were chosen as representative proteins, while pristine (PNPs), amino-modified (ANPs), and carboxyl-modified NPs (CNPs) were representative NPs with different charges. The presence of BPAF inhibited the mobility of PNPs/CNPs, but enhanced the release of ANPs in hyporheic zone, which was mainly related to their hydrophobicity changes and electrostatic interactions. Meanwhile, the NPs with high mobility and strong affinity to BPAF became effective carriers, promoting the cotransport of BPAF by 16.4 %-26.4 %. The formation of protein-coronas altered the mobility of NPs alone and their cotransport with BPAF, exhibiting a coupling effect with functional groups. BSA-corona promoted the transport of PNPs/CNPs, but this promoting effect was weakened by the presence of BPAF via increasing particle aggregation and hydrophobicity. Inversely, trypsin-corona aggravated the deposition of PNPs/CNPs, but competition deposition sites and increased energy barrier caused by coexisting BPAF reversed this effect, facilitating the cotransport of trypsin-PNPs/CNPs in hyporheic zone. However, BPAF and protein-coronas synergistically promoted the mobility of ANPs, owing to competition deposition sites and decreased electrostatic attraction. Although all of the NPs with two protein-coronas reduced dissolved BPAF in the effluents via providing deposition sites, the cotransport of total BPAF was improved by the NPs with high mobility (BSA-PNPs/CNPs) or high affinity to BPAF (BSA/trypsin-ANPs). However, the trypsin-PNPs/CNPs inhibited the transport of BPAF due to their weak mobility and adsorption with BPAF. The results provide new insights into the role of varying surface modifications on NPs in the vertical cotransport of NPs and associated contaminants in unsaturated hyporheic zone.

Robust Activity and Stability of P-Doped Fe-Carbon Composites Derived from MOF for Bromate Reduction.

Iron-based materials are effective for the reductive removal of the disinfection byproduct bromate in water, while the construction of highly stable and active Fe-based materials with wide pH adaptability remains greatly challenging. In this study, highly dispersed iron phosphide-decorated porous carbon (Fe2P(x)@P(z)NC-y) was prepared via the thermal hydrolysis of Fe@ZIF-8, followed by phosphorus doping (P-doping) and pyrolysis. The reduction performances of Fe2P(x)@P(z)NC-y for bromate reduction were evaluated. Characterization results showed that the Fe, P, and N elements were homogeneously distributed in the carbonaceous matrix. P-doping regulated the coordination environment of Fe atoms and enhanced the conductivity, porosity, and wettability of the carbonaceous matrix. As a result, Fe2P(x)@P(1.0)NC-950 exhibited enhanced reactivity and stability with an intrinsic reduction kinetic constant (kint) 1.53-1.85 times higher than Fe(x)@NC-950 without P-doping. Furthermore, Fe2P(0.125)@P(1.0)NC-950 displayed superior reduction efficiency and prominent stability with very low Fe leaching (4.53-22.98 µg L-1) in a wide pH range of 4.0-10.0. The used Fe2P(0.125)@P(1.0)NC-950 could be regenerated by phosphating, and the regenerated Fe2P(0.125)@P(1.0)NC-950 maintained 85% of its primary reduction activity after five reuse cycles. The study clearly demonstrates that Fe2P-decorated porous carbon can be applied as a robust and stable Fe-based material in aqueous bromate reduction.

Multiple-Emitting Luminescent Metal-Organic Framework as an Array-on-a-MOF for Rapid Screening and Discrimination of Nitroaromatics.

Fluorescence array technologies have attracted great interest in the sensing field because of their high sensitivity, low cost, and capability of multitarget detection. However, traditional array sensing relies on multiple independent sensors and thus often requires time-consuming and laborious measurement processes. Herein, we introduce a novel fluorescence array strategy of the array-on-a-metal-organic framework (MOF), which integrates multiple array elements into a single MOF matrix to achieve facile sensing and discrimination of multiple target analytes. As a proof-of-concept system, we constructed a luminescent MOF containing three different emitting channels, including a lanthanide ion (europium/Eu3+, red emission), a fluorescent dye (7-hydroxycoumarin-4-acetic acid/HCAA, blue emission), and the MOF itself (UiO-66-type MOF, blue-violet emission). Five structurally similar nitroaromatic compounds (NACs) were chosen as the targets. All three channels of the array-on-a-MOF displayed rapid and stable fluorescence quenching responses to NACs (response equilibrium achieved within 30 s). Different responses were generated for each channel against each NAC due to the various quenching mechanisms, including photoinduced electron transfer, energy competition, and the inner filter effect. Using linear discriminant analysis, the array-on-a-MOF successfully distinguished the five NACs and their mixtures at varying concentrations and demonstrated good sensitivity to quantify individual NACs (detect limit below the advisory concentration in drinking water). Moreover, the array also showed feasibility in the sensing and discrimination of multiple NACs in real water samples. The proposed "array-on-a-MOF" strategy simplifies multitarget discrimination procedures and holds great promise for various sensing applications.

Efficient Catalytic Oxidation of Ethylene at 0 °C on an in Situ Carbon Modified Pt Catalyst Supported on SBA-15.

The design of efficient catalysts for catalytic ethylene (C2H4) oxidation is of crucial importance for extending the shelf life of fruits and vegetables. Herein, a carbon modified SBA-15 supported Pt catalyst (Pt/CSBA-15) was prepared in situ by a facile solid phase grinding-infiltration-inert atmosphere calcination method. Characterization results reveal that in the Pt/CSBA-15 catalysts thin carbon layers are successfully formed in the hexagonal pores of SBA-15. Additionally, Pt particles are well dispersed in the channels of SBA-15, and Pt/CSBA-15 has a smaller Pt particle size than the catalyst without carbon modification (i.e., Pt/SBA-15). O2 is more feasibly adsorbed and activated on small-sized Pt particles, and in situ formed carbon species enhance the hydrophobicity of catalysts. As a result, both 3Pt/CSBA-15 and 5Pt/CSBA-15 are able to maintain 100% conversion of 50 ppm of C2H4 for more than 7 h at 0 °C. 3Pt/CSBA-15 even achieves 81.5% C2H4 conversion and 71.6% CO2 yield after 20 h, exhibiting much more prominent catalytic performances than 3Pt/SBA-15. DFT calculations and in situ FTIR measurements confirm that small-sized Pt particles possess strong O2 affinity to promote O2 adsorption, and in situ formed hydrophobic carbon layers efficiently suppress competitive H2O adsorption. Such a unique one-step catalyst preparation method for regulating the size of metal particles and the hydrophobicity of catalysts can be perfectly utilized to develop simple and efficient hydrophobic catalysts applied in low-temperature oxidation of C2H4.

Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon.

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 ± 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.

Ni12P5 Confined in Mesoporous SiO2 with Near-Unity CO Selectivity and Enhanced Catalytic Activity for CO2 Hydrogenation.

CO2 hydrogenation via the reverse water gas shift (RWGS) reaction is a promising strategy for CO2 utilization while constructing Ni-based catalysts with high catalytic activity and perfect CO selectivity remains a great challenging. Here, we demonstrate that the product selectivity for CO2 hydrogenation can be significantly tuned from CH4 to CO by phosphating of SiO2-supported Ni catalysts due to the geometric effect. Interestingly, nickel phosphide catalysts with different crystalline phases (Ni12P5 and Ni2P) differ sharply in CO2 conversion, and Ni12P5 is remarkably more active. Furthermore, we developed a facile strategy to confine small Ni12P5 nanoparticles in mesoporous SiO2 channels (Ni12P5@SBA-15). Enhanced activity is exhibited on Ni12P5@SBA-15, ascribed to the highly effective confinement effect. The in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations unveil that catalytic CO2 hydrogenation follows a direct CO2 dissociation route with adsorbed CO as the key intermediate. Notably, strong multibonded CO (threefold and bridge-bonded CO) is feasibly formed on the Ni catalyst accounting for CH4 as the dominant product whereas only weak linearly bonded CO exists on nickel phosphide catalysts resulting in almost 100% CO selectivity. The present results indicate that Ni12P5@SBA-15 combining the geometric effect and the confinement effect can achieve near-unity CO selectivity and enhanced activity for CO2 hydrogenation.

Hierarchical porous loofah-like carbon with sulfhydryl functionality for electrochemical detection of trace mercury in water.

Mercury is a common contaminant found in natural waters, which is highly toxic to human health. Thus, the facile and reliable monitoring of mercury in waters is of great significance. In this study, we fabricated a novel loofah-like hierarchical porous carbon with sulfhydryl functionality (S-LHC), and applied it as an ultrasensitive sensor for the electrochemical detection of mercury in water. The S-LHC was prepared through the direct pyrolysis of a triazole-rich metal-organic framework (MOF), followed by chemical modification using thioglycolic acid. The highly conductive N-doped carbon framework of S-LHC facilitated the electron transfer in mercury electrochemical sensing. Meanwhile, the open hierarchical pore structure and abundant sulfhydryl groups allowed the fast diffusion and effective enrichment of mercury ions. Consequently, the S-LHC sensor exhibited an exceptionally high sensitivity for mercury ions, with the mercury detection limit (0.36 nM) orders of magnitude lower than the regulated values in drinking water (typically 10∼30 nM). The constructed sensor also afforded good anti-interference ability and excellent stability for long-term detection of mercury in a variety of complex real water samples. The present study provides not only a facile method for mercury detection, but also a new idea for the construction of highly sensitive electrochemical sensors.

Amino-Functionalized Hierarchical Porous Carbon Derived from Zeolitic Imidazolate Frameworks for Ultrasensitive Electrochemical Sensing of Heavy Metals in Water.

Electrochemical sensing provides a feasible avenue to monitor heavy metal ions (HMIs) in water, whereas the construction of highly sensitive and selective sensors remains challenging. Herein, we fabricated a novel amino-functionalized hierarchical porous carbon by the template-engaged method using ZIF-8 as the precursor and polystyrene sphere as the template, followed by carbonization and controllable chemical grafting of amino groups for efficient electrochemical detection of HMIs in water. The amino-functionalized hierarchical porous carbon features an ultrathin carbon framework with a high graphitization degree, excellent conductivity, unique macro-, meso-, and microporous architecture, and rich amino groups. As a result, the sensor exhibits prominent electrochemical performance with significantly low limits of detection for individual HMIs (i.e., 0.93 nM for Pb2+, 2.9 nM for Cu2+, and 1.2 nM for Hg2+) and simultaneous detection of HMIs (i.e., 0.62 nM for Pb2+, 1.8 nM for Cu2+, and 0.85 nM for Hg2+), which are superior to most reported sensors in the literature. Moreover, the sensor displays excellent anti-interference ability, repeatability, and stability for HMI detection in actual water samples.

A nanozyme-like colorimetric sensing strategy based on persulfate activation on Co-based metal-organic frameworks.

A nanozyme-like colorimetric sensing strategy based on persulfate activation on Co-based metal-organic frameworks is developed for biomolecule detection in solution and on paper strips. By switching from H2O2 activation on nanozymes to catalytic persulfate activation, this general strategy provides higher sensitivity, faster speed, and wider application ranges for detection.

ZnO Nanorod-Immobilized Pt Single-Atoms as an Ultrasensitive Sensor for Triethylamine Detection.

Triethylamine (TEA) is a flammable and highly toxic gas, and the fast, accurate, and sensitive detection of gas TEA remains greatly challenging. Herein, we report a ZnO nanorod anchored with a single-atom Pt catalyst (Pt1/ZnO) as a gas sensor for TEA detection. The sensor shows high selectivity and high response to gas TEA with a response value of 4170 at 200 °C, which is 92 times higher than that of pure ZnO. Moreover, the Pt1/ZnO sensor has very short response and recovery times of only 34 and 76 s, respectively, and also has a high response to ppb-level TEA gas (100 ppb-21.6). The gas-sensing enhancement mechanism of the Pt1/ZnO sensor to gas TEA was systematically investigated using band structure analysis, in situ diffuse reflectance infrared Fourier transformation spectroscopy, and density functional theory calculations. The results show that the oxygen vacancies on Pt1/ZnO can effectively activate the adsorbed oxygen. Moreover, chemical bonds can be formed between Pt single atoms and N atoms in TEA to achieve effective adsorption and activation of TEA molecules, facilitating the reaction between TEA and the adsorbed oxygen on Pt1/ZnO, and thereby obtaining high gas-sensing performance. This work highlights the crucial role of Pt single-atom in improving the sensing performance for gas TEA detection, paving the way for developing more advanced gas sensors.

Effective catalytic hydrodechlorination removal of chloroanisole odorants in water using palladium catalyst confined in zeolite Y.

Chloroanisoles is a class of odorous pollutants commonly identified in drinking water. In the present study, we confined noble metal palladium (Pd) in the micropores of zeolite Y (ie-Pd@Y) using an ion exchange method, and applied it for the catalytic hydrodechlorination removal of chloroanisoles (represented by 2,4,6-trichloroanisole/TCA) in water. Pd supported on zeolite Y surface (im-Pd/Y, prepared by conventional impregnation method) was used as the benchmarking catalyst. The characterization results revealed that ie-Pd@Y had smaller Pd particle size and higher Pdn+/Pd0 ratio than im-Pd/Y. The catalytic hydrodechlorination of TCA followed a concerted dechlorination pathway and the Langmuir-Hinshelwood model. The ie-Pd@Y catalysts with different Pd loadings exhibit excellent catalytic activities with more than 95% of TCA removed within 30 min, which is far superior to the im-Pd/Y catalysts (27-70%). Moreover, due to the confinement effect of zeolite Y, ie-Pd@Y displayed enhanced catalytic stability as compared with im-Pd/Y. The initial activity of ie-Pd@Y was more than 20 times higher than that of im-Pd/Y after five reaction cycles. Additionally, with the assistance of sieving effect, ie-Pd@Y displayed much stronger capability against the interference from dissolved organic matter than im-Pd/Y. The present results demonstrate that the confined catalysts ie-Pd@Y can be applied in liquid phase catalytic hydrogenation to effectively eliminate halogenated odorants in waters.

Mechanism for selective binding of aromatic compounds on oxygen-rich graphene nanosheets based on molecule size/polarity matching.

Selective binding of organic compounds is the cornerstone of many important industrial and pharmaceutical applications. Here, we achieved highly selective binding of aromatic compounds in aqueous solution and gas phase by oxygen-enriched graphene oxide (GO) nanosheets via a previously unknown mechanism based on size matching and polarity matching. Oxygen-containing functional groups (predominately epoxies and hydroxyls) on the nongraphitized aliphatic carbons of the basal plane of GO formed highly polar regions that encompass graphitic regions slightly larger than the benzene ring. This facilitated size match-based interactions between small apolar compounds and the isolated aromatic region of GO, resulting in high binding selectivity relative to larger apolar compounds. The interactions between the functional group(s) of polar aromatics and the epoxy/hydroxyl groups around the isolated aromatic region of GO enhanced binding selectivity relative to similar-sized apolar aromatics. These findings provide opportunities for precision separations and molecular recognition enabled by size/polarity match-based selectivity.

Efficient and reductive removal of bromate using a novel and stable nanoscale zero-valent iron embedded in N-doped carbon derived from metal-organic frameworks.

Nanoscale zero-valent iron (nZVI) has drawn great interest in the remediation of contaminated waters. In this study, we prepared a novel and stable nZVI embedded in N-doped carbon matrix (nZVI@MOF-CN) using a facile direct carbonization method, in which an iron-containing metal-organic framework (MOF) served as both the iron and carbon sources, and melamine as the nitrogen source. The nZVI@MOF-CN composites were used in the removal of bromate in water, which could be effectively reduced by the surface electrons transferred from nZVI to the carbon encapsulation layer due to the Schottky-Mott effect. Doped nitrogen significantly facilitated the reduction of bromate by nZVI, because it enhanced the nZVI dispersion and bromate adsorption, and modulated the carbon matrix conductivity. The bromate reduction activity of nZVI@MOF-CN was more than 50 times higher that of its un-doped counterpart and a commercial nZVI. Moreover, owing to the protection of carbon encapsulation layer, nZVI@MOF-CN exhibited good stability and reusability. The leached concentration of iron ions of nZVI@MOF-CN was less than 5% of the commercial nZVI under the same reaction conditions. Commercial nZVI almost completely lost its bromate reduction activity after use (3% reduction efficiency in the examined time frame), while nZVI@MOF-CN maintained a reduction efficiency of 61%. The nZVI@MOF-CN could be effectively regenerated by hydrogenation reduction. After five reaction-regeneration cycles, nZVI@MOF-CN still achieved a bromate reduction efficiency of approximately 80%. These results suggest that MOF-derived nZVI materials are highly reactive and stable for the reductive removal of pollutants in water.

Efficient inhibition of cyanobacteria M. aeruginosa growth using commercial food-grade fumaric acid.

The control of cyanobacteria blooms is a global challenge. Here, we reported the efficient inhibition of M. aeruginosa by fumaric acid (FA), an intermediate metabolite of the tricarboxylic acid cycle. FA showed strong algicidal activity with an inhibition rate of 90.5% on the 8th day at a dose of 40 mg/L. The presence of FA caused severe membrane damage, as suggested by the fluorescence flow cytometry and morphology analysis. FA inhibited the formation of chlorophyll a, interrupting the photosynthesis system. It also induced oxidative stress in cells. Principal component analysis of the indicators suggested that the FA-treated sample had a significantly different inhibitory pattern than the acid-treated sample. Thus, the inhibitory effect was not solely caused by the pH effect. Untargeted metabolomic analysis revealed that 31 metabolites were differentially expressed in response to FA stress, which were mainly involved in the metabolite processes and the membranes. A commercial food-grade FA was able to inhibit the growth of M. aeruginosa similar to the analytical-grade FA. Our results suggest that FA can be potentially an efficient and low-risk chemical for inhibiting M. aeruginosa growth, which may find future applications in cyanobacteria bloom control.

Comparing Photoactivities of Dissolved Organic Matter Released from Rice Straw-Pyrolyzed Biochar and Composted Rice Straw.

Here, we systematically compared the photoactivity and photobleaching behavior between dissolved black carbon (DBC) from rice straw biochar and leached dissolved organic carbon (LDOC) from rice straw compost using complementary techniques. The Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis showed that DBC was dominated by polycyclic aromatic (55.1%) and tannin-like molecules (24.1%), while LDOC was dominated by lignin-like (58.9%) and tannin-like molecules (19.7%). Under simulated sunlight conditions, DBC had much higher apparent quantum yields for 3DOM* and 1O2 but much lower apparent quantum yields for •OH than LDOC. After a 168 h irradiation, the total number of LDOC formulas identified by FT-ICR MS decreased by 40.1% with concurrent increases in O/C and H/C ratios and also decreases in double bond equivalence minus oxygen (DBE - O) and average molecular weight identified by gel permeation chromatography. However, despite the large decreases in UVA254 and DOC, the total number of DBC formulas decreased only by 12.0% with nearly unchanged O/C ratio, DBE - O values, molecular weight distribution, and benzenepolycarboxylic aromatic condensation (BACon) index regardless of the decreased percentage of condensed aromatic carbon (ConAC %). Compared with LDOC, the photolysis of DBC was much less oxidative and destructive mainly via breakup of a small portion of the highly condensed aromatic rings, probably accompanied by photodecarboxylation.

Rapid detoxification of Microcystin-LR by selective catalytic hydrogenation of the Adda moiety using TiO2-supported Pd catalysts.

The hepatotoxicity of Microcystin-LR (MC-LR) is mainly caused by its Adda moiety. In this study, we used TiO2-supported Pd catalysts to selectively hydrogenate the CC bonds in the Adda moiety, achieving rapid detoxification of MC-LR in water under ambient conditions. MC-LR was removed within 5 min by catalytic hydrogenation on Pd(1.0)/TiO2 with a catalyst dosage normalized rate constant of 1.3 × 10-2 L mgcat-1 min-1, significantly more efficient than other catalytic treatment methods. The reactions proceeded in a highly selective manner towards catalytic hydrogenation at the CC bond of the Mdha moiety and subsequently the conjugated double bond of the Adda moiety, yielding two intermediates and one final product. Upon catalytic hydrogenation for 30 min on Pd(0.07)/TiO2, the toxicity of MC-LR (assessed by protein phosphatase 2A activity assay) drastically decreased by 90.8%, demonstrating effective detoxification. The influence of catalyst support, Pd content, initial MC-LR concentration, reaction pH, and catalytic stability were examined. Surface adsorption and the cationic Pd played a crucial role in the reaction kinetics. Our results suggest that catalytic hydrogenation is a highly effective and safe strategy for detoxifying MC-LR by selective reactions.

Screening and Discrimination of Perfluoroalkyl Substances in Aqueous Solution Using a Luminescent Metal-Organic Framework Sensor Array.

The extensive production and large-scale use of perfluoroalkyl substances (PFASs) have raised their presence in aquatic environments worldwide. Thus, the facile and reliable screening of PFASs in aqueous systems is of great significance. Herein, we designed a novel fluorescent sensor array for the rapid screening and discrimination of multiple PFASs in water. The sensor array comprised three highly stable zirconium porphyrinic luminescent metal-organic frameworks (i.e., PCNs) with different topological structures. The sensing mechanism was based on the static fluorescence quenching of PCNs by PFASs upon their adsorptive interactions. The fluorescence response patterns were characteristic for each PFAS because of their different adsorption affinities toward different PCNs. Through the interpretation of response patterns by statistical methods, the proposed PCN array successfully discriminated six different kinds of PFASs, each PFAS at different concentrations and PFAS mixtures at different molar ratios. The practicability of this array was further verified by effectively discriminating PFASs in two real water samples. Remarkably, the PCN sensors exhibited a very short response time toward PFASs (within 10 s) due to the ordered pore structure allowing fast PFAS diffusion. This study not only provides a facile method for rapid PFAS screening in waters but also broadens the application of luminescent metal-organic frameworks and array techniques in sensing fields.

High-Throughput Method for Natural Organic Matter Hydrophobicity Assessment Using an Ionic Liquid-Based Aqueous Two-Phase System.

Hydrophobicity of natural organic matter (NOM) is one of its fundamental properties that influence the environmental fate of pollutants and the performance of many water treatment unit processes. In this study, a high-throughput method was developed for NOM hydrophobicity measurement based on the phase separation technique in the 96-well format. It measures the partition coefficients of NOM (KATPS,IL) in an ionic liquid (IL)-based aqueous two-phase system (ATPS). The ATPS was made of 1-butyl-3-methylimidazole bromide solution and a salt solution containing potassium phosphate monobasic and potassium phosphate dibasic. The partition of NOM in IL-based ATPS is mainly affected by its hydrophobicity. log KATPS,IL linearly correlated with the commonly used NOM hydrophobicity scales, including (O + N)/C, O/C, and aromatic carbons. KATPS,IL provided a more accurate assessment of NOM hydrophobicity than spectroscopic indices. Furthermore, KATPS,IL can predict the organic carbon-water partition coefficients for hydrophobic organic chemical sorption to NOM based on the two-phase system model. The high-throughput KATPS,IL measurement and the two-phase system model can be applied to real surface water samples. Our results suggest that the proposed high-throughput method has great potential to be applied to monitor NOM hydrophobicity for environmental risk assessment and water treatment purposes.

Prediction of hydrophobic organic compound partition to algal organic matter through the growth cycle of Microcystis aeruginosa.

Algal organic matter (AOM) is an important source for the dissolved organic matter (DOM) pool in aquatic systems, particularly in eutrophic waters. In this study, we reported the dynamic pattern of AOM hydrophobicity during the growth cycle of Microcystis aeruginosa using the partition coefficients of AOM in the aqueous two-phase system (KATPS) as a simple quantitative measure. AOM hydrophobicity had significant and non-monotonic changes during the growth cycle. It increased in the lag and early exponential phases, then decreased in the late exponential and stationary phases, and rebounded in the decline phase. AOM hydrophobicity determined using the resin fractionation, SUVA254, and nuclear magnetic resonance methods shared similar non-monotonic pattern. Nevertheless, the correlations among these indicators were poor. The partition behavior of polycyclic aromatic hydrocarbons and chlorobenzenes to AOM was assessed based the KATPS dataset and the two-phase system (TPS) model. The TPS model showed good prediction power for the partition behavior of AOM with an RMSE of 0.23, suggesting that it was applicable to AOM from Microcystis aeruginosa. Our results indicate that algae activity will influence the overall hydrophobicity of the DOM pool depending on the growth phase, resulting in changes in the bioavailability of hydrophobic organic compounds in aquatic systems.

Efficient Reduction of Selenite to Elemental Selenium by Liquid-Phase Catalytic Hydrogenation Using a Highly Stable Multiwalled Carbon Nanotube-Supported Pt Catalyst Coated by N-Doped Carbon.

A stable catalyst, Pt/carbon nanotube (CNT) coated with N-doped carbon (Pt/CNT@CN), was designed to reduce selenite (Se(IV)) in water to elemental selenium by liquid-phase catalytic hydrogenation. Commercial Pt/C, pristine Pt/CNT, and carbon-coated Pt/CNT (Pt/CNT@C) were used for benchmarking. The Pt particles in Pt/CNT@CN were completely embedded beneath the coatings to minimize leaching and were not easily accessible to Se(IV). However, Schottky-Mott-type metal-carbon junctions that activate H2 were formed on the coated catalyst, facilitating effective reduction of Se(IV). The initial activity of Pt/CNT@CN (900.5 mg L-1 gcat-1 h-1) was two times higher than that of commercial Pt/C (448.6 mg L-1 gcat-1 h-1). The commercial Pt/C and uncoated Pt/CNT lost their initial activities during reuse and were almost inactive after 10 cycles due to significant Pt leaching (>90%) during the reaction and acid-washing regeneration processes. Pt/CNT@CN maintained 33% of the initial activity after the first cycle and stabilized over the following 9 cycles due to effective protection of Pt particles by carbon coatings. After 10 cycles, the activity of Pt/CNT@CN was over 20 times higher than that of Pt/C and uncoated Pt/CNT. Overall, catalytic hydrogenation using carbon-coated-supported Pt catalysts is an effective and promising approach to remove Se(IV) in water.