Frank-Kasper phases in charge transfer complexes enable tunable photoelectronic properties.

Understanding how particles pack in space and the mechanisms underlying symmetry selection across soft matter is challenging. The Frank-Kasper (F-K) phase of complex spherical packing is amongst the most fascinating phases; however, it has not been observed in discotic liquid crystals until now. Herein, we report the first observation of F-K phases of charge transfer complexes (CTCs) obtained from triphenylene derivatives as donors and 2,4,7-trinitro-9-fluorenone as the acceptor. The CTCs were characterized using experimental and theoretical calculations, indicating that the F-K A15 cubic lattice possesses a unit cell containing 8 sphere-like supramolecules, each of which was self-assembled from 3 CTC complexes. The lattice constant was only 3.2 nm, which is by far the smallest for the A15 phase. Interestingly, the supramolecular assembly can be regarded as the molecular column splitting into isolated spherical fragments, impeding charge transfer and turning it into one insulator. This provides a simple and effective method for preparing asymmetric complex compounds for the design of unconventional self-assembled nanostructures.

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.

Directional Assembly of Large-Area Silica Nanorod Film Using the Electric-Field-Assisted Capillary Channel Method.

The self-assembly of colloidal particles, especially colloidal particles with anisotropic geometry, is important for applications in the construction of many functional materials. Compared with the self-assembly of colloidal particles with isotropic geometries, not only does the geometric orientation among neighboring anisotropic particles need to be considered for the reduction of Gibbs free energy, the orientations of the particles are best to be externally influenced. Because of this, the preparation of assembled nanorod arrays with uniform alignment across a large area is still a significant challenge. In this work, an electric-field-assisted capillary channel method is reported, using an external electric field to influence the orientation of silica nanorods or FeOOH ellipsoids during assembly. By application of an external electric field, the alignment of the nanorods is effectively controlled. The capillary channel method provides continuous replenishment of a colloidal solution containing nanorods or spheres for assembly of large-area films. The area of the formed films was influenced by the assembly temperature, channel width, colloidal solution concentration, and solvent surface tension. The competition between the thermal Brownian motion and torque generated by the external electric field impacted the nanorod array quality in the film. While increasing the intensity of the electric field improved nanorod alignment, applying a potential greater than 6 V also produced a heating effect, negatively affecting the quality of the nanorod arrays. The nematic order parameter S which characterizes the degree of alignment of FeOOH ellipsoids with smaller length is significantly lower than the one for silica nanorods due to the higher critical field strength and the increased susceptibility to the effects of thermal motion. The assembly of silica nanorods at 35 °C under an effective potential of 4-6 V provides a compromise between achieving uniform nanorod orientation and maximizing the coverage area of the colloidal film.

New Mechanism via Dichlorocarbene Intermediate for Activated Carbon-Mediated Reductive Dechlorination of Carbon Tetrachloride by Sulfide in Aqueous Solutions.

Although activated carbon (AC) is widely used as an adsorbent and barrier for contaminated sediment remediation, little attention has been paid to its mediation effects on reductive dechlorination of chlorinated solvents by commonly presenting sulfide. Here, we reported that highly porous, graphitized AC (250 mg L-1) suspended in deoxygenated aqueous solutions could increase the pseudo-first-order rate constant of sulfide-induced dechlorination of carbon tetrachloride (CCl4) by more than 1 order of magnitude. Carbon disulfide (CS2) was the only main product, with no production of chloroform or dichloromethane. The minimum promotion of CCl4 reduction observed with electro-conductive but nonporous graphite and a microporous but electro-insulative resin (XAD-4) indicates that graphitic carbons and micropores both play key roles in AC-mediated dechlorination of CCl4 by sulfide. The detection of dichlorocarbene (:CCl2) by free radical trapping experiments combined with the high suitability of the Langmuir-Hinshelwood model led us to propose a new mediation mechanism: CCl4 molecules adsorbed within the deep regions of AC micropores formed by graphitic carbons accept two electrons transferred from sulfide to form :CCl2, which is impeded from hydrolysis and hydrogenolysis by the hydrophobic micropore and further reacts with sulfide to generate CS2. Consistently, the production of :CCl2 was very low when AC was replaced with graphite or XAD-4. The proposed mechanism was further validated by the enhanced mediation effects of another two carbonaceous materials (template-synthesized mesoporous carbon and covalent triazine-based framework) that are electro-conductive and have well-developed micropore structures. These findings highlight the importance of pore properties of carbonaceous materials as mediators or catalysts for reductive dechlorination reactions and shed light on the development of coupled adsorption-reaction systems for remediation.

Effects of different external factors on urban roadside plants for the reduction of airborne fine particulate matters.

With the progress of urbanization and industrialization in China, the consumption of fossil fuels blows up. The burning of fossil fuels releases large amounts of particulate matter, leads to smog, and the air quality is gradually getting worsen. Previous studies have shown that vegetation can effectively reduce airborne particles with different size fractions. And large amounts of previous studies pointed to the adsorption ability of urban forest for particles larger than 2.5 µm. The capacity of roadside plants for the capture of fine particles, especially for those smaller than 2.5 µm has been rarely reported. In this study, five external factors including leaf orientation, leaf height, planting location, planting form, and pollution concentration were tested to evaluate their impact on the dust retention capacity of different roadside plants. The results indicate that significant interspecies was found between tested plant species, and with the change of different external factors, the capturing capacity for the same roadside plants varied. The change of leaf orientation has limited effects on the amount of captured fine particles for the tested plants. While, the amount of captured particulate matter by leaves was inversely proportional to its growth height. Plants locating in the central of the road showed significantly higher capturing capacity than they, when they was set alongside the road. The total amount of captured fine particle by Ligustrum japonicum locating in the central green belt of road was about 5 times higher than it when it was planted in the green belt alongside the road. In addition, the correlation between the capturing capacity of roadside plants and its distance to the street curb was found to be negative.

Plants have been widely accepted as an environmentally friendly air particulate filter that can effectively remove fine particulate matter which can be harmful to humans. By analyzing the dust retention of plant leaves, this paper discussed the influence of different factors such as traffic pressure, planting position, and leaf orientation on the capture ability of roadside plants, in addition, we investigated particulate matter with a smaller size (PM_0.22). The mainly objective of this study is to investigate the factors affecting the dust retention efficiency of roadside plants and roadside plants as phytoremediation to improve city air quality which consists with the purpose of the journal.

Threshold Concentrations of Silver Ions Exist for the Sunlight-Induced Formation of Silver Nanoparticles in the Presence of Natural Organic Matter.

Sunlight-induced photoformation of silver nanoparticles (nAg), mediated by natural organic matter (NOM), is significantly affected by the concentration of Ag(I) and chloride. The initial photoformation rates of nAg in Suwannee River humic acid (SRHA) and Suwannee River natural organic matter (SRNOM) solutions were examined under simulated sunlight irradiation. A critical induction concentration (CIC) of Ag(I) (10 mg/L for SRHA and 5 mg/L for SRNOM, respectively) was observed, below which the nAg formation was minimal. The threshold is attributed to the interplay of reduction and oxidation reactions mediated by NOM, reflecting the need to achieve sufficiently fast growth of silver clusters to outcompete oxidative dissolution. The CIC can be reduced by scavenging oxidative radicals or be increased by promoting singlet oxygen and hydrogen peroxide generation. The presence of chloride effectively reduced the CIC by forming AgCl, which facilitates reduction reactions and provides deposition surfaces. SRNOM is more efficient in mediating photoformation of nAg than SRHA, owing to their differed phototransient generation. These results highlight prerequisites for the photoformation of nAg mediated by NOM, in which the photochemistry and solution chemistry are both important.

Aggregation Behavior of Dissolved Black Carbon: Implications for Vertical Mass Flux and Fractionation in Aquatic Systems.

The fluvial export of dissolved black carbon (DBC) is a major land-ocean flux in the global black carbon cycle, affecting the size of refractory carbon pool in the oceans. The aggregation behavior of DBC is a significant determinant of its transport and vertical mass flux. In this study, the aggregation kinetics and interaction energy of DBC leached from biochar were investigated. DBC was mainly stabilized by hydration force and underwent structural compacting in divalent cation solutions. Na+ and Mg2+ had limited impact on the colloidal stability of DBC due to the strong hydration of these cations. Ca2+ and Ba2+ readily destabilized DBC by forming inner-sphere complexes, reducing its hydrophilicity. Consistently, charge reversal of DBC was observed with high concentrations of Ca2+ and Ba2+. Simulated sunlight exposure led to photo-oxidation of DBC, increasing its colloidal stability. DBC behaved nonconservatively in laboratory mixing experiments using estuary water samples due to aggregation/sedimentation; while model aquatic humic acid behaved conservatively. Our results infer that there is a vertical mass flux of DBC and possible fractionation from the dissolved organic matter pool in the fluvial and estuarine systems, which have been overlooked in efforts to determine global carbon budgets and associated climate change implications.

Comparing molecular signatures of dissolved organic matter (DOM) in four large freshwater lakes differing in hydrological connectivity to the Changjiang River.

Freshwater lakes serve as active conduits for processing terrestrial dissolved organic matter (DOM), playing a crucial role in global carbon cycle. Little attention has been paid to how hydrological connectivity to a large river would affect the molecular signatures of DOM in lakes. Here, we systematically characterized and compared the molecular signatures of DOM in surface waters of four large freshwater lakes in the middle and lower Changjiang River basin that are directly connected to the river (Lake Dongting and Lake Poyang, referred to as Lakeconnected) or indirectly connected to the river (Lake Chao and Lake Tai, referred to as Lakenonconnected). The DOM in Lakeconnected was found to have similar total organic carbon (TOC)-normalized contents and characteristics of lignin phenols to the DOM in surface waters from the upstream Changjiang river, indicating allochthonous/terrestrial sources from riverine inputs. As indicated by the UV-vis and fluorescence analyses, the DOM in Lakeconnected overall had higher aromaticity and larger average molecular weight as well as stronger allochthonous feature compared to the DOM in Lakenonconnected. Consistently, the FT-ICR MS analysis revealed that the DOM in Lakeconnected had higher molecular diversity, higher unsaturation degree, and larger proportions of highly aromatic compounds. In contrast, the DOM in Lakenonconnected had larger proportions of lipids and peptide-like structures, but lower proportions of aromatic compounds, which could be ascribed to the enhanced autochthonous production and photodegradation due to pollution and eutrophication as well as longer water residence time. The results highlight the strong impacts of the hydrological connectivity to a large river on the molecular signatures of lake DOM. CAPSULE: The hydrological connectivity of the lakes to the Changjiang River has strong impacts on the molecular signatures of lake DOM.

[Clinical study of constructing nomogram model based on multi-dimensional clinical indicators to predict prognosis of knee osteoarthritis].

OBJECTIVE: To analyze the factors affecting the prognosis of patients with knee osteoarthritis, and to construct a nomogram prediction model in conjunction with multi-dimensional clinical indicators. METHODS: The clinical data of 234 patients with knee osteoarthritis who were treated in our hospital from January 2015 to June 2021 were retrospectively analyzed, including 126 males and 108 females；age more than 60 years old for 135 cases, age less than 60 years old for 99 cases. Lysholm knee function score was used to evaluate the prognosis of the patients, and the patients were divided into good prognosis group for 155 patients and poor prognosis group for 79 patients according to the prognosis. The clinical data of the subjects in the experimental cohort were analyzed by single factor and multiple factors. The patients were divided into experimental cohort and verification cohort, the results of the multiple factor analysis were visualized to obtain a nomogram prediction model, the receiver operating characteristic curve（ROC）, calibration curve and decision curve were used to evaluate the model's discrimination, accuracy and clinical benefit rate. RESULTS: The results of multivariate analysis showed that smoking, pre-treatment K-L grades of Ⅲ to Ⅳ, and high levels of interleukin 6 （IL-6） and matrix metallo proteinase-3 （MMP-3） were risk factors for the prognosis of patients with knee osteoarthritis. ROC test results showed that the area under the curve of the nomogram model in the experimental cohort and validation cohort was 0.806[95%CI（0.742, 0.866）] and 0.786[（95%CI（0.678, 0.893）], respectively. The results of the calibration curve showed that the Brier values of the experimental cohort and verification cohort were 0.151 points and 0.134 points, respectively. When the threshold probability value in the decision curve was set to 31%, the clinical benefit rates of the experimental cohort and validation cohort were 51% and 56%, respectively. CONCLUSION: The prognostic model of patients with knee osteoarthritis constructed based on multi-dimensional clinical data has both theoretical and practical significance, and can provide a reference for taking targeted measures to improve the prognosis of patients.

Effects of urbanization on woody plant phylogenetic diversity and its associations with landscape features in the high latitude northern hemisphere region, Northeast China.

Urbanization is one of the primary drivers of terrestrial modification, with marked biological homogenization worldwide but relatively poor knowledge of woody phylogenetic diversity. Here, we investigated 943 plots, about 93,000 woody plants from 130 species in Northeast China, and calculated six phylogenetic diversity indexes, and urbanization landscape metrics; the responses of phylogenetic diversity to urbanization and its coupling relationship with landscape features were explored at 25 km × 25 km, 50 km × 50 km and 75 km × 75 km grid scales. We found that urbanization had enhanced the evolutionary distinctiveness of woody plants, characterizing as increasing Faith phylogenetic diversity (FPD) and their mean pairwise distance (MPD) while decreasing the mean nearest taxon distance (MNTD); these trends were independent of landscape scales and gymnosperm inclusion or not. As indicated by increasing SesMPD (Standardized MPD), the dominant role of community assemblage changed from environmental filtering in low urbanization intensity (UI) to competitive exclusion in high UI regions. Artificial surface area (ASA) and its percentage, SHAPE_F (Shape index of forest), and PD_F (Patch density of forest) had a threshold effect on phylogenetic diversity. ASA%, GDP (gross domestic product), and population density were the most potent predictors for the variations of phylogenetic diversity, and GDP contributed the most (42.9%). A higher GDP accompanied a higher FPD, SesPD (Standardized FPD), and SesMNTD (Standardized MNTD); higher PD_F and lower SHAPE_F were associated with higher MNTD, MPD, and SesMPD. In conclusion, urbanization strongly modifies woody plant phylogenetic diversity. Identifying the threshold effects and significant factors for phylogenetic variations allows biodiversity assessment and conservation through proper landscape configuration under the urbanization context.

Time to Occurrence of Phlebitis After Continuous Infusion of Total Nutrient Admixture Through Peripheral Veins: An Experimental Animal Study.

OBJECTIVE: To study the limit time of phlebitis caused by continuous infusion of KabivenTM Pl and TNA (KabivenTM Pl+ alanyl glutamine + potassium aspartate) through a peripheral vein, and to provide a reference for clinical formulation of preventive measures for phlebitis. METHODS: White rabbits (n = 72) were randomly divided into three groups: group A (Normal saline), group B (Kabiven™ Pl), and group C (TNA). Blood was collected from the ear margin vein before administration and after three hours, four hours, five hours, and six hours of administration. CRP and TNF-ɑ were measured by enzyme-linked immunosorbent assay. Hematoxylin and eosin staining and immunohistochemical staining were performed on tissue samples taken from the insertion point of the indwelling needle, the tip of the indwelling needle, and 1 cm from the tip of the indwelling needle, closer to the heart, to analyze early pathological changes in blood vessels. RESULTS: (1) There were no visible inflammatory symptoms in groups A, B, or C within 6 hours. (2) Four hours after starting intravenous administration, the levels of inflammatory markers in groups B and C were higher than in group A, and (3) the degree of inflammatory cell infiltration in groups B and C was more severe than in group A. (4) In all groups, the inflammatory reaction at the tip of the indwelling needle was more severe than at the other two sites. CONCLUSION: When the emulsions TNA and Kabiven™ Pl are infused through a peripheral vein, (1) four hours may be considered as the maximum time for continuous intravenous infusion in the same vein before inflammatory changes become evident, and (2) systematic assessment of the tip of the indwelling needle should be considered for inclusion in the nursing plan for phlebitis monitorings.

Surface quinone-induced formation of aqueous reactive sulfur species controls pine wood biochar-mediated reductive dechlorination of hexachloroethane by sulfide.

Understanding the mechanisms controlling the redox transformation of organic contaminants mediated by biochar is of great significance for application of biochar in remediation of contaminated soils and sediments. Here we investigated the mediation effect of a pine wood-derived biochar (P-char) in comparison with multiwalled carbon nanotubes (MCNTs) and graphite on the reductive dechlorination of hexachloroethane by sulfide. Upon normalization of the mediator's surface area, the reduction rate of hexachloroethane follows an order of P-char < MCNTs < graphite. Aqueous polysulfides and polysulfide free radicals were readily produced by reacting sulfide only with P-char, and the supernatant separated from the reaction system could account for 83.4% of the pseudo-kinetic rate constant of hexachloroethane mediated by P-char. In contrast, MCNTs and graphite had weak abilities to produce reactive sulfur species, and the supernatant exhibited very low reduction capability (<20.7%) of hexachloroethane. Electron paramagnetic resonance (EPR) analysis demonstrated that the surface quinone moieties on P-char induced the formation of polysulfides and polysulfide free radicals from sulfide by serving as one-electron acceptors. Consistently, polysulfides prepared by reacting elemental sulfur with sulfide showed much stronger reducing capability compared to sulfide. Thus, the mediation effect of P-char was dominantly attributed to the surface quinone-induced formation of reactive reducing sulfur species, whereas the mediation effect of MCNTs and graphite mainly stemmed from the enhanced electron transfer by the graphitized carbon. These results showed for the first time that surface quinone-induced formation of aqueous reactive sulfur species could control biochar-mediated reductive dechlorination of chloroorganic contaminants by sulfides.

Mechanisms for sulfide-induced nitrobenzene reduction mediated by a variety of different carbonaceous materials: Graphitized carbon-facilitated electron transfer versus quinone-facilitated formation of reactive sulfur species.

Although it has long been known that carbonaceous materials (CMs) can facilitate the reduction of organic contaminants by sulfide, the underlying mechanisms and controlling factors, particularly the surface property dependence, are not well understood. Here, sulfide-induced nitrobenzene reduction was explored as a model reaction to compare the mediation efficiency of a variety of CMs, including rice straw-derived black carbon (R-BC) and pine wood-derived black carbon (P-BC), a commercial activated carbon (AC), multi-walled carbon nanotube (MCNT), and graphite. Given the same load (250 mg L-1 ), the observed pseudo-first-order rate constant (kobs ) of nitrobenzene reduction was ordered as AC > R-BC > MCNT > P-BC > graphite. The surface area-normalized rate constant (kSN ) was ordered as R-BC > graphite > MCNT > AC > P-BC. Neither the kobs nor the kSN followed the order of mediator's electron conductivity (graphite > MCNT > AC > P-BC > R-BC). For the low-graphitized R-BC and P-BC, increasing surface oxygen content by HNO3 oxidation enhanced nitrobenzene reduction, whereas decreasing the content by NaBH4 reduction impeded the reaction. Opposite trends were observed with the high-graphitized AC, MCNT, and graphite. The quinone moieties of low-graphitized CMs were found to facilitate nitrobenzene reduction by serving as one-electron acceptors to generate reactive reducing sulfur species (polysulfides and polysulfide free radicals) from sulfide. In contrast, the surface oxygen groups of high-graphitized CMs suppressed the reaction by lowering the electron conductivity. These results demonstrate that the types of CMs and their surface chemistry properties are key determinants in mediating redox transformation of organic contaminants.

A significant correlation between kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances.

Dissolved humic substances (DHS) are ubiquitous in surface and subsurface aquatic environments and greatly affect the redox transformation of organic contaminants as reactants and/or electron transfer mediators. However, little is known about the quantitative relationship between the mediation efficiency of DHS and the physicochemical properties of DHS. Using sulfide-induced nitrobenzene reduction as a model system, we measured the reduction rate of nitrobenzene in the presence of 12 different DHS (20 mgC·L-1), including 4 commercial humic substances (Suwannee River humic and fulvic acids and Pahokee Peat humic and fulvic acids) and 8 soil humic substances collected as leachates from a wide variety of soils. In addition to the UV-vis absorption and fluorescence spectra, the electron donating/accepting capacities (EDC/EAC) of the tested DHS were measured using an electrochemical approach. A significant linear correlation (r = 0.99, P < .0001) was observed between the observed pseudo-first-order rate constant (kobs) of nitrobenzene reduction and the sum of EDC and EAC which is defined as electron transfer capacity (ETC) of DHS. A relatively good positive correlation (r = 0.69, P < .2) was shown between the kobs and the specific UV-absorbance at 254 nm (SUVA254), whereas no good correlation was shown between the kobs and the fluorescence of the C1-C4 components identified by the excitation emission matrices and parallel factor (EEM-PARAFAC) analysis. This study provides a new framework for accurate prediction of the capability of DHS in mediating the redox transformation of organic contaminants. CAPSULE: A significant linear correlation exists between the kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances.

Sulfide-induced reduction of nitrobenzene mediated by different size fractions of rice straw-derived black carbon: A key role played by reactive polysulfide species.

Here we investigated the mediation efficiency of different size fractions of rice straw-derived black carbon (BC) using sulfide-induced nitrobenzene reduction as a model system. The bulk BC was divided into three size fractions: dissolved BC (size <0.45 µm), colloidal BC (0.45 µm < size < 1 µm), and particulate BC (size > 1 µm). With the presence of BC fractions (250 mg/L) nitrobenzene reduction by Na2S was significantly facilitated, wherein the mediation efficiency was positively correlated with the BC fraction's oxygen group content in an order of particulate BC < colloidal BC ≪ dissolved BC. Consistently, the oxidation treatment of particulate BC with O3 or HNO3 improved the mediation efficiency, whereas the reduction treatment with NaBH4 reduced the mediation efficiency. The supernatant collected with dialysis or filtration of suspension of BC materials pre-reacted with Na2S could effectively reduce nitrobenzene, suggesting that reactive reducing sulfur species were produced in aqueous solutions by reacting sulfide only with BC materials. This was evidenced by the fact that polysulfides and polysulfide radicals were both detected in the supernatant. As demonstrated by electron paramagnetic resonance analysis, the quinone moieties at the surface of BC materials accepted electrons from sulfide and turned into semiquinone free radicals, consequently leading to formation of reactive reducing sulfur species and thus enhanced nitrobenzene reduction. The strong mediation efficiency on redox reactions observed for colloidal BC and dissolved BC combined with their significant mobility in subsurface environments indicate that these carbonaceous materials may play an important role in the fate process of organic contaminants as both carriers and catalysts. CAPSULE: The surface quinone moieties of BC induce the formation of reactive reducing sulfur species by acting as one-electron acceptors and facilitate nitrobenzene reduction by sulfide.

Enhanced adsorption of bisphenol A, tylosin, and tetracycline from aqueous solution to nitrogen-doped multiwall carbon nanotubes via cation-π and π-π electron-donor-acceptor (EDA) interactions.

Doping heteroatoms in carbon nanotubes can substantially enhance the electronic polarizability of the carbon surface and thus may facilitate adsorptive interactions of organic contaminants. Here, the adsorption isotherms of three polar/ionizable emerging organic contaminants, bisphenol A, tylosin, and tetracycline from aqueous solutions to synthesized heteroatom nitrogen-doped multiwall carbon nanotubes (N-MCNT) were compared with those to commercial non-doped multiwall carbon nanotubes (MCNT) at pH ~ 6. N-MCNT exhibited much stronger adsorption (3-4 folds higher sorption distribution coefficients, Kd) towards the three adsorbates than MCNT. The hydroxyl group-substituted bisphenol A molecule is rich in π-electrons and thus interacts with the polarized π-electron-depleted N-heterocyclic aromatic ring on N-MCNT via π-π electron-donor-acceptor (EDA) interaction, whereas the protonated amino group and enone groups in the tylosin molecule are deficient in electrons and interact with the neighboring π-electron-rich aromatic ring on N-MCNT via cation-π and π-π EDA interactions, respectively. The tetracycline molecule contains both electron-rich moiety (phenol ring) and electron-depleted moieties (protonated amino group and enone groups), which interact with the corresponding π-electron-acceptor/donor sites on N-MCNT. The proposed adsorption mechanisms were tested by the effects of ionic strength (NaCl or CaCl2), co-present Cu2+ ion, and changing pH on adsorption, and further by the adsorption behavior of a model organic cation (tetraethylamine). These results indicate that enhanced adsorption of emerging organic contaminants to carbon nanotubes can be achieved by doping with heterocyclic nitrogen atoms to facilitate specific EDA interactions. Capsule: Nitrogen-doped multiwall carbon nanotubes exhibit enhanced adsorptive removal of bisphenol A, tylosin, and tetracycline from aqueous solutions.

Calculation for tensile strength and fracture toughness of granite with three kinds of grain sizes using three-point-bending test.

Tensile strength and fracture toughness, important parameters of the rock for engineering applications are difficult to measure. Thus this paper selected three kinds of granite samples (grain sizes = 1.01mm, 2.12mm and 3mm), used the combined experiments of physical and numerical simulation (RFPA-DIP version) to conduct three-point-bending (3-p-b) tests with different notches and introduced the acoustic emission monitor system to analyze the fracture mechanism around the notch tips. To study the effects of grain size on the tensile strength and toughness of rock samples, a modified fracture model was established linking fictitious crack to the grain size so that the microstructure of the specimens and fictitious crack growth can be considered together. The fractal method was introduced to represent microstructure of three kinds of granites and used to determine the length of fictitious crack. It is a simple and novel method to calculate the tensile strength and fracture toughness directly. Finally, the theoretical model was verified by the comparison to the numerical experiments by calculating the nominal strength σn and maximum loads Pmax.

Strong binding of apolar hydrophobic organic contaminants by dissolved black carbon released from biochar: A mechanism of pseudomicelle partition and environmental implications.

Dissolved black carbon (DBC), the soluble fraction of black carbon (BC), is an important constituent of dissolved organic matter pool. However, little is known about the binding interactions between hydrophobic organic contaminants (HOCs) and DBC and their significance in the fate process. This study determined the binding ability of DBC released from rice-derived BC for a series of apolar HOCs, including four polycyclic aromatic hydrocarbons and four chlorinated benzenes, using batch sorption and solubility enhancement techniques. Bulk BC and a dissolved soil humic acid (DSHA) were included as benchmark sorbents. The organic carbon-normalized sorption coefficient of phenanthrene to DBC was slightly lower than bulk BC, but was over ten folds higher than DSHA. Consistently, DBC was more effective than DSHA in enhancing the apparent water solubility of the tested HOCs, and the enhancement positively correlated with solute n-octanol-water partition coefficient, indicating the predominance of hydrophobic partition. The much higher binding ability of DBC relative to DSHA was mainly attributed to its higher tendency to form pseudomicellar structures as supported by the fluorescence quenching and the pH-edge data. Our findings suggest that DBC might play a significant role in the environmental fate and transport of HOCs as both sorbent and carrier.

Association of urban forest landscape characteristics with biomass and soil carbon stocks in Harbin City, Northeastern China.

BACKGROUND: Urban forests help in mitigating carbon emissions; however, their associations with landscape patterns are unclear. Understanding the associations would help us to evaluate urban forest ecological services and favor urban forest management via landscape regulations. We used Harbin, capital city of the northernmost province in China, as an example and hypothesized that the urban forests had different landscape metrics among different forest types, administrative districts, and urban-rural gradients, and these differences were closely associated with forest carbon sequestration in the biomass and soils. METHODS: We extracted the urban forest tree coverage area on the basis of 2 GF-1 remote sensing images and object-oriented based classification method. The analysis of forest landscape patterns and estimation of carbon storage were based on tree coverage data and 199 plots. We also examined the relationships between forest landscape metrics and carbon storage on the basis of forest types, administrative districts, ring roads, and history of urban settlements by using statistical methods. RESULTS: The small patches covering an area of less than 0.5 ha accounted for 72.6% of all patches (average patch size, 0.31 ha). The mean patch size (AREA_MN) and largest patch index (LPI) were the highest in the landscape and relaxation forest and Songbei District. The landscape shape index (LSI) and number of patches linearly decreased along rural-urban gradients (p < 0.05). The tree biomass carbon storage varied from less than 10 thousand tons in the urban center (first ring road region and 100-year regions) to more than 100 thousand tons in the rural regions (fourth ring road and newly urbanized regions). In the same urban-rural gradients, soil carbon storage varied from less than five thousand tons in the urban centers to 73-103 thousand tons in the rural regions. The association analysis indicated that the total forest area was the key factor that regulates total carbon storage in trees and soils. However, in the case of carbon density (ton ha-1), AREA_MN was strongly associated with tree biomass carbon, and soil carbon density was negatively related to LSI (p < 0.01) and AREA_MN (p < 0.05), but positively related to LPI (p < 0.05). DISCUSSION: The urban forests were more fragmented in Harbin than in other provincial cities in Northeastern China, as shown by the smaller patch size, more complex patch shape, and larger patch density. The decrease in LSI along the rural-urban gradients may contribute to the forest carbon sequestrations in downtown regions, particularly underground soil carbon accumulation, and the increasing patch size may benefit tree carbon sequestration. Our findings help us to understand how forest landscape metrics are associated with carbon storage function. These findings related to urban forest design may maximize forest carbon sequestration services and facilitate in precisely estimating the forest carbon sink.

A Coupled Thermal-Hydrological-Mechanical Damage Model and Its Numerical Simulations of Damage Evolution in APSE.

This paper proposes a coupled thermal-hydrological-mechanical damage (THMD) model for the failure process of rock, in which coupling effects such as thermally induced rock deformation, water flow-induced thermal convection, and rock deformation-induced water flow are considered. The damage is considered to be the key factor that controls the THM coupling process and the heterogeneity of rock is characterized by the Weibull distribution. Next, numerical simulations on excavation-induced damage zones in Äspö pillar stability experiments (APSE) are carried out and the impact of in situ stress conditions on damage zone distribution is analysed. Then, further numerical simulations of damage evolution at the heating stage in APSE are carried out. The impacts of in situ stress state, swelling pressure and water pressure on damage evolution at the heating stage are simulated and analysed, respectively. The simulation results indicate that (1) the v-shaped notch at the sidewall of the pillar is predominantly controlled by the in situ stress trends and magnitude; (2) at the heating stage, the existence of confining pressure can suppress the occurrence of damage, including shear damage and tensile damage; and (3) the presence of water flow and water pressure can promote the occurrence of damage, especially shear damage.