A temporally relaxed theory of physically or chemically non-equilibrium solute transport in heterogeneous porous media.

Groundwater constitutes a critical component in providing fresh water for various human endeavors. Never-theless, its susceptibility to contamination by pollutants represents a significant challenge. A comprehensive understanding of the dynamics of solute transport in groundwater and soils is essential for predicting the spatial and temporal distribution of these contaminants. Presently, conventional models such as the mobile-immobile (MIM) model and the rate-limited sorption (RLS) model are widely employed to describe the non-Fickian behavior of solute transport. In this research, we present a novel approach to solute transport that is founded on the temporally relaxed theory of Fick's Law. Our methodology introduces two relaxation times to account for solute particle collisions and attachment, leading to the derivation of a new advection-dispersion equation. Our findings indicate that the relaxation times possess similar properties to the transport parameters in the MIM and RLS models, and our solution can be applied to accurately predict transport parameters from soil column experiments. Additionally, we discovered that the relaxation times are proportional to the magnitude of Peclet number. This innovative approach provides a deeper insight into solute transport and its impact on groundwater contamination.

Expression Patterns and Functional Analysis of Three SmTAT Genes Encoding Tyrosine Aminotransferases in Salvia miltiorrhiza.

Tyrosine aminotransferase (TAT, E.C. 2.6.1.5) is a pyridoxal phosphate-dependent aminotransferase that is widely found in living organisms. It catalyzes the transfer of the amino group on tyrosine to α-ketoglutarate to produce 4-hydroxyphenylpyruvic acid (4-HPP) and is the first enzyme for tyrosine degradation. Three SmTATs have been identified in the genome of Salvia miltiorrhiza (a model medicinal plant), but their information is very limited. Here, the expression profiles of the three SmTAT genes (SmTAT1, SmTAT2, and SmTAT3) were studied. All three genes expressed in different tissues and responded to methyl jasmonate stimuli. SmTAT proteins are localized in the cytoplasm. The recombinant SmTATs were subjected to in vitro biochemical properties. All three recombinant enzymes had TAT activities and SmTAT1 had the highest catalytic activity for tyrosine, followed by SmTAT3. Also, SmTAT1 preferred the direction of tyrosine deamination to 4-HPP, while SmTAT2 preferred transamination of 4-HPP to tyrosine. In parallel, transient overexpression of SmTATs in tobacco leaves revealed that all three SmTAT proteins catalyzed tyrosine to 4-HPP in vivo, with SmTAT1 exhibiting the highest enzymatic activity. Overall, our results lay a foundation for the production of tyrosine-derived secondary metabolites via metabolic engineering or synthetic biology in the future.

Experimental investigation of solute transport across transition interface of porous media under reversible flow directions.

Understanding solute transport through macroscopic interfaces is essential to understand the effects of geological heterogeneity on contaminant transport in porous media. Studies of solute transport in compartmental porous media have noted the asymmetry of breakthroughs (BTCs) in solute movement across material interfaces, indicating the presence of discontinuous concentration that makes solute transport directionally dependent. Transition interfaces are more common in nature than sharp interfaces. To understand solute transport across transition interfaces, well-controlled laboratory experiments were performed. A numerical model was also built to understand mass accumulation and concentration discontinuity through transition as well as sharp interfaces. We conclude that directionally dependent asymmetry of BTCs was found with both sharp and transition interfaces. The asymmetry of BTCs was more pronounced at a transition interface than at a sharp interface. The mobile and immobile (MIM) model can better capture the directionally dependent transport of solutes through a sharp/transition interface than the advection-dispersion equation (ADE). The mobile water partition coefficient (ß) and mass transfer coefficient (ω) in MIM were lager in the direction from fine sand to coarse sand (F-C). The time difference between tracer replace and tracer input is greater in the presence of an interface, especially transition interfaces. Even at small Reynolds numbers (1 × 10-4 to 0.116), solute transport across a discontinuous interface under reversible flow directions is most likely dominated by convective dispersion rather than an assumed diffusion process.

Investigating the Influence of Electronic Effects of Functional Groups on the Fluorescence Mechanism of Probes in Water Samples.

This study investigates the fluorescence quenching mechanism of formaldehyde detection probe Naph1 and its contrast probe Naph3 in water samples and discussed the effect of the electron-donating group and electron-withdrawing group on fluorescence characteristics based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT). We optimized the structures of the four probes Naph1, Naph1-S, Naph3, and Naph3-S (Scheme 1) and calculated the absorption and emission spectra, which were in good agreement with the experiment. Frontier molecular orbitals (FMOs) were used to analyze the charge arrangement in the excited state. To investigate the intramolecular proton transfer (ESIPT) phenomenon, a potential energy curve was constructed. The amount of fragment charge transfer was analyzed by the IFCT method, and then it was determined whether there was an intramolecular charge transfer (ICT) process. It was found that there was an ICT process in Naph3. The electronic effect of the functional groups did not determine the ICT characteristics and the fluorescence characteristics of the substance. Furthermore, the spin-orbit coupling  (SOC) constant based on the intersystem crossing (ISC) was supplemented, which showed that the fluorescence quenching of Naph1 and Naph3 was caused by the ISC and the corresponding quenching of Naph3-S was caused by charge transfer (CT) in the excited state.

Adsorption/Oxidation of arsenic in groundwater by nanoscale Fe-Mn binary oxides loaded on zeolite.

Nanoscale Fe-Mn binary oxides loaded on zeolite (NIMZ) is synthesized and characterized. The as-synthesized adsorbent is amorphous with 126 m2/g surface area; it is effective for the adsorption of both As(III) and As(V) in synthetic groundwater. It has high adsorption capacities of 296.23 and 201.10 mg/g for As(III) and As(V), respectively. For the adsorption of 2 mg/L arsenic, the aqueous concentration quickly decreases to less than 10 /microg/L within 30 min. During the adsorption of As(III), the in-aqueous measurement of As(V) shows a low concentration in the initial stage and disappears afterward. The fraction of As(V) on NIMZ gradually increases with time, proving the oxidation of As(III). The adsorption of As(III) and As(V) decreases with increasing pH. The anions of SiO3(2-), H2PO4(-), and HCO3(-) significantly compete with arsenic for the adsorption sites. The innersphere surface complexes are formed by As(III) or As(V) with the hydroxyl groups on the surface of NIMZ.

Multivariate analysis of the heterogeneous geochemical processes controlling arsenic enrichment in a shallow groundwater system.

The effects of various geochemical processes on arsenic enrichment in a high-arsenic aquifer at Jianghan Plain in Central China were investigated using multivariate models developed from combined adaptive neuro-fuzzy inference system (ANFIS) and multiple linear regression (MLR). The results indicated that the optimum variable group for the AFNIS model consisted of bicarbonate, ammonium, phosphorus, iron, manganese, fluorescence index, pH, and siderite saturation. These data suggest that reductive dissolution of iron/manganese oxides, phosphate-competitive adsorption, pH-dependent desorption, and siderite precipitation could integrally affect arsenic concentration. Analysis of the MLR models indicated that reductive dissolution of iron(III) was primarily responsible for arsenic mobilization in groundwaters with low arsenic concentration. By contrast, for groundwaters with high arsenic concentration (i.e., > 170 µg/L), reductive dissolution of iron oxides approached a dynamic equilibrium. The desorption effects from phosphate-competitive adsorption and the increase in pH exhibited arsenic enrichment superior to that caused by iron(III) reductive dissolution as the groundwater chemistry evolved. The inhibition effect of siderite precipitation on arsenic mobilization was expected to exist in groundwater that was highly saturated with siderite. The results suggest an evolutionary dominance of specific geochemical process over other factors controlling arsenic concentration, which presented a heterogeneous distribution in aquifers. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Environmental Science and Health, Part A, to view the supplemental file.

Enhanced arsenic removal by graphene oxide chitosan composites through FeOx decoration: Influences and mechanism.

Iron decoration has been recognized as one of the most important paths to enhance contaminant adsorption by carbon-based composites. In this study, varying amounts of Fe (II) are used for the modification of graphene oxide chitosan (GOCS) materials to assess the impact of iron oxide (FeOx) morphology on the composites and their efficiency in arsenic (As) removal. Results show that incorporating 0.08 mol Fe(II) into GOCS yields better As removal performance, leading to a remarkable enhancement by 5 times for As(V) and 6 times for As(III). The iron minerals in the material consist of goethite (FeO(OH)) and magnetite (Fe3O4), with FeO(OH) playing a predominant role in As removal through the complexation and electrostatic attraction of -OH and Fe - O groups. The adsorption capacity for As (Qe) decreases with the increasing pH and the mass and volume ratio (m/v) but increases with the increasing initial concentration (C0). Besides, the presence of SO42- and HPO42- can significantly reduce As removal by the FeOx-modified GOCS. Under the conditions of pH = 3, m/v = 1.0 g/L, and C0 = 10 mg/L, a maximum Qe value reaches 61.94 mg/g. The adsorption is well-fitted to a pseudo-second-order kinetic model and is an endothermic, spontaneous, and monolayer adsorption process.

Iron modified chitosan/coconut shell activated carbon composite beads for Cr(VI) removal from aqueous solution.

Iron modified chitosan/coconut shell activated carbon (Fe/CSCC) composite bead is synthesized to remove Cr(VI) and is characterized to reveal the influencing factors and reaction mechanism. Results show that the adsorption capacity (Qe) of Cr(VI) increases with the increase of iron loading, contact time (t), Cr(VI) initial concentration (C0), and temperature (T), but decreases with the increase of pH, and mass and volume ratio (m/v). After 0.1 mol FeCl3 modification, the removal efficiency of Cr(VI) by Fe/CSCC reaches as high as 97.25 % at pH = 3, m/v = 1.0 g/L, t = 2880 min, C0 = 25 mg/L, and T = 25 °C. The coexisting ions of SO42-, HPO4-, and Ca2+ lead to the decrease of Qe by 7.82, 5.05, and 5.50 mg/g, respectively, and the inhibition effect increases with their increasing concentrations. Fe/CSCC adsorption for Cr(VI) is an endothermic spontaneous process, and a chemical and monolayer adsorption, which is better fitted to a pseudo-second-order kinetic. The fitted maximum Qe is 64.49 mg/g by using the Langmuir model. Moreover, after five cycles of regeneration, the Qe value only drops about 3.46 mg/g. Characterization analysis of BET, XRD, FTIR, XPS, and SEM-EDS indicates that Cr(VI) is mainly adsorbed by Fe/CSCC through electrostatic attraction and complexation, which is related to the -COOH and - NH2 groups, and Fe - O groups, respectively.

As(III) removal by a recyclable granular adsorbent through dopping Fe-Mn binary oxides into graphene oxide chitosan.

Graphene oxide chitosan composite (GOCS) is recognized as an environmentally friendly composite adsorbent because of its stability and abundant functional groups to adsorb heavy metals, and Fe-Mn binary oxides (FMBO) have attracted increasing interest due to their high removal capacity of As(III). However, GOCS is often inefficient for heavy metal adsorption and FMBO suffers poor regeneration for As(III) removal. In this study, we have proposed a method of dopping FMBO into GOCS to obtain a recyclable granular adsorbent (Fe/MnGOCS) for achieving As(III) removal from aqueous solutions. Characterization of BET, SEM-EDS, XRD, FTIR, and XPS are carried out to confirm the formation of Fe/MnGOCS and As(III) removal mechanism. Batch experiments are conducted to investigate the effects of operational factors (pH, dosage, coexisting ions, etc.), as well as kinetic, isothermal, and thermodynamic processes. Results show that the removal efficiency (Re) of As(III) by Fe/MnGOCS is about 96 %, which is much higher than those of FeGOCS (66 %), MnGOCS (42 %), and GOCS (8 %), and it increases slightly with the increasing molar ratio of Mn and Fe. This is because amorphous Fe (hydro)oxides (mainly in the form of ferrihydrite) complexation with As(III) is the major mechanism to remove As(III) from aqueous solutions, and it is accompanied by As(III) oxidation mediated by Mn oxides and the complexation of As(III) with oxygen-containing functional groups of GOCS. Charge interaction plays a weaker role in As(III) adsorption, therefore Re is persistently high over a wide range of pH values of 3-10. But the coexisting PO43- can greatly decrease Re by 24.11 %. As(III) adsorption on Fe/MnGOCS is endothermic and its kinetic process is controlled by pseudo-second-order with a determination coefficient of 0.95. Fitted by the Langmuir isotherm, the maximum adsorption capacity is 108.89 mg/g at 25 °C. After four times regeneration, there is only a slight decrease of <10 % for the Re value. Column adsorption experiments show that Fe/MnGOCS can effectively reduce As(III) concentration from 10 mg/L to <10 µg/L. This study provides new insights into binary polymer composite modified by binary metal oxides to efficiently remove heavy metals from aquatic environments.

Atmospheric Vapor Impact on Desert Vegetation and Desert Ecohydrological System.

The ability of plants to absorb unsaturated atmospheric water vapor is a controversial topic. To study how vegetation in arid areas survives under limited water resources, this study uses Tamarisk in the Ulan Buh Desert of China as an example. The in-situ observation of a newly designed Lysimeter and sap flow meter system were used to monitor the precipitation infiltration and the utilization efficiency of Tamarisk of atmospheric vapor. The results show that the annual precipitation of 84 mm in arid areas could still result in deep soil recharge (DSR) with a recharge rate of 5 mm/year. Furthermore, DSR is detectable even in the winter, and the 5-year average DSR was 5.77% of the annual precipitation. It appears that the small precipitation events are critically important for the survival of Tamarisk. When the atmospheric relative humidity reaches 70%, Tamarisk leaves can absorb the unsaturated atmospheric vapor, which accounts for 13.2% of the annual precipitation amount. To adapt to the arid environment, Tamarisk can harvest its water supply from several sources including atmospheric vapor and micro-precipitation events (whose precipitation is below the measurement limit of 0.2 mm of the precipitation gauge) and can still permit a certain amount of recharge to replenish the deep soil moisture. Such an ecohydrological dynamic is of great significance to desert vegetation.

Analysis of Growing Season Normalized Difference Vegetation Index Variation and Its Influencing Factors on the Mongolian Plateau Based on Google Earth Engine.

Frequent dust storms on the Mongolian Plateau have adversely affected the ecological environmental quality of East Asia. Studying the dynamic changes in vegetation coverage is one of the important means of evaluating ecological environmental quality in the region. In this study, we used Landsat remote sensing images from 2000 to 2019 on the Mongolian Plateau to extract yearly Normalized Difference Vegetation Index (NDVI) data during the growing season. We used partial correlation analysis and the Hurst index to analyze the spatiotemporal characteristics of the NDVI before and after the establishment of nature reserves and their influencing factors on the GEE cloud platform. The results showed that (1) the proportion of the region with an upwards trend of NDVI increased from 52.21% during 2000-2009 to 67.93% during 2010-2019, indicating a clear improvement in vegetation due to increased precipitation; (2) the increase in precipitation and positive human activities drove the increase in the NDVI in the study region from 2000 to 2019; and (3) the overall trend of the NDVI in the future is expected to be stable with a slight decrease, and restoration potential is greater for water bodies and grasslands. Therefore, it is imperative to strengthen positive human activities to safeguard vegetation. These findings furnish scientific evidence for environmental management and the development of ecological engineering initiatives on the Mongolian Plateau.

SmJAZ4 interacts with SmMYB111 or SmMYC2 to inhibit the synthesis of phenolic acids in Salvia miltiorrhiza.

Jasmonic acid (JA), as an important plant hormone, can induce the synthesis of phenolic acids in Salvia miltiorrhiza Bunge, a model medicinal plant, but the specific mechanism remains to be further elucidated. JA-responsive SmMYB111 positively regulates the biosynthesis of salvianolic acid B (SalB), but the molecular mechanism is unclear. Here, we found that SmMYB111 directly binds to the promoters of SmTAT1 and SmCYP98A14 and activates their transcription. Yeast two hybrid and bimolecular fluorescent complementation assay indicated that SmMYB111 interacts with SmJAZ4. Furthermore, we systematically characterized the function of SmJAZ4, which was highly expressed in flowers and roots and located in the nucleus and cell membrane. The contents of phenolic acids in the SmJAZ4-overexpressed transgenic plantlets and SmJAZ4-overexpressed transgenic hairy roots decreased significantly. SmJAZ4 interacts with SmMYC2 or SmMYB111 to repress their transcriptional activation activity on target enzyme genes of the biosynthesis pathway of phenolic acids. Overall, the molecular mechanism of SmJAZ4-SmMYC2/SmMYB111 module participating in JA signaling regulation of SalB biosynthesis was elucidated, which give a clue for the molecular regulation of phenolic acids biosynthesis in S. miltiorrhiza.

Effect of long-term saline mulched drip irrigation on soil-groundwater environment in arid Northwest China.

Water shortage and soil salinization are the two main factors that are limiting the sustainability of agriculture in arid and semi-arid areas. The mulched drip irrigation (MDI) with brackish groundwater is widely used in the arid areas of Northwest China. In this study, field experiments were carried out to study the effect of long-term MDI with brackish groundwater on the soil and groundwater environment. It was found that the groundwater level decreased in the Peacock river watershed steadily from 2008 to 2019, resulted from escalating groundwater exploitation due to the expanding agricultural irrigation area and increasing irrigation water demand. The decline of groundwater level reduced the evaporation of phreatic surface (ETg) and groundwater recharge from MDI (Rg). The ETg and Rg would be very small, where ETg tended to be zero and Rg would decrease to a constant value, while the water table depth was larger than 3 m. In addition, MDI had little effect on the soil moisture content (SMC) during the MDI period while the groundwater level was shallow (less than 1.9 m), and it increased SMC gradually as the cycle of irrigations increased while the groundwater level was deep (greater than 4.2 m). MDI reduced the concentration of soluble salt ions (Na+, K+ and Cl-) and increased the concentration of Ca2+ and SO42- in the soil. The accumulation of Ca2+ and SO42- in bare soil was more serious than that in the mulched land. The SMC, soil ions concentrations, soil salinity and the total dissolved solids of groundwater decreased significantly with the decrease of the groundwater level, and the salinization degree of the soil and groundwater tended to be weak in the field experimental site. However, groundwater level dropped too much caused by increasing agricultural irrigation would be harmful to the sustainable ecological environment.

On the role of rock matrix to heat transfer in a fracture-rock matrix system.

In this study, a fully coupled analytical model is developed for thermal energy transfer in a single fracture-rock matrix system where the coupling implies that the governing equations of thermal transfer in the fracture and rock matrix are supplemented with the continuity conditions of temperature and thermal flux at the interfaces of the fracture-rock matrix. The proposed model accounts for thermal convection, longitudinal thermal conduction and thermal dispersion in the fracture, and transverse thermal conduction in the rock matrix. The fully coupled two-dimensional model is established to investigate the thermal energy transfer processes, assess the spatiotemporal temperature distribution in the fracture and rock matrix system and investigate the role of the rock matrix. The solutions are verified with the existing studies and proven to be accurate and robust. The present study demonstrates that: 1) thermal dispersion in the fracture plays an important role in the temperature distribution in the fracture and rock matrix domains, and longitudinal thermal conduction in the fracture has minor effects on the temperature distribution in the system; 2) transverse thermal conduction in the rock matrix is a critical parameter that determines the spatiotemporal temperature distribution in both the fracture and the rock matrix domains. Ignoring thermal conduction in the rock matrix will lead to a significant overestimation of temperature in the short and long terms; 3) the sensitivity analysis implies that thermal energy transfer in the system is sensitive to the fluid velocity in the fracture, thermal dispersivity in the fracture and thermal conductivity in the rock matrix, and less sensitive to thermal conductivity in the fracture.

Removal of Cr(VI) from Wastewater Using Graphene Oxide Chitosan Microspheres Modified with α-FeO(OH).

Graphene oxide and chitosan microspheres modified with α−FeO(OH) (α−FeO(OH)/GOCS) are prepared and utilized to investigate the performance and mechanism for Cr(VI) removal from aqueous solutions and the possibility of Fe secondary pollution. Batch experiments were carried out to identify the effects of pH, mass, and volume ratio (m/v), coexisting ions, time (t), temperature (T), and Cr(VI) initial concentration (C0) on Cr(VI) removal, and to evaluate adsorption kinetics, equilibrium isotherm, and thermodynamics, as well as the possibility of Fe secondary pollution. The results showed that Cr(VI) adsorption increased with C0, t, and T but decreased with increasing pH and m/v. Coexisting ions inhibited Cr(VI) adsorption, and this inhibition increased with increasing concentration. The influence degrees of anions and cations on the Cr(VI) adsorption in descending order were SO42− > PO42− > NO3− > Cl− and Ca2+ > Mg2+ > Mn2+, respectively. The equilibrium adsorption capacity of Cr(VI) was the highest at 24.16 mg/g, and the removal rate was 97.69% under pH = 3, m/v = 1.0 g/L, T = 298.15 K, and C0 = 25 mg/L. Cr(VI) adsorption was well fitted to a pseudo-second-order kinetic model and was spontaneous and endothermic. The best fit of Cr(VI) adsorption with the Langmuir and Sips models indicated that it was a monolayer and heterogeneous adsorption. The fitted maximum adsorption capacity was 63.19 mg/g using the Sips model under 308.15 K. Cr(VI) removal mainly included electrostatic attraction between Cr(VI) oxyanions with surface Fe−OH2+, and the adsorbed Cr(VI) was partially reduced to Cr(III) and then precipitated on the surface. In addition, there was no Fe secondary pollution during Cr(VI) adsorption.

Exploring the influence of intermolecular hydrogen bonding on the fluorescence properties of HQCT and HQPH fluorescent chemosensors.

Recently, two trace water detection probes, 8-hydroxyquinoline-2-carboxaldehyde thiosemicarbazone(HQCT) and 8-hydroxyquinoline-2-carboxaldehyde (pyridine-2-carbonyl)-hydrazine(HQPH) have been successfully designed in the experiment. The original intramolecular proton transfer can be prevented by the water molecules, leading to fluorescence quenching. In order to investigate the fluorescence quenching mechanism, the effect of water molecules on the excited state proton transfer process will be studied in detail. In this contribution, the six models have been optimized and the related analysis have been carried out. When water molecules are involved in the proton transfer process, the energy barrier decreases significantly and the conversion of the enol structure to the keto structure is accelerated. Moreover, the intermolecular hydrogen bonding, not participating in the proton transfer process, can facilitate the proton transfer process by affecting the distribution of the electrostatic potential within the molecule, which in turn lowers the energy barrier for proton transfer.

On As(III) Adsorption Characteristics of Innovative Magnetite Graphene Oxide Chitosan Microsphere.

A magnetite graphene oxide chitosan (MGOCS) composite microsphere was specifically prepared to efficiently adsorb As(III) from aqueous solutions. The characterization analysis of BET, XRD, VSM, TG, FTIR, XPS, and SEM-EDS was used to identify the characteristics and adsorption mechanism. Batch experiments were carried out to determine the effects of the operational parameters and to evaluate the adsorption kinetic and equilibrium isotherm. The results show that the MGOCS composite microsphere with a particle size of about 1.5 mm can be prepared by a straightforward method of dropping FeCl2, graphene oxide (GO), and chitosan (CS) mixtures into NaOH solutions and then drying the mixed solutions at 45 °C. The produced MGOCS had a strong thermal stability with a mass loss of <30% below 620 °C. The specific surface area and saturation magnetization of the produced MGOCS was 66.85 m2/g and 24.35 emu/g, respectively. The As(III) adsorption capacity (Qe) and removal efficiency (Re) was only 0.25 mg/g and 5.81% for GOCS, respectively. After 0.08 mol of Fe3O4 modification, more than 53% of As(III) was efficiently removed by the formed MGOCS from aqueous solutions over a wide pH range of 5−10, and this was almost unaffected by temperature. The coexisting ion of PO43− decreased Qe from 3.81 mg/g to 1.32 mg/g, but Mn2+ increased Qe from 3.50 mg/g to 4.19 mg/g. The As(III) adsorption fitted the best to the pseudo-second-order kinetic model, and the maximum Qe was 20.72 mg/g as fitted by the Sips model. After four times regeneration, the Re value of As(III) slightly decreased from 76.2% to 73.8%, and no secondary pollution of Fe happened. Chemisorption is the major mechanism for As(III) adsorption, and As(III) was adsorbed on the surface and interior of the MGOCS, while the adsorbed As(III) was partially oxidized to As(V) accompanied by the reduction of Fe(III) to Fe(II). The produced As(V) was further adsorbed through ligand exchange (by forming Fe−O−As complexes) and electrostatic attraction, enhancing the As(III) removal. As an easily prepared and environmental-friendly composite, MGOCS not only greatly adsorbs As(III) but also effectively removes Cr(VI) and As(V) (Re > 60%) and other metals, showing a great advantage in the treatment of heavy metal-contaminated water.

Exploring the relationship between the "ON-OFF" mechanism of fluorescent probes and intramolecular charge transfer properties.

In this study, the excited state charge distribution characteristics and fluorescence mechanism of HClO detection probes HN-ClO (weak fluorescence) and HN-ClO-F (strong fluorescence) probes were investigated based on density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results of electrostatic potential (ESP) map and hole-electron analysis show that the HN-ClO and HN-ClO-F probes have obvious charge separation characteristics in the excited state. The excited state energy decomposition and Merz-Kollman charge analysis demonstrate the existence of distinct planar intramolecular charge transfer (PICT) features in HN-ClO and HN-ClO-F. Due to the strong charge coupling caused by the planar structure, the fluorescence of HN-ClO-F could occur. Furthermore, the weak fluorescence of HN-ClO is caused by inter-system crossing (ISC) between S1 and T1 state. Our result proves that the ICT process could exist in HN-ClO-F, but the PICT process does not cause fluorescence quenching, which have provided an excellent supplement to the mechanism of fluorescent probes. The conclusion is consistent with the fluorescence phenomenon observed in the experiment.

On Inflow to a Tunnel in a Fractured Double-Porosity Aquifer.

Inflow to a tunnel is a great public concern and is closely related to groundwater hydrology, geotechnical engineering, and mining engineering, among other disciplines. Rapid computation of inflow to a tunnel provides a timely means for quickly assessing the inflow discharge, thus is critical for safe operation of tunnels. Dewatering of tunnels is another engineering practice that should be planned. In this study, an analytical solution of the inflow to a tunnel in a fractured unconfined aquifer is obtained. The solution takes into account either the spherical or slab-shaped matrix block and the unsteady state interporosity flow. The instantaneous drainage water table and anisotropic hydraulic conductivities of the fractures network are also considered. Both uniform flux and uniform head boundary condition are considered to simulate the constant head boundary condition in the tunnel. The effects of the hydraulic parameters of the fractured aquifer on the inflow variation of the tunnel are explored. The application of the presented solution to obtain the optimum location and discharge of the well to minimize the inflow to a tunnel is illustrated.

Iron oxides decorated graphene oxide/chitosan composite beads for enhanced Cr(VI) removal from aqueous solution.

This study is the first to evaluate the effects of Iron oxides (FeOx) species and their decoration on graphene oxide/chitosan (GO/CS) composites for Cr(VI) removal and the possibility of Fe secondary pollution. Results show that Fe(III) is a better decoration material than Fe(II) and decoration through immersion-evaporation shows a higher adsorption capacity of Cr(VI) (Qe) than co-precipitation. Fe2O3-GO/CS as the only eco-friendly composite for enhanced Cr(VI) removal is further used for batch adsorption experiments, characterization, kinetics, isotherms, and thermodynamic studies. It is found that Cr(VI) removal mainly includes electrostatic attraction between Cr(VI) oxyanions and surface -NH3+ and -OH2+, and the adsorbed Cr(VI) partially reduces to Cr(III). Qe increases with the increasing initial Cr(VI) concentration, contact time, and temperature, while decreases with the increasing pH and mass and volume ratio (m/v). The coexisting ions (Cl-, NO3-, SO42-, PO43-, As, Fe, and Pb) can cause an obvious decrease of Qe. The removal efficiency (Re) and Qe are 94.3% and 83.8 mg/g, respectively under the optimal conditions. After five times of regeneration, Re is still as high as 84% and Qe drops about 2.6%. Cr(VI) adsorption is spontaneous and endothermic, which is best fitted with the Sips model, and the fitted maximum Qe is 131.33 mg/g.