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.

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.