Synthesis and Peroxide Activation Mechanism of Bimetallic MOF for Water Contaminant Degradation: A Review.

Metal-organic framework (MOF) materials possess a large specific surface area, high porosity, and atomically dispersed metal active sites, which confer excellent catalytic performance as peroxide (peroxodisulfate (PDS), peroxomonosulfate (PMS), and hydrogen peroxide (H2O2)) activation catalysts. However, the limited electron transfer characteristics and chemical stability of traditional monometallic MOFs restrict their catalytic performance and large-scale application in advanced oxidation reactions. Furthermore, the single-metal active site and uniform charge density distribution of monometallic MOFs result in a fixed activation reaction path of peroxide in the Fenton-like reaction process. To address these limitations, bimetallic MOFs have been developed to improve catalytic activity, stability, and reaction controllability in peroxide activation reactions. Compared with monometallic MOFs, bimetallic MOFs enhance the active site of the material, promote internal electron transfer, and even alter the activation path through the synergistic effect of bimetals. In this review, we systematically summarize the preparation methods of bimetallic MOFs and the mechanism of activating different peroxide systems. Moreover, we discuss the reaction factors that affect the process of peroxide activation. This report aims to expand the understanding of bimetallic MOF synthesis and their catalytic mechanisms in advanced oxidation processes.

The potential of green biochar generated from biogas residue as a heterogeneous persulfate activator and its non-radical degradation pathways: Adsorption and degradation of tetracycline.

Advanced oxidation aided by sulfate radicals (SO4-) is an effective option for the treatment of refractory pollutants from aqueous solutions. In this work, a metal-free biochar catalyst was prepared using pyrolyzed biogas residue as the raw material. The biogas residue carbon (BRC) obtained at 800 °C showed excellent catalytic activity and adsorption capacity for the removal of tetracycline (TC) with 97.9% of removal efficiency. Such performance is accounted for by the rich pores and accelerated electron transformability conferred by its defect structure with the crucial role of pyrolysis temperature in regulating catalyst properties. The BRC-800/peroxymonosulfate (PMS) system worked predominantly through non-radical pathways with high stability/recyclability without being interfered by organic/inorganic compounds in an actual water environment. The exceelent removal performance is also supported by the kinetic reaction rate of the BRC-800/PMS system as estimated to be 0.03017 min-1. This work provides a simple and effective path for modifying biogas residue waste for versatile applications.

A comprehensive exploration on distribution, risk assessment, and source quantification of heavy metals in the multi-media environment from Shaying River Basin, China.

Comprehensively understand the distribution of pollutants in the multi-media environment at basin scale is of major importance to the ecological risk assessment and pollution control. In this study, multi-media contamination characteristics of eight heavy metals in the water, soil, and sediment from the Shaying River Basin of China have been analyzed to probe their ecological risks and potential sources. Results revealed that heavy metal concentrations in pore water were higher than those in surface water. While the mean concentrations of most heavy metals increased follow the order of bankside soil (BS)

The potential of microplastics as adsorbents of sodium dodecyl benzene sulfonate and chromium in an aqueous environment.

Considering the omnipresence of microplastics (MPs) in aquatic environments, they are expected to exert significatn impacts as carriers for diverse waterborne pollutants. In this work, the adsorptive behavior of two ionic components (i.e., sodium dodecyl benzene sulfonate (SDBS) and Cr(VI)) has been explored against the two types of MPs as model adsorbents, namely poly (ethylene terephthalate) (PET) and polystyrene (PS). The influence of key variables (e.g., pH, particle size, and dose of the MPs) on their adsorption behavior is evaluated from various respects. The maximum adsorption capacity values of SDBS on PET and PS are estimated to be 4.80 and 4.65 mg⋅g-1, respectively, while those of Cr(VI) ions are significantly lower at 0.080 and 0.072 mg⋅g-1, respectively, The adsorptive equilibrium of SDBS is best described in relation to pH and MP size by a Freundlich isotherm. In contrast, the adsorption behavior of Cr(VI) is best accounted for by a Langmuir isotherm to indicate its adsorption across at least two active surface sites.

Fe3O4 nanoparticles loading on cow dung based activated carbon as an efficient catalyst for catalytic microbubble ozonation of biologically pretreated coal gasification wastewater.

Cow dung based activated carbon was successfully modified by Fe3O4 nanoparticles as the novel catalyst (Fe3O4 nanoparticles@CDAC) to improve the microbubble ozonation treating biologically pretreated coal gasification wastewater (BPCGW). When the pH, ozone dosage, ozone bubble diameter and catalyst dosage of the ozonation were 7, 0.4 L/min, 5 µm and 3 g/L, the chemical oxygen demand (COD) removal efficiency reached 74% and the ratio of biochemical oxygen demand in five days/COD (BOD5/COD) increased from 0.04 to 0.52, which were attributed to the electron transfer of Fe2+ and Fe3+ in Fe3O4 and enhanced hydroxyl radicals generation by the reaction of iron ions and ozone. Meanwhile, benzene derivatives, naphthalene and aromatic proteins were significantly removed while multiple chain hydrocarbons and their derivatives composed the main residual organic matters. The catalytic activity was slightly decreased even the catalyst has been reused for five times. Therefore, catalytic microbubble ozonation using Fe3O4 nanoparticles@CDAC represented excellent performance treating BPCGW and it is a promising process for wastewater advanced treatment.

Toxicological Assessment of Ammonia Exposure on Carassius auratus red var. Living in Landscape Waters.

To understand the toxic mechanism of ammonia and identify effective biomarkers on the oxidative stress for the fish Carassius auratus red var., acute and chronic toxicity tests were conducted. The 96-h LC50 of total ammonia nitrogen (TAN) for C. auratus was 135.4 mg L-1, the corresponding unionized ammonia (NH3) concentration was 1.5 mg L-1. The activities of superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), glutathione-peroxidase (GSH-Px) and glutathione (GSH) showed an increase with a subsequent falling, while the malondialdehyde (MDA) increased during the chronic test. The SOD, MDA, and GSH could be effective biomarkers to evaluate the TAN oxidative stress, the maximum acceptable toxicant concentration (MATC) was 11.3 mg L-1 for TAN. To our knowledge, this is the first study to propose biomarkers to evaluate potential environmental risk and establish a risk threshold for TAN in C. auratus.

A green recycling process of the spent lead paste from discarded lead-acid battery by a hydrometallurgical process.

In this study, a green recycling process of discarded lead-acid battery paste, which could avoid both the smelting and electro-winning route has been developed. Leaching reagents containing sodium citrate, acetic acid and hydrogen peroxide were reacted with spent lead paste in aqueous media at the pH of 5-6. Lead paste was leached and formed into lead citrate precursor, which was recrystallized and separated from the solution. The optimal conditions for the leaching process at room temperature were found to be the: concentration of acetic acid solution of 0.92 mol L-1; concentration of sodium citrate solution of 0.478 mol L-1; initial mass ratio of solid spent lead paste to liquid (solid/liquid ratio) of 1/5 g/mL; and reaction time of 2 hours. The results showed that the desulphurization efficiency of lead paste was up to 99.9%. The optimal conditions for lead citrate re-crystallization from the leaching mixed solution were found to be the re-crystallization temperature of 55oC for 5 hours in a water bath. The lead citrate precursor synthesized from discarded lead-acid battery pastes was the chemical formula of Pb3(C6H5O7)2·3H2O with columnar shape in the length of 30-50 µm, which was easily separated from the leaching solution. The results of kilogram-scale experiments made progress easier for obtaining the ultrafine lead oxide product (PbO and Pb) from discarded lead-acid battery paste.

A new method for water quality assessment: by harmony degree equation.

Water quality assessment is an important basic work in the development, utilization, management, and protection of water resources, and also a prerequisite for water safety. In this paper, the harmony degree equation (HDE) was introduced into the research of water quality assessment, and a new method for water quality assessment was proposed according to the HDE: by harmony degree equation (WQA-HDE). First of all, the calculation steps and ideas of this method were described in detail, and then, this method with some other important methods of water quality assessment (single factor assessment method, mean-type comprehensive index assessment method, and multi-level gray correlation assessment method) were used to assess the water quality of the Shaying River (the largest tributary of the Huaihe in China). For this purpose, 2 years (2013-2014) dataset of nine water quality variables covering seven monitoring sites, and approximately 189 observations were used to compare and analyze the characteristics and advantages of the new method. The results showed that the calculation steps of WQA-HDE are similar to the comprehensive assessment method, and WQA-HDE is more operational comparing with the results of other water quality assessment methods. In addition, this new method shows good flexibility by setting the judgment criteria value HD0 of water quality; when HD0 = 0.8, the results are closer to reality, and more realistic and reliable. Particularly, when HD0 = 1, the results of WQA-HDE are consistent with the single factor assessment method, both methods are subject to the most stringent "one vote veto" judgment condition. So, WQA-HDE is a composite method that combines the single factor assessment and comprehensive assessment. This research not only broadens the research field of theoretical method system of harmony theory but also promotes the unity of water quality assessment method and can be used for reference in other comprehensive assessment.

Preliminary results of water quality assessment using phytoplankton and physicochemical approaches in the Huai River Basin, China.

Water pollution has been a significant issue in the Huai River Basin (HRB) of China since the late 1970s. In July and December 2013, two field investigations were carried out at 10 sites along the main streams of the basin. The monitoring indices contained both physicochemical variables and the structure and composition of phytoplankton communities. The correlations between communities and physicochemical variables were analyzed using cluster analysis and redundancy analysis. Moreover, water quality was evaluated using the comprehensive nutrition state index (TLI) and Shannon-Wiener diversity index (H). Results indicated that more phytoplankton species were present in December than in July, but total density was less in December. Phytoplankton communities in the midstream of the Shaying River were affected by the same physicochemical factors throughout the year, but ammonia nitrogen and total phosphorus had the greatest influence on these sites in July and December, respectively. The water pollution status of the sampling sites was much greater in the Shaying River midstream than at other sites. TLI was more suitable than H for assessing water quality in the study area. These results provide valuable information for policy makers and stakeholders in water quality assessment, water ecosystem restoration, and sustainable basin management in the HRB.

Description and Application of a Mathematical Method for the Analysis of Harmony.

Harmony issues are widespread in human society and nature. To analyze these issues, harmony theory has been proposed as the main theoretical approach for the study of interpersonal relationships and relationships between humans and nature. Therefore, it is of great importance to study harmony theory. After briefly introducing the basic concepts of harmony theory, this paper expounds the five elements that are essential for the quantitative description of harmony issues in water resources management: harmony participant, harmony objective, harmony regulation, harmony factor, and harmony action. A basic mathematical equation for the harmony degree, that is, a quantitative expression of harmony issues, is introduced in the paper: HD = ai - bj, where a is the uniform degree, b is the difference degree, i is the harmony coefficient, and j is the disharmony coefficient. This paper also discusses harmony assessment and harmony regulation and introduces some application examples.

Experimental analysis of the impact of sluice regulation on water quality in the highly polluted Huai River Basin, China.

Impact assessment of sluice regulation on water quality is one of the crucial tasks in the present river management. However, research difficulties remain because of insufficient in situ data and numerous influencing factors in aquatic environments. The Huaidian Sluice, the main control sluice of the Shaying River, China, was selected for this study. Three field experimental programs were designed and carried out to analyze spatial and temporal variations in water quality parameters under various sluice regulation conditions and to explore the impacts of regulation mechanisms on water quality. Monitoring data were used to simulate water quality under different scenarios by the water quality analysis simulation program (WASP). Results demonstrate that the influences of sluice regulation on permanganate index (CODMn) and ammonia nitrogen (NH4-N) concentrations (indicators of water quality) were complex and nonlinear and presented different trends of increase or decrease from different regulation modes. Gate openings of different widths and different flow rates affected CODMn and NH4-N concentrations differently. Monitoring results and numerical simulation results indicate that the sluice opening should be small. Flow discharge through the sluice should be greater than 10 m(3) s and less than 60 m(3) s to maintain low CODMn concentrations, and discharge should be low (e.g., 14 m(3) s) to maintain low NH4-N concentrations. This research provides an experimental basis for further research on the construction of water quality models and for the development of reasonable regulations on water quality and quantity.

Comparison of engineered nanoparticle transport in columns of three different lengths: Transport experiments and multi-observation point modeling.

This study focuses on the effectiveness of commonly-used 15 cm column lengths for investigating nanoparticle transport in porous media. Experimental tests examined the transport and retention behaviors of two types of nanoparticles, graphene oxide (GO) and titanium dioxide (TiO2) nanoparticles, in saturated sand columns of different lengths (15, 30 and 45 cm), while considering key environmental factors like ionic strength (IS, 1-50 mM), flow rate (1-3 mL min-1), and grain size (150-850 µm). In the 15 cm columns, both GO and TiO2 transport decreased with higher IS and lower flow rate; grain size affected GO and TiO2 differently. Smaller grain size increased GO retention in the sand columns through straining, thus weakening GO mobility, whereas increased fluid shear force suppressed the ripening of TiO2, enhancing its migration. Similar environmental effects were noted in longer columns (30 and 45 cm), but fitted transport parameters (Smax and k) and predicted long-term mobility (Lmax) indicated that 15 cm columns might underestimate nanoparticle mobility. Blocking and ripening models based on single and multiple observation points to simulate nanoparticle transport and retention showed that predictions aligned well with experimental data. These results indicate that using combinations of columns of different lengths to achieve multiple observation points improves model prediction accuracy; in single-column experiments, the 45 cm and 30 cm columns respectively better predict the mobility range of GO and TiO2 compared to 15 cm columns.

The Fate of Microplastics, Derived from Disposable Masks, in Natural Aquatic Environments.

This paper mainly reviews the fate of microplastics, released from used face masks, in the water environment. Through previous experiments, the amount of fiber microplastics released from used face masks into aqueous environments was not negligible, with the maximum microplastics releasing amount reaching 10,000 piece·day-1 for each mask. Microplastic derived from these masks often occurred in the shape of polymeric fibers that resulted from the breakage of the chemical bonds in the plastic fibers by the force of water flow. The potential contact forces between microplastics (originating from face masks) with other pollutants, primarily encompass hydrophobic and electrostatic interactions. This critical review paper briefly illustrates the fate of microplastics derived from disposable face masks, further devising effective strategies to mitigate the environmental impact of plastic particle release from the used personal protective equipment.

Understanding the pivotal role of ubiquitous Yellow River suspend sediment in efficiently degrading metronidazole pollutants in water environments.

Sulfite-based advanced oxidation technology has received considerable attention for its application in organic pollutants elimination. However, the potential of natural sediments as effective catalysts for sulfite activation has been overlooked. This study investigates a novel process utilizing suspended sediment/sulfite (SS/S(IV)) for degradation of metronidazole (MNZ). Our results demonstrate that MNZ degradation efficiency can reach to 93.1 % within 90 min with 12.0 g SS and 2.0 mM sulfite. The influencing environmental factors, including initial pH, SS dosage, S(IV) concentration, temperature, and co-existing substances were systematically investigated. Quenching experiments and electron paramagnetic resonance analyses results indicate that SO3•- is the primary active substance responsible for MNZ degradation, with involvement of SO4•-, SO5•-, and •OH. X-ray photoelectron spectroscopy and Mössbauer spectra reveal that Fe (III)-silicates play a crucial role in activating S(IV). Furthermore, analysis of degradation intermediates and pathways of MNZ is conducted using liquid chromatography with mass spectrometry (LC -MS). The toxicity of MNZ and its intermediates were also systematically evaluated by the T.E.ST. program and wheat seeds germination test. This study offers valuable insight into the activation of sulfite by natural sediments and could contribute to the development of SS-based advanced oxidation processes (AOPs) for the in-situ remediation of antibiotics-contaminated water environments.

Influence of changes in hydrodynamic conditions on cadmium transport in tidal river network of the Pearl River Delta, China.

With rapid economic development, the Pearl River Delta (PRD) of China has experienced a series of serious heavy metal pollution events. Considering complex hydrodynamic and pollutants transport process, one-dimensional hydrodynamic model and heavy metal transport model were developed for tidal river network of the PRD. Then, several pollution emergency scenarios were designed by combining with the upper inflow, water quality and the lower tide level boundary conditions. Using this set of models, the temporal and spatial change process of cadmium (Cd) concentration was simulated. The influence of change in hydrodynamic conditions on Cd transport in tidal river network was assessed, and its transport laws were summarized. The result showed the following: Flow changes in the tidal river network were influenced remarkably by tidal backwater action, which further influenced the transport process of heavy metals; Cd concentrations in most sections while encountering high tide were far greater than those while encountering middle or low tides; and increased inflows from upper reaches could intensify water pollution in the West River (while encountering high tide) or the North River (while encountering middle or low tides).

[Influence of phthalates from Shaying river on children's intelligence and secretion of thyroid hormone].

OBJECTIVE: To investigate the effect of phthalates exposure from drinking water on children's intelligence and secretion of thyroid hormone. METHODS: Two villages in S County were selected randomly as polluted area and control area according to the distance from the Shaying river basin. Phthalates including DEP, DBP, DMP, DEHP were measured both in the river water and drinking water using HPLC method. Children aged 8 to 13 years old studying in the village primary school were recruited by cluster sampling (n = 154). The combined Reven Test was used to test children intelligence and ELISA method was used to determined thyroid hormone levels. RESULTS: The concentrations of phthalates (DEP, DBP) were exceeding standards of surface water quality in any of the three sections of the river. Compared to the control area, the concentration of DEP and DBP in drinking water were significant higher in the polluted area than that in control area (P < 0.05). Children from polluted area had significant higher FT4 concentration compared to children from control area (P < 0.05). Intelligence level in children from polluted area was lower than that from control area (P < 0.05). CONCLUSION: The drinking water has been polluted by Shaying river and thyroid hormones levels of children were affected in the polluted areas. It is necessary to verify if this change is related to the phthalates.

Incorporating carbon sequestration toward a water-energy-food-carbon planning with uncertainties.

Water-energy-food nexus (WEFN) is the core content in the United Nations 2030 Agenda for Sustainable Development. However, the value of soil and crops' carbon sink function has not yet been fully considered in the managment practices of WEFN system. Here, we developed a water-energy-food-carbon nexus (WEFCN) planning framework that incorporates carbon sequestration and multiple mathematical optimization methods into the practical WEFN management for Henan Province, which is one of major grain-producing areas in China. Uncertainties from multiple objectives, scenarios, and different stakeholder interests are captured. We found that wheat has the largest carbon sequestration, followed by corn and oil-bearing crops, while other crops have implicit carbon sequestration. Since chemical fertilizer produces the most carbon emissions, the usage of chemical fertilizer needs to be reasonably controlled. Overall, the proposed framework supports optimal decision-making for regional-scale WEFCN management and further unlocks the hidden value of agricultural carbon mitigation.

The Potential of Spent Coffee Grounds @ MOFs Composite Catalyst in Efficient Activation of PMS to Remove the Tetracycline Hydrochloride from an Aqueous Solution.

The efficient removal of Tetracycline Hydrochloride (TC) from wastewater, which is a difficult process, has attracted increasing attention. Aiming to synchronously achieve the goal of natural waste utilization and PMS activation, we have combined the MOFs material with waste coffee grounds (CG). The catalytic activity of the CG@ZIF-67 composite in the TC removal process was thoroughly evaluated, demonstrating that the TC removal rate could reach 96.3% within 30 min at CG@ZIF-67 composite dosage of 100 mg/L, PMS concertation of 1.0 mM, unadjusted pH 6.2, and contact temperate of 293.15 K. The 1O2 and ·SO4- in the CG@ZIF-67/PMS/TC system would play the crucial role in the TC degradation process, with 1O2 acting as the primary ROS. The oxygen-containing functional groups and graphite N on the surface of CG@ZIF-67 composite would play a major role in efficiently activating PMS and correspondingly degrading TC. In addition, the CG@ZIF-67/PMS/TC system could withstand a wide pH range (3-11). The application of CG in preparing MOF-based composites will provide a new method of removing emerging pollutants from an aqueous solution.

A Comprehensive Exploration on Occurrence, Distribution and Risk Assessment of Potentially Toxic Elements in the Multi-Media Environment from Zhengzhou, China.

Road dust (RD), roadside soils (RS) and river surface sediments (sediments) are important materials for evaluating contaminant levels in urban areas. This study aims to investigate the contaminant characteristics, pollution levels and ecological risks of RD, RS and sediments of potentially toxic elements (PTEs), including Cr, Ni, Cu, Zn, As, Cd, Hg and Pb, in the central urban area of Zhengzhou. Results reveal that RD shows a higher concentration of PTEs when compared to the other two environments. The spatial distribution characteristics suggest that PTEs in RD, RS and sediments may come from different sources. The geo-accumulation index (Igeo) was used to describe that the RD was moderately to extremely contaminated with Cd and Hg, while both RS and sediments were significantly enriched with Cd and Hg. For RD, RS and sediments, the potential ecological risk (RI) demonstrates a high potential ecological risk from Cd and Hg. Overall, PTEs in Zhengzhou road dust present a moderate risk.

Application and Comparison of Different Models for Quantifying the Aquatic Community in a Dam-Controlled River.

In order to develop a better model for quantifying aquatic community using environmental factors that are easy to get, we construct quantitative aquatic community models that utilize the different relationships between water environmental impact factors and aquatic biodiversity as follows: a multi-factor linear-based (MLE) model and a black box-based 'Genetic algorithm-BP artificial neural networks' (GA-BP) model. A comparison of the model efficiency and their outputs is conducted by applying the models to real-life cases, referring to the 49 groups of seasonal data observed over seven field sampling campaigns in Shaying River, China, and then performing model to reproduce the seasonal and inter-annual variation of the water ecological characteristics in the Huaidian (HD) site over 10 years. The results show that (1) the MLE and GA-BP models constructed in this paper are effective in quantifying aquatic communities in dam-controlled rivers; and (2) the performance of GA-BP models based on black-box relationships in predicting the aquatic community is better, more stable, and reliable; (3) reproducing the seasonal and inter-annual aquatic biodiversity in the HD site of Shaying River shows that the seasonal variation of species diversity for phytoplankton, zooplankton, and zoobenthos are inconsistent, and the inter-annual levels of diversity are low due to the negative impact of dam control. Our models can be used as a tool for aquatic community prediction and can become a contribution to showing how quantitative models in other dam-controlled rivers to assisting in dam management strategies.