Multiscale levels CO2 decouple reinforcement in China.

Decoupling economic growth from CO2 emissions is imperative for China. Meanwhile, establishing a consistent and comprehensive decoupling inventory that includes national (N), regional and provincial (RP), and city and county (CC) levels is essential for further policy formulation. This research aims to investigate the decoupling status using the "N-RP-CC" approach while considering changes in decoupling trends at the different levels. A combination of the Tapio decoupling model and cluster analysis is employed to study the decoupling's spatiotemporal characteristics and trends. The study first calculates the decoupling value for "national, 7; regions, 30; provinces, 1501 CCs" in China, 2006-2017. The results show that there continues to be an improvement in the decoupling trend at the national level. Conversely, the regional scale exhibits a more vulnerable decoupling trend compared to the national level, with weak and extended negative decoupling observed in northeastern and northern China. Moreover, provincial heterogeneities are increasingly evident, with poor decoupling statuses appearing in Jilin, Heilongjiang, Liaoning, and Xinjiang, as well as many central provinces. Additionally, although more than half of CCs exhibit weak decoupling during most years, seven different states of decoupling were also identified during the time frame. These findings further indicate that spatiotemporal heterogeneities extend beyond RP scales within CCs. Taking the Yangtze River as a boundary line reveals a severe situation in northern areas along with rapid development trends observed in southern regions. Finally, we clustered 1414 CCs based on their industrial proportions for 2017 which further highlights increasingly prominent heterogeneities that should be carefully considered. Based on these findings, policy recommendations such as spatial organization and optimization and technique investment are proposed to achieve CO2 emission decoupling under the N-RP-CC levels.

A novel hydrangea-like magnetic composite Fe3O4@MnO2@ZIF-67 for efficient selective adsorption of Pd(II) from metallurgical wastewater.

The selective adsorption of palladium from wastewater is a feasible solution to solving palladium pollution and resource scarcity. Because traditional solvent extraction methods often involve the use of considerable amounts of organic solvents, research is focused on investigating adsorption techniques that can selectively remove palladium from wastewater. In this paper, the magnetic composite Fe3O4@MnO2@ZIF-67 was synthesized and its performance for the adsorption of Pd(II) in acidic water was investigated. Fe3O4@MnO2@ZIF-67 was characterized by various analytical methods such as TEM, SEM, EDS, BET, XRD, FTIR, zeta potential analysis, VSM, and TGA. The effects of palladium ion concentration, contact time, pH, and temperature on adsorption were evaluated. The kinetics were shown to follow the pseudo-second-order kinetic model and Elovich model, and the rate-limiting step was chemisorption. Thermodynamic studies showed that increasing the temperature promoted the adsorption of Pd(II), and the maximum uptake capacity of Fe3O4@MnO2@ZIF-67 for Pd(II) was 531.91 mg g-1. Interestingly, Fe3O4@MnO2@ZIF-67 exhibited superior selectivity for Pd(II) in the presence of Ir(IV), Pt(IV), and Rh(III). The adsorbent can be used repeatedly for selective adsorption of palladium. Even at the fifth cycle, the uptake rate of Pd(II) remained as high as 83.1%, and it showed a favorable adsorption capacity and selectivity for Pd(II) in real metallurgical wastewater. The adsorption mechanism was analyzed by SEM, FTIR, XRD, XPS, and DFT calculations, which indicated that electrostatic interactions and coordination with nitrogen-containing groups were involved. Fe3O4@MnO2@ZIF-67 is a promising adsorbent for the efficient adsorption and selective separation of palladium ions.

Persulfate enhanced removal of bisphenol A by copper oxide/reduced graphene oxide foam: Influencing factors, mechanism and degradation pathway.

The CuO/reduced graphene oxide foam (CuO/RGF) with excellent recyclability was prepared via hydrothermal method followed by freeze drying treatment for bisphenol A (BPA) removal via activating peroxydisulfate (PDS). SEM, XRD, XPS, FT-IR, BET, and TG techniques were used to investigate the structure and property of CuO/RGF. The effect of degradation conditions (pH, PDS amount, Cl-, HCO3-, HA and FA) on BPA removal by CuO/RGF were investigated. The result presented that CuO nanosheet was inserted into the RGF carrier with three-dimensional structure. The degradation rate constant of BPA over CuO/RGF (0.00917 min-1) was 1.24 and 6.46 times higher than those of BPA over CuO (0.00714 min-1) and RGF (0.00142 min-1). More importantly, the pore structure of RGF can successfully limit the release of Cu (II) compared to pure CuO. According to quenching test as well as electron spin resonance (EPR) spectra, BPA degradation was triggered by 1O2, •OH and SO4•-, which was the combination of nonradical (1O2) and radical activation of PDS (•OH and SO4•-). The possible degradation route of BPA was proposed based on intermediates obtained by combining solid phase extraction pretreatment technique with high performance liquid-mass spectrometry. After assessing the viability of MCF-7 cells, we can see that the estrogenic activities of treated solution reduced without producing stronger endocrine disruptors.

Outstanding Performance of the Deep Eutectic Solvent-Based Aqueous Biphasic System Constructed with Sodium Citrate for a Green Gold Separation.

Aqueous biphasic systems (ABSs) that are based on deep eutectic solvents (DESs) are environmentally benign systems to use for metal ion separation. In this work, a series of DESs was synthesized for the first time with PEG 400 as hydrogen bond donors and tetrabutylphonium bromide (P4Br), tetrabutylammonium bromide (N4Br), or tetrabutylammonium chloride (N4Cl) as hydrogen bond acceptors, and then they were combined with citrate (Na3C6H5O7), which is eco-friendly, to construct an ABS for use in the separation of Au(I) from an aurocyanide solution. Phase diagrams of DESs + Na3C6H5O7 + H2O systems were constructed using the experimentally measured data. Multiple factors that affect the efficiency of the gold extraction were studied; these factors were the species of salt or DES and their content, the equilibrium pH, the oscillation time, and the initial gold concentration. Gold(I) is preferentially retained in the DES-rich phase, and the P4Br:PEG 1:2 + Na3C6H5O7 + H2O system has a high extraction efficiency of 100.0% under optimized conditions. FT-IR, NMR, and TEM characterizations and DFT calculations show that the migration of Au(I) from the salt-rich to the DES-rich phase follows an ion exchange mechanism. Specifically, Au(CN)2- replaces Br- in the original P4Br and generates a stable ion pair with the quaternary phosphonium salt cation, P+, and this replacement is driven by electrostatic attractions. A new strong hydrogen bond network simultaneously forms between the anionic Au(CN)2- and the -OH group in the PEG 400 component. Finally, the gold of Au(I)-loaded P4Br:PEG 1:2 can be successfully reduced by sodium borohydride with an efficiency of 100.0%. The strategy to extract gold(I) from alkaline cyanide solutions using an ABS based on DESs as proposed in this work provides a potential platform for developing green technology for recovering gold.

PARP-1 inhibits DNMT1-mediated promoter methylation and promotes linc01132 expression in benzene-exposed workers and hydroquinone-induced malignant transformed cells.

Hydroquinone (HQ), one of the main active metabolites of benzene, can induce the abnormal expression of long non-coding RNA (lncRNA). Studies have shown that lncRNA plays an important role in the occurrence of hematologic tumors induced by benzene or HQ. However, the molecular mechanism remains to be elucidated. Here, we investigated the molecular mechanism by which poly(ADP-ribose)polymerase 1 (PARP-1) interacts with DNA methyltransferase 1 (DNMT1) to regulate promoter methylation mediated linc01132 expression in HQ-induced TK6 malignant transformed cells (HQ-MT). The results revealed that the expression of linc01132 was increased in benzene-exposed workers and HQ-MT cells. The methylation of linc01132 promoter region was inhibited. Furthermore, in HQ-MT cells treated with 5-Aza-2'-deoxycytidine (5-AzaC) (DNA methyltransferase inhibitor) or trichostatin A (TSA) (histone deacetylation inhibitor), the expression of linc01132 was increased due to the regulation of DNA promoter methylation level by inhibiting DNMT1 expression. The methylation level of linc01132 promoter was correlated negatively with the expression of linc01132 in benzene-exposed workers, indicating that DNA methylation may contribute the expression of linc01132. Knockout of DNMT1, not DNMT3b, increased the expression of linc01132 as well as the demethylation of linc01132 promoter in HQ-MT cells. It was found that by knockdown PARP-1, the expression of DNMT1 in the nucleus was increased by immunofluorescence confocal microscopy, leading to the inhibition of hypermethylation in the promoter region of linc01132. Therefore, PARP-1 inhibits DNA methyltransferase (DNMT)-mediated promoter methylation and plays a role in linc01132 expression in benzene-exposed workers or HQ-MT cells, and is associated with benzene or HQ induced leukemia progression.

Microwave- and ultrasonic-assisted synthesis of 2D La-based MOF nanosheets by coordinative unsaturation degree to boost phosphate adsorption.

The metal or metal clusters and organic ligands are relevant to the selectivity and performance of phosphate removal in MOFs, and the electron structure, chemical characteristics, and preparation method also affect efficiency and commercial promotion. However, few reports focus on the above, especially for 2D MOF nanomaterials. In this work, two 2D Ln-TDA (Ln = La, Ce) nanosheets assembled via microwave- and ultrasonic-assisted methods are employed as adsorbents for phosphate (H2PO4 -, HPO4 2-) removal for the first time. Their microstructure and performance were characterized using XRD, TEM, SEM, AFM, FTIR, zeta potential, and DFT calculations. The prepared 2D Ln-TDA (Ln = La, Ce) nanosheets exposed more adsorption sites and effectively reduced the restrictions of mass transfer. Based on this, the Langmuir model was employed to estimate the maximum adsorption capacities of the two kinds of nanosheets, which reached 253.5 mg g-1 and 259.5 mg g-1, which are 553 times and 3054 times larger than those for bulk Ln-TDA (Ln = La, Ce), respectively. Additionally, the kinetic data showed that the adsorption equilibrium time is fast, approximately 15 min by the pseudo-second-order model. In addition, the prepared products not only have a wide application range (pH = 3-9) but also offer eco-safety in terms of residuals (no Ln leak out). Based on the XPS spectra, FTIR spectra and DFT calculations, the main adsorption mechanisms included ligand exchange and electrostatic interactions. This new insight provides a novel strategy to prepare 2D MOF adsorbents, achieving a more eco-friendly method (microwave- and ultrasonic-assisted synthesis) for preparing 2D Ln-based MOF nanosheets by coordinative unsaturation to boost phosphate adsorption.

Integrated ABR and UASB system for dairy wastewater treatment: Engineering design and practice.

This work designed and assessed the engineering performance of dairy wastewater treatment by an integrated system consisting of an anaerobic baffled reactor (ABR) and an upflow anaerobic sludge blanket (UASB). With fats adsorbed and decomposed, proteins were first denatured coagulated into solids in the ABR treatment process, and this process created suitable conditions for sludge retention in the sludge bed of the UASB. As a result, the combined system achieved a substantial reduction in excess sludge from 3 to 5 t/d to 3 t/m, notable biogas generation, and 98% COD removal, while the other pollutants in the effluent met relevant standards. In addition, the system attained an excellent performance in terms of the energy consumption and water treatment agent amount. Two active plants achieved operation costs lower than 0.5 kW h/t, while stable operations under ambient temperature conditions lasted longer than three years. Engineering practices both technically and economically affirmed the potential of the proposed system for dairy wastewater treatment.

Effect of ferric chloride on phosphorus immobilization and speciation in Dianchi Lake sediments.

Immobilization of phosphorus in lake sediments and control of internal-loading phosphorus release have become crucial aspects of eutrophication lake management. In this study, the immobilization efficiency of phosphorus by ferric chloride in Dianchi Lake sediments was investigated. In addition, effects of the dosage of ferric chloride and contact time on the release of phosphorus from sediments were investigated. Laboratory experiments revealed that ferric chloride can effectively inhibit the release of phosphorus from sediments. At a ferric chloride dosage of 10 mg/g, the total phosphorus concentration of the overlying water was reduced by ~87%. With the increase in the contact time, the amount of phosphorus immobilized by ferric chloride increased. To further evaluate the feasibility of ferric chloride for immobilising phosphorus in sediments, an amplification experiment with a water volume of 50 L was carried out. By the addition of 6 mg/g of ferric chloride, the total phosphorus concentration of the overlying water was still less than 0.01 mg/L after 100 days. At the same time, the phosphorus species in the sediment after treatment with ferric chloride were analyzed. Results revealed that ferric chloride mainly converts unstable exchangeable phosphorus (Ex-P), ferric phosphate (Fe-P) and organic phosphorus (Or-P) into more stable occluded phosphate (O-P), reducing the possible release of phosphorus from sediments. Practical applications of ferric chloride to control the release of phosphorus from Dianchi Lake sediments were discussed.

Preparation of Nano-Copper Sulfide and Its Adsorption Properties for 17α-Ethynyl Estradiol.

In the present work, a tubular nano-copper sulfide was successfully synthesized by hydrothermal method. The physical and chemical properties of the prepared materials were characterized by XRD, SEM, TEM, and BET. The synthesized copper sulfide was used as an adsorbent for removing 17α-ethynyl estradiol (EE2) and exhibited excellent adsorption properties. At 25 °C, 15 mg of adsorbent was applied for 50 mL of 5 mg/L EE2 solution, adsorption equilibrium was reached after 180 min, and the adsorption rate reached nearly 90%. In addition, the kinetics, isothermal adsorption, and thermodynamics of the adsorption process were discussed on the basis of theoretical calculations and experimental results. The theoretical maximum adsorption capacity of copper sulfide was calculated to be 147.06 mg/g. The results of this study indicated that copper sulfide was a stable and efficient adsorbent with promising practical applications.

The comparative study of two reusable phosphotungstic acid salts/reduced graphene oxides composites with enhanced photocatalytic activity.

In this work, two recyclable phosphotungstic acid salts/reduced graphene oxides were successfully prepared. The prepared samples were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), Raman spectroscopy, and photoluminescence spectroscopy (PL). The structure and catalytic performance of two composites were comparatively investigated, and the reduced graphene oxide mass ratios in K3[PW12O40]/reduced graphene oxide (denoted as KPW-RGO) and (NH4)3[PW12O40]/reduced graphene oxide (denoted as NH4PW-RGO) were optimized and their roles in them were explored. The results indicate that the Keggin structures of KPW and NH4PW are still kept after being anchored on the RGO surface, but their morphologies change a lot in composites. The photocatalytic activities of KPW-3RGO (0.01989 min-1) are 5.42 times than that of KPW (0.00367 min-1), and NH4PW-1RGO (0.0184 min-1) is 2.26 times than that of NH4PW (0.00814 min-1). The enhanced photocatalytic activity is mainly ascribed to photo-induced interfacial charge transfer on the heterojunction between RGO and NH4PW or KPW and strong adsorption ability of RGO towards MO. Moreover, NH4PW-1RGO and KPW-3RGO had much better photocatalytic activity, good recyclable ability, and stability compared to HPW-RGO, which cannot be recycled.

One-step hydrothermal synthesis of CTAB-modified SiO2 for removal of bisphenol A.

A stable SiO2 material marked as CTAB-Ms(x) was synthesized by a novel sol-gel method. It was modified with hexadecyl trimethyl ammonium bromide (CTAB), which resulted in high adsorption capacity. Its microstructure and surface functional groups were characterized by scanning electron microscope, transmission electron microscope and Fourier transform infrared. The results showed that CTAB-Ms(x) had a core/shell structure in which the core was a CTAB micelle and the shell was SiO2. The prepared material was applied to adsorb bisphenol A (BPA). Pseudo-first-order kinetics equation, pseudo-second-order kinetics equation, Langmuir adsorption isotherm model, Temkin adsorption isotherm model, and thermodynamic equations were used to fit and analyze the experiment results. The theoretical maximum adsorption capacities calculated according to linear and non-linear forms of the Langmuir isotherm were 370.37 mg·g-1 and 198.80 mg·g-1, and the adsorption equilibrium time was 120 min. A mechanism study showed that the high adsorption capacity was attributed to the solubilization effect of the CTAB micelle.

Arsenic pollution and its treatment in Yangzonghai lake in China: In situ remediation.

In this study, the effect of direct atomization and spraying a ferric chloride (FeCl3) solution to decrease the arsenic concentration and its pollution in Yangzonghai Lake, China, was investigated. Ten ships were used for spraying 6-8t of FeCl3 in the lake every day since October 2009. After spraying, the average concentration of arsenic in Yangzonghai Lake, which has an area of 31 km(2), an average depth of 20 m, and a water storage capacity of 604 million m(3), started to decrease from 0.117 mg L(-1). On 20 September 2010, the lowest arsenic level of 0.021 mg L(-1) was attained, with an arsenic removal rate as high as 82.0%. However, the source of pollution was not eliminated, and local rainfall mainly occurred in September; hence, arsenic concentration from October to December increased to 0.078 mg L(-1). At the beginning of 2011, the As concentration decreased and remained at 0.025-0.028 mg L(-1) from May to September. During the 2 years of FeCl3 treatment, the water quality improved from V Class to II-III Class of the Chinese standards, which remained consistent for 12 months. The total cost for this in situ water treatment was 29 million RMB, which was less than a hundredth of the expected expenditure of 4-7 billion RMB. The treatment method achieved goals such as high arsenic removal rate, easy operation, low cost, and ecological security. In this study, the changing patterns of the concentration of arsenic in Yangzonghai Lake from June 2008 to December 2014 were analyzed, and the following problems were discussed: the stability of iron-arsenic precipitates in the lake, the concentrations of ferric and chloride ions in the lake, the pH of the lake during treatment, the stability of iron-arsenic precipitates in the lakebed sediments, and the variation of phytoplankton species in the lake.

Commentary on "Arsenic mobility in the arsenic-contaminated Yangzonghai Lake in China" by Changliang Yang et al. [Ecotoxicology and Environmental Safety, 107(2014)321-327].

This commentary concerns some inaccuracy in recently published paper "Arsenic mobility in the arsenic-contaminated Yangzonghai Lake in China". Yang et al. raised an incorrect conclusion that after treatment with FeCl3 using the flocculation method, the sediments in the Yangzonghai Lake released As in the summer. The fundamental flaws of the paper which led to the incorrect conclusion were unreasonable sampling method for determining As concentration at various water depth and the wrong lake water volume of 6.04×10(8)m(3) (actually 4.8×10(8)m(3)) for calculating inventory of As in Yangzhonghai in August 2012. Then the authors attribute the As release in summer to the high concentration of HCO3(-) without any support of experimental data. Meanwhile, the authors designed a microbiological experiment to illustrate that increasing capacity of anaerobic microorganism could lead to As releasing from sediments. In our view point, this microbiological experiment was nonsense for evaluating the stability of As in sediments of Yangzonghai lake since the experimental conditions were greatly different from the natural conditions. Therefore, we conclude that the conclusions put forward by YANG are incorrect.

The influence of transition metal ions on collagen mineralization.

The ions in body fluid play an important role in bone formation besides being a synthesizing material. Transition metal ions Co(2+), Ni(2+), Zn(2+), Fe(3+), Mn(2+), Cu(2+), Cd(2+) and Hg(2+) doped hydroxyapatite (HAP)/collagen composites were synthesized successfully in the presence of collagen traces at mild acidic pH for the first time. However, the amount of doped Hg(2+) and Cd(2+) was relatively low. Meanwhile, through soaking the collagen sponge as a template in simulated body fluid (SBF) which contains different transition metal ions (Mn(2+), Cu(2+), Ni(2+), Co(2+), Cd(2+), Hg(2+)), bone-like HAP/collagen composites were synthesized. Hg(2+) had a certain inhibitory effect on the formation of HAP crystals on the surface of the collagen sponge while Co(2+) can promote the formation of HAP on the collagen sponge. For both HAP/collagen composites and HAP/collagen sponge, it was found that transition metal ions Mn(2+) had a significant effect on the morphology of HAP particles and could induce to form floc-like HAP particle aggregates.

Creating nanoscopic collagen matrices using atomic force microscopy.

The atomic force microscope (AFM) is introduced as a biomolecular manipulation machine capable of assembling biological molecules into well-defined molecular structures. Native collagen molecules were mechanically directed into well-defined, two-dimensional templates exhibiting patterns with feature sizes ranging from a few nanometers to several hundreds of micrometers. The resulting nanostructured collagen matrices were only approximately 3-nm thick, exhibited an extreme mechanical stability, and maintained their properties over the time range of several months. Our results directly demonstrate the plasticity of biological assemblies and provide insight into the physical mechanisms by which biological structures may be organized by cells in vivo. These nanoscopic templates may serve as platforms on non-biological surfaces to direct molecular and cellular processes.

Assembly of collagen into microribbons: effects of pH and electrolytes.

Collagen represents the major structural protein of the extracellular matrix. Elucidating the mechanism of its assembly is important for understanding many cell biological and medical processes as well as for tissue engineering and biotechnological approaches. In this work, conditions for the self-assembly of collagen type I molecules on a supporting surface were characterized. By applying hydrodynamic flow, collagen assembled into ultrathin ( approximately 3 nm) highly anisotropic ribbon-like structures coating the entire support. We call these novel collagen structures microribbons. High-resolution atomic force microscopy topographs show that subunits of these microribbons are built by fibrillar structures. The smallest units of these fibrillar structures have cross-sections of approximately 3 x 5nm, consistent with current models of collagen microfibril formation. By varying the pH and electrolyte of the buffer solution during the self-assembly process, the microfibril density and contacts formed within this network could be controlled. Under certain electrolyte compositions the microribbons and microfibers display the characteristic D-periodicity of approximately 65 nm observed for much thicker collagen fibrils. In addition to providing insight into the mechanism of collagen assembly, the ultraflat collagen matrices may also offer novel ways to bio-functionalize surfaces.