Simultaneous removal of Cu(Ⅱ) and Cr(Ⅵ) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide(Cl-LDH) was prepared to simultaneously remove Cu(Ⅱ)and Cr(VI) from aqueous solution. The coexisting Cu(Ⅱ)(20 mg/L) and Cr(VI)(40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(Ⅱ) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(Ⅱ) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(Ⅱ) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(Ⅱ)(200 mg/L) and Cr(VI)(400 mg/L). The affecting factors(such as solution initial p H, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of p H values and the concentrations of Mg~(2+) and Al~(2+)in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl-in Cl-LDH interlayer, isomorphic substitution of Mg~(2+) with Cu~(2+), formation of Cu_2Cl(OH)_3precipitation, and the adsorption of Cr(VI) by Cu_2Cl(OH)_3. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

Stability of Fe–As composites formed with As(V) and aged ferrihydrite

During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.     

A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

Organic aerosol molecular composition and gas–particle partitioning coefficients at a Mediterranean site (Corsica)

Molecular speciation of atmospheric organic matter was investigated during a short summer field campaign performed in a citrus fruit field in northern Corsica(June 2011). Aimedat assessing the performance on the field of newly developed analytical protocols, this work focuses on the molecular composition of both gas and particulate phases and provides an insight into partitioning behavior of the semi-volatile oxygenated fraction. Limonene ozonolysis tracers were specifically searched for, according to gas chromatography–mass spectrometry(GC–MS) data previously recorded for smog chamber experiments. A screening of other oxygenated species present in the field atmosphere was also performed. About sixty polar molecules were positively or tentatively identified in gas and/or particle phases. These molecules comprise a wide range of branched and linear, mono and di-carbonyls(C_3–C7),mono and di-carboxylic acids(C_3–C_18), and compounds bearing up to three functionalities.Among these compounds, some can be specifically attributed to limonene oxidation and others can be related to α- or β-pinene oxidation. This provides an original snapshot of the organic matter composition at a Mediterranean site in summer. Furthermore, for compounds identified and quantified in both gaseous and particulate phases, an experimental gas/particle partitioning coefficient was determined. Several volatile products, which are not expected in the particulate phase assuming thermodynamic equilibrium, were nonetheless present in significant concentrations. Hypotheses are proposed to explain these observations, such as the possible aerosol viscosity that could hinder the theoretical equilibrium to be rapidly reached.     

Application of constructed wetlands for wastewater treatment in tropical and subtropical regions (2000–2013)

Constructed wetlands (CWs) have been successfully used for treating various wastewaters for decades and have been identified as a sustainable wastewater management option for developing countries. With the goal of promoting sustainable engineered systems that support human well-being but are also compatible with sustaining natural (environmental) systems, the application of CWs has become more relevant. Such application is especially significant for developing countries with tropical climates, which are very conducive to higher biological activity and productivity, resulting in higher treatment efficiencies compared to those in temperate climates. This paper therefore highlights the practice, applications, and research of treatment wetlands under tropical and subtropical conditions since 2000. In the present review, removal of biochemical oxygen demand (BOD) and total suspended solid (TSS) was shown to be very efficient and consistent across all types of treatment wetlands. Hybrid systems appeared more efficient in the removal of total suspended solid (TSS) (91.3%), chemical oxygen demand (COD) (84.3%), and nitrogen (i.e., 80.7% for ammonium (NH)₄-N, 80.8% for nitrate (NO)₃-N, and 75.4% for total nitrogen (TN)) as compared to other wetland systems. Vertical subsurface flow (VSSF) CWs removed TSS (84.9%), BOD (87.6%), and nitrogen (i.e., 66.2% for NH₄-N, 73.3% for NO₃-N, and 53.3% for TN) more efficiently than horizontal subsurface flow (HSSF) CWs, while HSSF CWs (69.8%) showed better total phosphorus (TP) removal compared to VSSF CWs (60.1%). Floating treatment wetlands (FTWs) showed comparable removal efficiencies for BOD (70.7%), NH₄-N (63.6%), and TP (44.8%) to free water surface (FWS) CW systems.     

Magnetic micro-particle conditioning–pressurized vertical electro-osmotic dewatering (MPEOD) of activated sludge: Role and behavior of moisture and organics

In this study, a magnetic micro-particle conditioning–pressurized vertical electro-osmotic dewatering (MPEOD) process with magnetic micro-particle conditioning–drainage under gravity–mechanical compression–electrical compression (MMPC–DG–MC–EC) stages was established to study the distribution and migration of water, extracellular polymeric substances (EPS), and other organic matter in the activated sludge (AS) matrix at each stage. Results showed that the MPEOD process could attain 53.52% water content (WC) in dewatered AS with bound water (BW) and free water (FW) reduction rates of 82.97% and 99.67%, respectively. The coagulation and time-delayed magnetic field effects of magnetic micro-particles (MMPs) along the MMPC–DG–MC stages initiated the transformation of partial BW to FW in AS. EC had a coupling driving effect of electro-osmosis and pressure on BW, and the changes in pH and temperature at EC stage induced the aggregation of AS flocs and the release of partial BW. Additionally, MMPs dosing further improved the dewatering performance of AS by acting as skeleton builders to provide water passages. Meanwhile, MMPs could disintegrate sludge cells and EPS fractions, thereby reducing tryptophan-like protein and byproduct-like material concentrations in LB-EPS as well as protein/polysaccharide ratio in AS matrix, which could improve AS filterability. At EC stage, the former four Ex/Em regions of fluorescence regional integration analysis for EPS were obviously reduced, especially the protein-like substances in LB- and TB-EPS, which contributed to improvement of AS dewaterability.     

The effect of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ) and Pb(Ⅱ) adsorption

The effects of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ)and Pb(Ⅱ)adsorption were investigated.After combination with DBM,the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of kaolinite and goethite improved compared with the application of the minerals independently.The modeling results of potentiometric titration data proved that the site concentrations of kaolinite and goethite increased by 80%and 30%,respectively after combination with DBM.However,the involvement of functional groups in the DBM/mineral combinations resulted in lower concentrations of observed sites than the theoretical values and led to the enhancement of desorption rates by NH_4NO_3 and EDTA-Na_2.The DBM-mineral complexes might also help to prevent heavy metals from entering DBM cells to improve the survivability of DBM in heavy metal-contaminated environments.During the combination process,the extracellular proteins of DBM provided more binding sites for the minerals to absorb Cu(Ⅱ)and Pb(Ⅱ).In particular,an especially stable complexation site was formed between goethite and phosphodiester bonds from EPS to enhance the Pb(Ⅱ)adsorption capacity.So,we can conclude that the DBM–mineral complexes could improve the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of minerals and protect DBM in heavy metal-contaminated environments.     

Preparation and characterization of a novel hybrid chelating material for effective adsorption of Cu(Ⅱ) and Pb(Ⅱ)

The discharge of heavy metal ions such as Cu~2+and Pb~2+poses a severe threat to public health and the environment owing to their extreme toxicity and bioaccumulation through food chains Herein, we report a novel organic–inorganic hybrid adsorbent, Al(OH)_3-poly(acrylamide dimethyldiallylammonium chloride)-graft-dithiocarbamate(APD), for rapid and effectiv removal of Cu~2+and Pb~2+. In this adsorbent, the "star-like" structure of Al(OH)3 poly(acrylamide-dimethyldiallylammonium chloride) served as the support of dithiocarbamat(DTC) functional groups for easy access of heavy metal ions and assisted development of larg and compact floccules. The synthesized adsorbent was characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), and thermogravimetric analysis(TGA). APD was demonstrated to hav rapid adsorption kinetics with an initial rate of 267.379 and 2569.373 mg/(g·min) as well a superior adsorption capacities of 317.777 and 586.699 mg/g for Cu~2+and Pb~2+respectively. Th adsorption process was spontaneous and endothermic, involving intraparticle diffusion and chemical interaction between heavy metal ions and the functional groups of APD. To assess it versatility and wide applicability, APD was also used in turbid heavy metal wastewater, and performed well in removing suspended particles and heavy metal ions simultaneously through flocculation and chelation. The rapid, convenient and effective adsorption of Cu~2+and Pb~2+give APD great potential for heavy metal decontamination in industrial applications.     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

A comparative investigation of NdSrCu_(1-x)Co_xO_(4-δ) and Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ) (x: 0-0.4) for NO decomposition

A series of single-phase T-structured NdSrCu_(1-x)Co_xO_(4-δ) with oxygen vacancies and T'-structured Sm_(1.8)Ce_(0.2)Cu_(1-x)Co_xO_(4-δ) (x:0-0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-progranuned desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCut_xCoxO4_b catalysts were of oxygen vacancies whereas the Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ) ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level,the oxygen vacancy density of NdSrCu_(1-x)Co_xO_(4-δ) decreased while the over-stoichiometric oxygen amount of Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ)increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO_(3.702) catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr~(-1), and 600-900℃, the catalytic activity of NO decomposition followed the order of NdSrCuO_(3.702)> NdSrCu_(0.8)Co_(0.2)O_(3.736) > NdSrCu_(0.6)Co_(0.4)O_(3.789) > Sm_(1.8)Ce_(0.2)Cu_(0.6)Co_(0.4)O_(4.187)> Sm_(1.8)Ce_(0.2)Cu_(0.8)Co_(0.2)O_(4.104)> Sm_(1.8)Ce_(0.2)CuO_(4.045), in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu~(3+)/Cu~(2+) redox ability of NdSrCu_(1-x)Co_xO_(4-δ) account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

Synthesis, characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(VI) adsorption from aqueous solution

Lagerstroemia speciosa bark (LB) embedded magnetic nanoparticles were prepared by co-precipitation of Fe²⁺ and Fe³⁺ salt solution with ammonia and LB for Cr(VI) removal from aqueous solution. The native LB, magnetic nanoparticle (MNP), L. speciosa embedded magnetic nanoparticle (MNPLB) and Cr(VI) adsorbed MNPLB particles were characterized by SEM–EDX, TEM, BET-surface area, FT-IR, XRD and TGA methods. TEM analysis confirmed nearly spherical shape of MNP with an average diameter of 8.76 nm and the surface modification did not result in the phase change of MNP as established by XRD analysis, while led to the formation of secondary particles of MNPLB with diameter of 18.54 nm. Characterization results revealed covalent binding between the hydroxyl group of MNP and carboxyl group of LB particles and further confirmed its physico-chemical nature favorable for Cr(VI) adsorption. The Cr(VI) adsorption on to MNPLB particle as an adsorbent was tested under different contact time, initial Cr(VI) concentration, adsorbent dose, initial pH, temperature and agitation speed. The results of the equilibrium and kinetics of adsorption were well described by Langmuir isotherm and pseudo-second-order model, respectively. The thermodynamic parameters suggest spontaneous and endothermic nature of Cr(VI) adsorption onto MNPLB. The maximum adsorption capacity for MNPLB was calculated to be 434.78 mg/g and these particles even after Cr(VI) adsorption were collected effortlessly from the aqueous solution by a magnet. The desorption of Cr(VI)-adsorbed MNPLB was found to be more than 93.72% with spent MNPLB depicting eleven successive adsorption–desorption cycles.     

Removal of hexavalent chromium from contaminated waters by ultrasound-assisted aqueous solution ball milling

Batch mode experiments were conducted to study the removal of hexavalent chromium(Cr(Ⅵ)) from aqueous solutions using ultrasound-assisted aqueous solution ball milling.The results show that the reduction rate of Cr(Ⅵ) by ultrasound-assisted aqueous solution ball milling was significantly faster than that by ball milling or ultrasound treatment alone,and an initial Cr(Ⅵ) concentration of 166 mg/L could be decreased to 0.35 mg/L at 120 min.The decisive factors, including initial concentration of Cr(Ⅵ), p H value, ultrasonic frequency and filling gas, were studied. It was found that the optimal ultrasonic frequency for ultrasound-assisted aqueous solution ball milling device was 20 k Hz, and the rate of Cr(Ⅵ)reduction as a function of filling gas followed the order: Ar air N_2 O_2. Samples were characterized by X-ray diffraction, fluorescence measurements, atomic absorption and the diphenylcarbazide colorimetric method. The Cr(Ⅵ) transformed into a precipitate that could be removed from the contaminated water, after which the water could be reused.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag

Basic oxygen furnace slag(BOFS) has the potential to remove hexavalent chromium(Cr(VI))from wastewater by a redox process due to the presence of minerals containing Fe2+. The effects of the solution p H, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope(SEM) equipped with an energy dispersive spectrometer(EDS)system and X-ray diffractometer(XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe2+released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe2+responsible for Cr(VI) removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum(Ca SO4·2H2O)could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2+and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps.     

Rapid adsorption of toxic Pb(Ⅱ) ions from aqueous solution using multiwall carbon nanotubes synthesized by microwave chemical vapor deposition technique

Multiwall carbon nanotubes(MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(Ⅱ)binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared(FT-IR), Brunauer, Emmett and Teller(BET), Field Emission Scanning Electron Microscopy(FESEM) analysis, and the adsorption of Pb(Ⅱ) was studied as a function of p H,initial Pb(Ⅱ) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmaxwas calculated to be 104.2 mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ΔH0, ΔS0and ΔG0were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal(99.9%) of Pb(Ⅱ) are at p H 5, MWCNT dosage 0.1 g, agitation speed 160 r/min and time of 22.5 min with the initial concentration of 10 mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(Ⅱ) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). The wire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH₂-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu^2 + adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N₂ adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH₂-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu^2 + on NH₂-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH₂-Mn-SBA-15 for Cu^2 + was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu^2 + by NH₂-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu^2 +. The NH₂-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption–desorption experiments showed that the NH₂-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.     

圩区河道底泥腐殖酸对重金属和抗生素的共吸附

为识别重金属、抗生素与腐殖酸之间的相互作用,提取圩区河道底泥中腐殖酸,以铜（Cu²⁺）与土霉素（OTC）及诺氟沙星（NOR）作为探针物,研究了腐殖酸在单一Cu²⁺体系、单一OTC体系、单一NOR体系以及Cu²⁺+OTC和Cu²⁺+NOR共存体系下的吸附行为,利用扫描电镜、红外光谱、X射线衍射和BET等方法进行了物相表征,并就可能存在的作用机制进行了分析讨论.结果表明,腐殖酸属典型的无定型非结晶体,其表面荷负电,具有非均匀多孔结构,孔径分布在介孔尺度,以3.76~6.40 nm孔体积占比最大.单一体系下,腐殖酸对Cu²⁺、OTC和NOR的饱和吸附量分别为33.043、19.521和26.676 mg·g^-1;在质量浓度比为1：1的Cu²⁺+OTC和Cu²⁺+NOR共存体系下,Cu²⁺的饱和吸附量分别为38.053 mg·g^-1和39.187 mg·g^-1,OTC和NOR的饱和吸附量分别为25.965 mg·g^-1和32.728 mg·g^-1.单一和共存体系下的吸附特征具有相似性,吸附过程符合准二级动力学方程,吸附等温线遵循Sips模型,吸附热力学特征为自由能降低、熵变和熵变增加的自发型吸热反应,反应类型接近于化学性吸附和络合性吸附.共存体系中的Cu²⁺与OTC及NOR可生成络合物,这增加了腐殖酸可吸附的物种数量,而已吸附的Cu²⁺亦可通过吸附架桥等形式结合OTC和NOR,吸附量因此较单一体系下有所增加.腐殖酸所含羧基、酚羟基、酮基和醛基等含氧官能团普遍参与了吸附反应.     

BS+DAS复配修饰膨润土吸附Cr(Ⅵ)和Cd2+的研究

为了研究两性-阴离子复配修饰膨润土对Cr(VI)和Cd2+的吸附性能差异及其机理,并为两性复配修饰黏土矿物治理重金属污染水体提供依据,采用阴离子型有机修饰剂1-癸烷磺酸钠(DAS)复配修饰两性修饰剂十二烷基二甲基甜菜碱(BS-12或BS)修饰膨润土,研究各供试土样对Cr(VI)和Cd2+的等温吸附曲线及不同温度、pH值和离子强度条件对吸附的影响.结果表明,Langmuir模型能较好地拟合各修饰土样对不同类型重金属离子(Cr(VI)和Cd2+)的吸附曲线,其对Cr(VI)和Cd2+的平衡吸附量均呈现BS+150DAS(150%CEC DAS复配修饰膨润土)BS+100DASBS+50DASBS+25DASBSCK(膨润土)的趋势,且对Cr(VI)、Cd2+的最大吸附量(qm)分别为85.92 mmol·kg-1(100BS+150DAS)和321.89 mmol·kg-1(100BS+150DAS).各供试土样对Cr(VI)和Cd2+的吸附均表现为自发、焓增和熵增的特征,升温可增加其对Cr(VI)和Cd2+的最大吸附量.酸性环境有利于各修饰土样对Cr(VI)的吸附,而不利于对Cd2+的吸附.离子强度增加均降低了各修饰土样对Cr(VI)和Cd2+的吸附.     

Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu^2 +–Fe^3 + combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn^2 +–Fe^3 + combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn^2 +–Fe^3 +, while together with 0.2 mmol/L N,N′-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the F_OF₁-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe^3 + was added separately disappeared in both cases, which might be a result of competing processes between Fe^3 + and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.