腐殖酸-高岭土复合体形成机制及对三氯乙烯的吸附

为探究土壤中有机组分与无机矿质组分相互作用的机制,以腐殖酸代表有机质、高岭土代表无机矿质,制备不同有机质含量的腐殖酸-高岭土复合体模拟样品,进行三氯乙烯的吸附实验研究.结果表明,各吸附剂样品对三氯乙烯的吸附符合Freundlich等温模型,且吸附量的实际值与理论叠加值有明显差异,说明复合体样品中腐殖酸与高岭土之间存在相互作用.结合红外光谱、比表面积孔分析等多类表征,推测腐殖酸与高岭土相互作用的机制为:腐殖酸含量较低时,腐殖酸分子首先分布于高岭土表面的活性位点上,随着腐殖酸含量的增加(有机质-矿质质量比O/M为0.02~0.04),部分腐殖酸分子进入高岭土表面的孔隙,达到相对稳定后腐殖酸分子继续作用于高岭土表面形成第一层腐殖酸分子膜(O/M为0.04~0.08),随着腐殖酸含量继续增加(O/M为0.08~0.10),更多的腐殖酸分子通过与第一层腐殖酸膜相互作用而在高岭土表面进行第二层叠加,同时第一层被压缩,第二层叠加相对稳定后(O/M为0.10~0.16),仍有部分腐殖酸叠加至第二层之上进行第三层叠加,随后内层腐殖酸进一步被压缩(O/M为0.16~0.24),但可能仍有少量腐殖酸分子和聚集体继续下一层叠加.     

Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm², pH 4.09, 80 mmol/L Na₂SO₄, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm² (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.     

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide–natural organic matter complexes

The phosphorus(P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid(HA) complexes were analyzed using the ultrafiltration method in this study.With an initial P concentration of 20 mg/L(I =0.01 mol/L and pH = 7),it was shown that the colloid(1 kDa-0.45 μm) component of P accounted for 10.6%,11.6%,6.5%,and 4.0%of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite(FH),goethite(GE),ferrihydrite-humic acid complex(FH-HA),goethite-humic acid complex(GE-HA),respectively.The 1 kDa component of P was still the predominant fraction in the supernatant,and underestimated colloidal P accounted for 2.2%,55.1%,45.5%,and 38.7%of P adsorption onto the solid surface of FH,FH-HA,GE and GE-HA,respectively.Thus,the colloid P could not be neglected.Notably,it could be interpreted that Fe~(3+) hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant.And colloidal adsorbent particles co-existing in the supernatant were another important reason for it.Additionally,dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant.Ultimately,we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P,even when considering other contaminants such as organic pollutants,heavy metal ions,and arsenate at the sediment/soil-water interface in the real environment.     

Using a fire propagation model to assess the efficiency of prescribed burning in reducing the fire hazard

We examined how fire hazard was affected by prescribed burning and fuel recovery over the first six years following treatment. Eight common Mediterranean fuel complexes managed by means of prescribed burning in limestone Provence (South-Eastern France) were studied, illustrating forest and woodland, garrigue and grassland situations. The coupled atmosphere-wildfire behaviour model FIRETEC was used to simulate fire behaviour (ROS, intensity) in these complex vegetations. The temporal threshold related to the effectiveness of prescribed burning in reducing the fire hazard was assessed from derivated fuel dynamics after treatment. The study showed that prescribed burning treatment was effective for the first two years in most of the Mediterranean plant communities analysed. Thereafter, all forests and shrublands were highly combustible with a fire line intensity of more than 5000 kW/m except for pine stands with or without oak (medium intensity of 2000 kW m⁻¹ 3 years after treatment). Low fire line intensity (900 kW m⁻¹) was obtained for grassland which was entirely treatment-independent since the resprouter hemicryptophyte, Brachypodium retusum, is highly resilient to fire. Fire behaviour was greatly affected by fuel load accumulation of Quercus ilex in woodland, and by standing necromass of Rosmarinus officinalis in treated garrigue. Pure pine stands with shrub strata similar to garrigue showed a lower fire intensity due to wind speed decrease at ground level under tree canopy, underlining the advantage of maintaining a proportion of canopy cover in strategic fuel-break zones.     

环糊精对Fe(Ⅲ)引发双酚A光降解的影响

环糊精口α-CD、β-CD和γ-CD能分别与双酚A形成1:1主-客体包结物.在250W金属卤化物灯(λ≥365 nm)光照下,研究了在Fe(Ⅲ)-OH配合物体系中,不同环糊精对双酚A光降解的影响.结果表明,β-CD能较大地促进双酚A的光降解,α-CD次之,而γ-CD对双酚A的光降解存在一定的抑制;并且CDs浓度的变化对双酚A光降解的初始速率有明显的影响.双酚A光降解的初始速率随着β-CD和α-CD浓度增大而增加,当β-CD=60μmol/L时达到最大,然后随着浓度增大而降低,而BPA的光降解初始速率随γ-CD浓度的增加总的趋势是减小的.通过计算机软件Gaussian98,采用PM3方法模拟了环糊精与双酚A的包结行为,进一步说明3种环糊精与双酚A形成主-客体包结物对光降解的影响.     

Mutagenic activity of transition‐metal complexes: Relation structure‐mutagenic and antibacterial activity for some Pd(II), Pt(II) and Rh(I) complexes†

The inhibitory and mutagenic action of some Pd(II), Pt(II) and Rh(I) complexes towards various bacterial strains has been evaluated, and some correlations have been found between the chemical behaviour of the complexes and their selective biological activity: most of the complexes cause only a DNA damage repaired by the excision repair system. Particularly, the Rh(I) complexes used in this work show selective antibacterial effects on defective but no effect on wild‐type strains.     

Preparation,characterization and toxic activity of oxovanadium(IV) mixed-ligand complexes

New oxovanadium(IV) mixed-ligand complexes of the general composition [VO(L)(A)], where KHL?=?potassium salt of salicylideneglycine, A¹?=?bis(benzylidene)ethylenediamine, A²?=?bis (acetophenone)ethylenediamine, A³?=?di(2-pyridyl)amine, A⁴?=?bis(benzylidene)-1,8-diaminonaphthalene, A⁵?=?thiophene-o-carboxaldene-aniline, A⁶?=?thiophene-o-carboxaldene-p-anisidine, have been synthesized by the interaction of these ligands with vanadyl sulphate. The mixed-ligand complexes have been characterized on the basis of elemental analysis, magnetic measurements, electronic and infrared spectra. An octahedral structure has tentatively been assigned to all of the mixed-ligand complexes. The mixed-ligand complexes show higher toxic activity against the Salmonella typhi, Escherichia coli and Serratia mercescen as compared to the ligands, vanadyl sulphate and control (dimethyl sulphoxide). The mixed-ligand complexes were also tested against a standard drug (tetracycline).     

Synthesis,structural elucidation,electro-chemical behaviour and fungitoxic activity of transition metal(II) mixed-ligand complexes with some Schiff bases

The Schiff bases, potassium salt of salicylidene-β-alanine [KHL], bis(benzylidene)ethylenediamine [SB¹] and thiophene-o-carboxaldene-p-toluidine [SB²], and mixed-ligand complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have been prepared. They were characterized by elemental analyses, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.), infrared spectra and electronic spectra. The mixed-ligand complexes were found to have the general composition [M(L)(SB)(H₂O)]. All the mixed-ligand complexes were found to have six-coordinated octahedral geometry. The fungitoxic activity of the ligands, metal salts, control (DMSO), bavistin, emcarb, and mixed-ligand complexes were screened against Aspergillus niger, Fusarium oxysporum and Aspergillus flavus. All the mixed-ligand complexes show higher fungitoxic activity as compared to the Schiff bases, metal nitrate and control (dimethyl sulphoxide, DMSO), and moderate fungitoxic activity as compared to the fungicides (bavistin and emcarb).     

Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of pH and fluoride at different molar ratios of fluoride to Al (R_F:Al) on the removal of cadmium (Cd²⁺) and phosphate by Al coagulation. Fluoride at R_F:Al ≥ 3:1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R_F:Al of 10:1 whereas at lowered R_F:Al (i.e., ≤ 6:1), an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at pH 7 and 8 and that of phosphate at pH 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R_F:Al. The Al fluoride interactions include the formation of Al–F complexes and the adsorption of fluoride onto Al(OH)₃ precipitates, i.e., the formation of Al(OH)_nF_m. Al–F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower pH. Al–F complexes at high R_F:Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R_F:Al shows little effect on Al coagulation behavior towards Cd^2 + and phosphate, and the spent defluoridation adsorbent, i.e., aluminum (Al) hydro(oxide) with adsorbed fluoride at R_F:Al of below 0.1:1, may be reclaimed as a coagulant after being dissolved.