UV/草酸铁络合物光解对硫磷的研究

研究了紫外光（UV）/草酸铁络合物对对硫磷的光解作用,结果表明,UV/草酸铁络合物能快速有效地光解对硫磷,且较UV/TiO2的光解效果好。对硫磷光解率随着其初始浓度的增加而降低;pH为3-5时其光解速率最快;[Fe(Ⅲ）]与[OX^2-]之比（OX^2-代表草酸根）和溶液中的溶解氧对其光解有显著影响。     

污染场地不同深度土壤有机-矿质复合体中有机氯农药的分布

采用物理方法将某农药厂土壤分成4种粒径的有机-矿质复合体组分,粘粒、粉粒、细砂和粗砂,研究有机氯农药在土壤不同有机-矿质复合体组分中的分布特征及有机质含量对污染物质赋存分布的影响。结果表明,粉粒组分中污染物质六六六含量较高,粘粒组分中滴滴涕含量较高。粘粒和粉粒组分中污染物质的含量与相应的有机质含量间呈现显著相关关系,而在细砂和粗砂中这种相关性不显著。lgKoc值与污染物质含量的相关性分析结果与有机质的相关性分析结果相似。有机质可能是影响场地土壤有机氯农药分布的重要因素之一。本研究的结果可为污染场地的风险控制和环境修复提供基础依据。     

Ca~(2+)对煤中含氮活性基团阻化效应研究

为揭示CaCl2抑制煤炭自燃发生的机理,提高阻化效果,采用Gaussian03软件包,对Ca2+与煤中含N活性基团形成的配位体的结构及分子前沿轨道、稳定化能、自然键轨道和净电荷布居、电荷转移进行系统研究。结果表明,Ca2+能够与煤中含N活性基团形成二配体、三配体及四配体配合物,形成四配体的稳定化能与前沿轨道能级能隙差较大,说明四配体配合物最为稳定,而且形成配合物后,煤含N活性结构中的-NH2基团对前沿轨道的贡献大大减少,同时轨道能级大幅增加,增加了煤活性结构的稳定性,提高了煤活性结构的抗氧化性。     

Adsorption of picloram on clays nontronite,illite and kaolinite: equilibrium and herbicide-clays surface complexes

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite?<?illite?<?nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.     

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.     

有机氯农药污染场地表层土壤有机-矿质复合体中污染物的分布

采用湿法物理分级方法将北京市某农药厂遗留场地表层土壤分成4种粒径的有机-矿质复合体组分:粘粒、粉粒、细砂和粗砂(<2 ìm、2～20ìm、20～200ìm、>200 ìm),研究有机氯农药在其中的分布特征及土壤不同有机-矿质复合体组分中有机质和矿物质组成的差异对污染物赋存分布的影响.结果表明,污染物质六六六(HCHs)和滴滴涕(DDTs)在粉粒中分布较多,含量分别为463.1 mg·kg-1和1225.6 mg·kg-1,粗砂中分布最少,含量仅为157.8 mg·kg-1和384.5 mg·kg-1.1gKoc与污染物质在粘粒上的分布量存在显著的相关关系.通过对有机-矿质复合体进行x射线衍射分析发现,场地土壤粘粒和粉粒中粘土矿物含量较高.由于有机-矿质复合体中粘土矿物组成和含量存在差别,这在一定程度上影响了污染物质在其中的分布.同时,所研究的场地土壤中污染物易于富集的粒径范围与报道的北京大气颗粒物上HCHs和DDTs有较多吸附的粒径相近.因此,应当重视污染场地表层土壤对大气污染的可能贡献及其环境风险.