The interaction of boron with goethite: experiments and CD-MUSIC modeling

Boron (B) is an essential element for plants and animals growth that interacts with mineral surfaces regulating its bioavailability and mobility in soils, sediments, and natural ecosystems. The interaction with mineral surfaces is quite important because of a narrow range between boron deficiency and toxicity limits. In this study, the interaction of boric acid with goethite (α-FeOOH) was measured in NaNO₃ background solution as a function of pH, ionic strength, goethite and boron concentration representing as adsorption edges and isotherms. Boron adsorption edges showed a bell-shaped pattern with maximum adsorption around pH 8.50, whereas adsorption isotherms were rather linear. The adsorption data were successfully described with the CD-MUSIC model in combination with the Extended Stern (ES) model. The charge distribution (CD) of inner-sphere boron surface complexes was calculated from the geometry optimized with molecular orbital calculations applying density functional theory (MO/DFT). The CD modeling suggested dominant binding of boric acid as a trigonal inner-sphere complex with minor contributions of a tetrahedral inner-sphere complex (at high pH) and a trigonal outer-sphere complex (at low pH). The interpretation with the CD model is consistent with the spectroscopic observations.     

Review of the complexation of tetravalent actinides by ISA and gluconate under alkaline to hyperalkaline conditions

Isosaccharinic (ISA) and gluconic acids (GLU) are polyhydroxy carboxylic compounds showing a high affinity to metal complexation. Both organic ligands are expected in the cementitious environments usually considered for the disposal of low- and intermediate-level radioactive wastes. The hyperalkaline conditions imposed by cementitious materials contribute to the formation of ISA through cellulose degradation, whereas GLU is commonly used as a concrete additive. Despite the high stability attributed to ISA/GLU complexes of tetravalent actinides, the number and reliability of available experimental studies is still limited. This work aims at providing a general and comprehensive overview of the state of the art regarding Th, U(IV), Np(IV), and Pu(IV) complexes with ISA and GLU.In the presence of ISA/GLU concentrations in the range 10^− 5–10^− 2 M and absence of calcium, An(IV)(OH)_x(L)_y complexes (An(IV) = Th, U(IV), Np(IV), Pu(IV); L = ISA, GLU) are expected to dominate the aqueous speciation of tetravalent actinides in the alkaline pH range. There is a moderate agreement among their stability, although the stoichiometry of certain An(IV)-GLU complexes is still ill-defined. Under hyperalkaline conditions and presence of calcium, the species CaTh(OH)₄(L)₂(aq) has been described for both ISA and GLU, and similar complexes may be expected to form with other tetravalent actinides.In the present work, the available thermodynamic data for An(IV)–ISA/GLU complexes have been reviewed and re-calculated to ensure the internal consistency of the stability constants assessed. Further modelling exercises, estimations based on Linear Free-Energy Relationships (LFER) among tetravalent actinides, as well as direct analogies between ISA and GLU complexes have also been performed. This approach has led to the definition of a speciation scheme for the complexes of Th, U(IV), Np(IV) and Pu(IV) with ISA and GLU forming in alkaline to hyperalkaline pH conditions, both in the absence and presence of calcium.     

Influence of complexation on lead(II) and cadmium(II) percolation through a clay liner

Wastes are usually stocked in waste disposals without any pre-treatment. Runoff waters lead to the formation of leachates containing mineral and organic pollutants. In order to prevent groundwater contamination, a double barrier is placed on the landfill bottom. The first one is an active barrier made up of a draining system and a geomembrane, and the second one, consisting of a clay liner allowing pollutant retention, is considered as a passive system. The aim of this work is to evaluate the complexation impact on the organic and inorganic retention. Percolations on columns filled with clay are performed, which allow a better knowledge of the transfer of metallic pollutants, complexed or not, through a model porous media, considering charge and conditional stability of complexes.     

络合萃取法处理甲苯二异氰酸酯氢化废水的试验研究

研究络合萃取处理甲苯二异氰酸酯（TDI）生产氢化废水的工艺过程,考察了pH值、萃取相比、萃取温度、萃取时间等因素对萃取效果的影响,并通过正交试验对工艺条件进行优化,结果表明：采用酸性含磷类萃取剂,煤油为稀释剂,在pH值为8.0、萃取温度为25℃、萃取时间为3 min、萃取相比为1.5︰1优化条件下,对氢化废水中苯胺类的萃取率大于97％。负载萃取剂以31%的盐酸作反萃剂,反萃取相比为20︰1条件下可实现完全再生,反萃液经处理可回收2,4-二氨基甲苯和2,6-二氨基甲苯。     

Unravelling the effects of complexation of transition metal ions on the hydroxylation of catechol over the whole pH region

Catechol pollutants (CATPs) serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes. Little information is available on the effects of complexation of metal ions on CATPs degradation. This work presents a systematical study of •OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes (AOPs). Results show that the pH-dependent complexation of metal ions (Zn²⁺, Cu²⁺, Ti⁴⁺ and Fe³⁺) promotes the deprotonation of catechol under neutral and even acidic conditions. The radical adduct formation (RAF) reactions are both thermodynamically and kinetically favorable for all dissociation and complexation species, and OH/O⁻ group-containing C positions are more vulnerable to •OH attack. The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation. At pH 7, the apparent rate constant (k_app) values for different systems follow the order of catechol+Ti⁴⁺ ≈ catechol+Zn²⁺ > catechol+Cu²⁺ > catechol+Fe³⁺ > catechol. The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs. The toxicity assessment indicates that the •OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.