Humic substances. Part III. sorptive interactions with environmental chemicals†

The formation of covalent binding to DNA of a carcinogen is now widely accepted to represent a classical mechanism of tumour induction in mammals. This mechanism does not operate with metals since no covalent binding of these agents to DNA does occur. Nevertheless, somatic mutations as typical consequences of DNA‐damage have been reported to be induced by metals in various model systems. Beside DNA‐alkylation such damages can be caused by changes in the conformation of DNA or in the fidelity of DNA‐repair. The activity of the repair enzymes DNA‐polymerases is indeed impaired by many metal ions at least in vitro. It is not yet established whether these mechanisms are also important in the intact mammalian organism. Much evidence has accumulated during the last years that a disturbance of the balance of cations and especially metal ions represents another possible mechanism of tumour induction. The tumours found with high doses of chelating agents such as nitrilo‐triacetic acid (NTA) have to be discussed in this context. Since most—if not—all of the speculative mechanisms of metal carcinogenesis resemble classical pharmacological reactions the existence of a threshold level is likely. So metal carcinogenesis will not be a problem of the environmental contamination at trace levels but a problem of occupational medicine.     

过氧化氢/草酸铁体系太阳光催化降解染料废水的研究

以过氧化氢 /草酸铁络合物作光氧化剂 ,利用太阳光对 10种水溶性染料模拟废水进行了光氧化降解试验研究 ,发现在日光照射下 ,过氧化氢 /草酸铁络合物能使染料溶液迅速降解。以活性艳蓝KN R为代表 ,研究各种因素对光降解的影响。结果表明 ,溶液pH为 2 0～ 4 0时 ,光降解速率快 ;溶液中Fe3 + 与草酸根的摩尔比为 1∶3时 ,光解效果最好 ;提高H2 O2 浓度可以提高光降解速率 ,但H2 O2 的利用率会降低。     

Antimony sorption at gibbsite-water interface

Antimony (Sb) is extensively used in flame retardants, lead-acid batteries, solder, cable coverings, ammunition, fireworks, ceramic and porcelain glazes and semiconductors. However, the geochemical fate of antimony (Sb) remained largely unexplored. Among the different Sb species, Sb (V) is the dominant form in the soil environment in a very wide redox range. Although earlier studies have examined the fate of Sb in the presence of iron oxides such as goethite and hematite, few studies till date reported the interaction of Sb (V) with gibbsite, a common soil Al-oxide mineral. The objective of this study was to understand the sorption behavior of Sb (V) on gibbsite as a function of various solution properties such as pH, ionic strength (I), and initial Sb concentrations, and to interpret the sorption-edge data using a surface complexation model. A batch sorption study with 20 g L⁻¹ gibbsite was conducted using initial Sb concentrations range of 2.03-16.43 μM, pH values between 2 and 10, and ionic strengths (I) between 0.001 and 0.1 M. The results suggest that Sb (V) sorbs strongly to the gibbsite surface, possibly via inner-sphere type mechanism with the formation of a binuclear monodentate surface complex. Weak I effect was noticed in sorption-edge data or in the isotherm data at a low surface coverage. Sorption of Sb (V) on gibbsite was highest in the pH range of 2-4, and negligible at pH 10. Our results suggest that gibbsite will likely play an important role in immobilizing Sb (V) in the soil environment.     

UV-vis/草酸铁络合物/H2O2法处理垃圾渗滤液的研究

在紫外光照下,利用H2O2和草酸铁络合物对垃圾渗滤液进行了处理,探讨了紫外光照时间、pH值、fenton试剂、草酸铵对垃圾渗滤液中CODCr去除率的影响.结果表明:UV-vis/草酸铁络合物/H2O2法对垃圾渗滤液CODCr去除率有较好的效果,当操作条件是:pH取3,反应时间为1 h,H2O2投加量为1.4 mL,H2O2/FeSO4·7H2O投加比(摩尔比)为5∶1,草酸铵投加量为5.5 mL时,CODCr的去除率达到了78.8%.     

Pteris vittata – Revisited: Uptake of As and its speciation, impact of P, role of phytochelatins and S

Pteris vittata is known to hyperaccumulate As but the mechanism is poorly understood. We found an increase of As concentration with increasing soil solution As concentrations, but P application had no impact, although plant P concentrations responded to different rates of P supply. As in fronds was dominantly (82–89%) present in the form of AsIII. In roots we detected 45% as AsIII which is higher than reported in previous studies and supports substantial As-reduction to take place in roots. We detected PC2/3GS–AsIII, PC2–GS–AsIII and (PC2)2–AsIII in increasing amounts with application of As. The total amount of PC was in the range reported previously and far too small to assign a significant role in As detoxification to PCs. The close correlation between S and As in fronds and the lack of data on sulphur uptake and metabolism indicates the need for a detailed investigation on sulphur nutritional status and As metabolism in P. vittata.     

Reduced activity of alkaline phosphatase due to host–guest interactions with humic superstructures

Nuclear Magnetic Resonance (NMR) spectroscopy was applied to directly study the interactions between the alkaline phosphatase enzyme (AP) and two different humic acids from a volcanic soil (HA-V) and a Lignite deposit (HA-L). Addition of humic matter to enzyme solutions caused signals broadening in ¹H-NMR spectra, and progressive decrease and increase of enzyme relaxation (T₁ and T₂) and correlation (τ_C) times, respectively. Spectroscopic changes were explained with formation of ever larger weakly-bound humic–enzyme complexes, whose translational and rotational motion was increasingly restricted. NMR diffusion experiments also showed that the AP diffusive properties were progressively reduced with formation of large humic–enzyme complexes. The more hydrophobic HA-L affected spectral changes more than the more hydrophilic HA-V. ¹H-NMR spectra also showed the effect of progressively greater humic–enzyme complexes on the hydrolysis of an enzyme substrate, the 4-nitrophenyl phosphate disodium salt hexahydrate (p-NPP). While AP catalysis concomitantly decreased NMR signals of p-NPP and increased those of nitrophenol, addition of humic matter progressively and significantly slowed down the rate of change for these signals. In agreement with the observed spectral changes, the AP catalytic activity was more largely inhibited by HA-L than by HA-V. Contrary to previous studies, in which humic–enzyme interactions were only indirectly assumed from changes in spectrophotometric behavior of enzyme substrates, the direct measurements of AP behavior by NMR spectroscopy indicated that humic materials formed weakly-bound host–guest complexes with alkaline phosphatase, and the enzyme catalytic activity was thereby significantly inhibited. These results suggest that the role of extracellular enzymes in soils may be considerably reduced when they come in contact with organic matter dissolved in the soil solution.     

On the dissolution kinetics of humic acid particles. Effect of monocarboxylic acids

The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4–10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid < acetic acid < propionic acid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment.     

ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.     

二(2-乙基己基)磷酸(D2EHPA)萃取Fe3+的萃合物结构

以分离制革污泥淋滤液中Fe3+和Cr3+为背景,研究了二(2-乙基己基)磷酸(D2EHPA)分别从氯化物和硫酸盐介质中萃取Fe3+的效率,并应用配位化学理论结合MINTEQ程序,推测了可能的萃合物结构,讨论了D2EHPA浓度、溶液pH、溶液中阴离子对萃合物结构的影响.结果表明,在低Cl-浓度介质中,萃合物结构为FeA3...