Competitive effect of iron(III) on metal complexation by humic substances: characterisation of ageing processes

Aiming at an assessment of counteractive effects on colloid-borne migration of actinides in the event of release from an underground repository, competition by Fe(III) in respect of metal complexation by dissolved organic matter was investigated for the example of Eu(III) as an analogue of trivalent actinides. Complexation with different humic materials was examined in cation exchange experiments, using (59)Fe and (152)Eu as radioactive tracers for measurements in dilute systems as encountered in nature. Competitive effects proved to be significant when Fe is present at micromolar concentrations. Flocculation as a limiting process was attributed to charge compensation of humic colloids. Fe fractions bound to humic acids (HA) were higher than 90%, exceeding the capacity of binding sites at high Fe concentrations. It is thus concluded that the polynuclear structure of hydrolysed Fe(III) is maintained when bound to HA, which is also inferred from UV-Vis spectrometry. The competitive effect was found to be enhanced if Fe and HA were in contact before Eu was added. Depending on the time of Fe/HA pre-equilibration, Eu complexation decreased asymptotically over a time period of several weeks, the amount of bound Fe being unchanged. Time-dependent observations of UV-Vis spectra and pH values revealed that the ageing effect was due to a decline in Fe hydrolysis rather than structural changes within HA molecules. Fe polycations are slowly degraded in contact with humic colloids, and more binding sites are occupied as a consequence of dispersion. The extent of degradation as derived from pH shifts depended on the Fe/HA ratio.     

Effect of humic matter on metal adsorption onto clay materials: Testing the linear additive model

Migration of contaminants with low affinity for the aqueous phase is essentially governed by interaction with mobile carriers such as humic colloids. Their impact is, however, not sufficiently described by interaction constants alone since the humic carriers themselves are subject to a solid–liquid distribution that depends on geochemical parameters.In our study, co-adsorption of the REE terbium (as an analogue of trivalent actinides) and humic acid onto three clay materials (illite, montmorillonite, Opalinus clay) was investigated as a function of pH. ¹⁶⁰Tb(III) and ¹³¹I-labelled humic acid were employed as radiotracers, allowing experiments at very low concentrations to mimic probable conditions in the far-field of a nuclear waste repository. Humate complexation of Tb was examined by anion and cation exchange techniques, also considering competitive effects of metals leached from the clay materials.The results revealed that desorption of metals from clay barriers, occurring in consequence of acidification processes, is generally counteracted in the presence of humic matter. For all clay materials under study, adsorption of Tb was found to be enhanced in neutral and acidic systems with humic acid, which is explained by additional adsorption of humic-bound Tb.A commonly used composite approach (linear additive model) was tested for suitability in reconstructing the solid–liquid distribution of Tb in ternary systems (Tb/humic acid/clay) on the basis of data determined for binary subsystems. The model can qualitatively explain the influence of humic acid as a function of pH, but it failed to reproduce our experimental data quantitatively. It appears that the elementary processes (metal adsorption, metal–humate complexation, humic acid adsorption) cannot be considered to be independent of each other. Possible reasons are discussed.     

Competitive complexation of metal ions with humic substances

The surface complexation model was applied to simulate the competitive complexation of Ni, Ca and Al with humic substances. The presence of two types of binding sites in humic acid, carboxylic and phenolic functional groups, were assumed at both low and high pH conditions. Potentiometric titrations were used to characterize the intrinsic acidity constants of the two binding sites and their concentrations. It was found that the diffuse-layer model (DLM) could fit the experimental data well under different experimental conditions. Ni and Ca ions strongly compete with each other for reactions with the humic acid but Al showed little influence on the complexation of either Ni or Ca due to its hydrolysis and precipitation at pH approximately 5. The surface complexation constants determined from the mono-element systems were compared with those obtained from the multiple-element system (a mixture of the three metal ions). Results indicate little changes in the intrinsic surface complexation constants. Modeling results also indicate that high concentrations of Ca in the contaminated groundwater could strongly inhibit the complexation of Ni ions whereas an increase in pH and the humic concentration could attenuate such competitive interactions. The present study suggests that the surface complexation model could be useful in predicting interactions of the metal ions with humic substances and potentially aid in the design of remediation strategies for metal-contaminated soil and groundwater.     

两种不同形态的铝盐混凝剂的吸附电中和特征

通过吸附历时过程,饱和吸附量,吸附过程Ｎａ＾＋离子交换释放,絮凝前后高岭土微粒的ζ电位测定等实验考察ＡｌＣｌ３（ＡＣ）和聚合铝两种不同形态的铝盐对高岭土悬浮水样的吸附电中和特征,并探讨了其作用机理。     

Joint influence of surfactants and humic matter on PAH solubility. Are mixed micelles formed?

Mobilization of polycyclic aromatic hydrocarbons (PAH) by surfactants, present at contaminated sites or deliberately introduced for remediation purposes, is inevitably associated with the influence of humic substances, which are ubiquitous in natural systems. Therefore, the solubilizing effects of anthropogenic and natural amphiphiles must be considered in their combined action since synergistic or antagonistic effects may be expected, for instance, as a consequence of mixed micellization.

In this paper, solubilization of ¹⁴C-labeled pyrene in single-component and mixed solutions of surfactants and humic acid (coal-derived) was investigated up to the micellar concentration range. At low concentrations, antagonistic effects were observed for systems with cationic as well as anionic surfactants. Solubility enhancements in the presence of humic acid were canceled on addition of a cationic surfactant (DTAB) since charge compensation at humic colloids entailed precipitation. Solubility was also found to be decreased in the presence of an anionic surfactant (SDS), which was attributed to a competitive effect in respect of pyrene–humic interaction. This explanation is based on octanol–water partitioning experiments with radiolabeled humic acid, yielding evidence of different interaction modes between humic colloids and cationic/anionic surfactants. At higher concentrations, the effects of humic acid and SDS were found to be additive. Thus, a formation of mixed micelles is very unlikely, which was confirmed by size exclusion chromatography of mixed systems. It can be concluded that remediation measures on the basis of micellar solubilization are not significantly affected by the presence of natural amphiphilic compounds.     

Migration of uranium(IV)/(VI) in the presence of humic acids in quartz sand: a laboratory column study

The migration behavior of U(IV) and U(VI) in the presence of humic acid was studied in a quartz sand system. Laboratory column experiments were performed using humic acid, U(VI) in humic acid absence, U(IV) and U(VI) in humic acid presence, and for comparison a conservative tracer. In experiments using humic acid, both redox species of U migrate nearly as fast as the conservative tracer. Humic acid accelerates the U(VI) breakthrough compared to the humic acid-free system. There are strong indications for a similar effect on the U(IV) transport. At the same time, a part of U(IV) and U(VI) associated with the humic acid is immobilized in the quartz sand due to humic colloid filtration thus producing a delaying effect. Tailing at a low concentration level was observed upon tracer elution. The experimental breakthrough curves were described by reactive transport modeling using equations for equilibrium and kinetic reactions. The present study demonstrates that humic acids can play an important role in the migration of actinides. As natural organic matter is ubiquitous in aquifer systems, the humic colloid-borne transport of actinides is of high relevance in performance assessment.     

混凝絮凝法去除腐质酸的研究

进行了混凝絮凝法去除水中腐殖酸的研究，结果表明，同传统的絮凝剂相比，微生物絮凝剂不仅用量少，去除效果好(去除率可达60％)，而且不产生二次污染，可应用于废水特别是给水中腐殖酸的去除工艺中，对絮凝剂的絮凝机理进行了初步研究，研究表明，微生物絮凝剂去除腐殖酸主要是通过架桥完成的，不同于A12(SO4)3的电中和机理。     

Purification of industrial phosphoric acid (54 %) using Fe-pillared bentonite

The current problem of excess impurities in industrial phosphoric acid (IPA) 54 % P₂O₅ makes phosphates industries look toward low-cost but efficient adsorbents. In the present study, iron-oxide-modified bentonite (Fe-PILB) was prepared and investigated as a possible adsorbent for the removal of organic matter (OM) like humic acid (HA), chromium (Cr(III)), and zinc (Zn(II)) from IPA aqueous solutions. These adsorbents were characterized using XRD, TEM, and BET. The adsorption of impurities is well described by the pseudo-second-order model. The results indicate that Fe-PILB has a good ability to resist co-existing anions and the low-pH condition of IPA and owns a relatively high-removal capacity of 80.42 and 25 % for OM, Cr(III), and Zn(II). The mechanism of adsorption may be described by the ligand and ion exchange that happened on the active sites. The selected order of adsorption OM?>?Cr³⁺?>?Zn²⁺ showed the importance of the competitive phenomenon onto bentonite materials’ pore adsorption. For the adsorption of OM at the low pH of IPA, H-bond complexation was the dominant mechanism. From the adsorption of heavy metals and OM complex compounds contained in IPA 54 % on Fe-PILB, the bridging of humic acid between bentonite and heavy metals (Zn(II) or Cr(III)) is proposed as the dominant adsorption mechanism (bentonite-HA-Me). Overall, the results obtained in this study indicate Fe-pillared bentonite possesses a potential for the practical application of impurity (OM, Zn(II), and Cr(III)) removal from IPA aqueous solutions.     

Bioavailability of HOC depending on the colloidal state of humic substances: a case study with PCB-77 and Daphnia magna

Condensed organic matter with higher affinity for hydrophobic organic compounds (HOC) is currently held responsible for slow desorption and concomitant lower bioavailabilities of HOC in sediments and soils. In an experiment with Daphnia magna and IHSS Peat Humic Acid (PHA), we showed that the bioconcentration factor (BCF) of 3,3',4,4'-tetrachlorobiphenyl (PCB-77) was directly related to the charge of the humic colloid, as predicted by the metal-humic binding model WHAM. Consistent with the type of binding to the humic acid (counter-ion accumulation vs. specific binding), increasing the concentration of Na+ and Ca2+ ions generated opposite effects on colloid charge and HOC binding by the humic acid. Condensation as a colloidal phenomenon in solution as well as on surfaces needs to be addressed as a contributor to lower bioavailabilities and, possibly, to slower desorption kinetics.     

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation–proton exchange with HA (i.e., pK_MHA) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK_MHA values is more suitable for use in Model V for the simulation of REE complexation with HA.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.     

Complexation of arsenate with humic substance in water extract of compost

The interactions of environmental toxicants with organic substances affect the speciation and dynamics, and subsequent toxicity, mobility, and fate of toxicants in the environment. For the purpose of understanding the complexation of As(V) with humic substances, arsenate-containing solutions with As concentrations from 1 to 8 mg l⁻¹ were prepared to react with the water extract of compost (WEC). All the reaction systems including the control were incubated for 48 h at 25 °C. The complexation of As(V) with humic substance was examined by dialysis and ion exchange techniques. From 30% to 51% of added As(V) reacted with organic substance in WEC to form an As–metal–organic complex. This was verified as a hydrophobic organic fraction after separation of As–metal–organic complex fraction from the hydrophilic fraction by XAD-8 resin. The complex substance was also identified as a humic substance by the method of proton binding formation function determination. This suggests that cations, such as Ca and Mg, and especially Fe, Al, and Mn act in cation bridging in the complexation of As(V) with humic substance. The role of metals in the complexation of As(V) with humic substance in terrestrial and especially aquatic environments thus merits close attention.     

The role of humic acid in the toxicity of arsenite to the diatom Navicula sp.

Dissolved organic matter (DOM) affects arsenite [As(III)] toxicity by altering its sorption equilibrium at the cell wall interface. A better understanding of such mechanism is of great importance to assess As(III) ecotoxicity in aquatic systems. Batch experiments were conducted to study the effects of DOM on the regulation of As(III) sorption and toxicity in the diatom Navicula sp. The influence of humic acid (HA) on As(III) toxicity was assessed by measuring algal growth, chlorophyll a, and reactive oxygen species (ROS), whereas As(III) mobility across the cell wall was estimated by determining the concentration of intracellular, cell-wall-bound, and free As(III) ions in cell media. Results showed that the effects of HA on arsenite toxicity varied depending on various combinations of As(III)-HA concentrations. EC₅₀ had an approximate threefold increase from 8.32 (HA-free control) to 22.39 μM (at 20 mg L^?1 HA) when Navicula sp. was exposed to 1.0–100.0 μM of As(III), compared to an overall low complexation ratio of HA-As(III) in a range of 0.91–6.00 %. The cell wall-bound and intracellular arsenic content decreased by 19.8 and 20.3 %, respectively, despite the lower arsenite complexation (2.10?±?0.16 % of the total As). Meanwhile, intracellular ROS was decreased by 12.6 % in response to 10.0 μM As(III) and 10 mg L^?1 HA vs. the HA-free control. The significant contrast indicated that complexation alone could not explain the HA-induced reduction in arsenite toxicity and other factors including HA–cell surface interactions may come into play. Isotherms describing adsorption of HA to the Navicula sp. cells combined with morphological data by scanning electron microscopy revealed a protective HA floccule coating on the cell walls. Additional Fourier transform infrared spectroscopic data suggested the involvement of carboxylic groups during the adsorption of both HA and As(III) on the Navicula sp. cell surface. Collective data from this study suggest that cell wall-bound HA can moderate As(III) toxicity through the formation of a protective floccule coating occupying As(III) sorption sites and decreased effective functional groups capable of binding As(III). Our findings imply that As(III) toxicity can be alleviated due to the increased hindrance to cellular internalization of As(III) in the presence of naturally abundant DOM in water.     

Role of magnetite and humic acid in radionuclide migration in the environment

Sorption of ¹³⁷Cs, ⁹⁰Sr, ¹⁵⁴Eu and ¹⁴¹Ce by magnetite has been studied at varying pH (4 to 11) in the presence and absence of humic acid. The sorption studies have also been carried out at varying ionic strength (0.01 to 0.2 M NaClO₄) and humic acid concentration (2 to 20 mg/L). Percentage sorption of ¹³⁷Cs and ⁹⁰Sr was found to be pH dependent, with the sorption increasing with increasing pH of the suspension. At any pH, the percentage sorption of ⁹⁰Sr was higher than that of ¹³⁷Cs. The results have been explained in terms of the electrostatic interaction between the positively charged metal ions and the surface charge of the magnetite which becomes increasingly negative with increasing pH. On the other hand, ¹⁵⁴Eu and ¹⁴¹Ce were found to be strongly sorbed by the magnetite at all pH values, with the sorption being independent of pH. The strong sorption of trivalent and tetravalent metal ions suggests the role of complexation reactions during sorption, apart from the electrostatic interactions. However, in the case of ¹⁴¹Ce surface precipitation of Ce(III) formed by reduction of Ce(IV) in the presence of magnetite cannot be ruled out. Presence of humic acid (2 mg/L) was found to have negligible effect on sorption of all metal ions.     

Macroscopic and vibration spectroscopic evidence for specific bonding of arsenate on gibbsite

The As(V) adsorption onto gibbsite under different experimental conditions was examined. Macroscopic data suggests strong As(V) bonding on gibbsite possibly via a bidendate binuclear complexation mechanism. The As(V) adsorption was quantified with the charge distribution multi-site ions complexation (CD-MUSIC) model distributing the anion charge over 0- and 1-planes according to the modified Pauling's bond valence theory. In the dual-adsorbates system of As(III) and As(V), the As(III) adsorption was predicted up to pH 8 utilizing the binding constants derived for single-adsorbate data. However, with pH > 8, the modeled As(III) adsorption data is overestimating the experimental values.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Effect of humic acid on water chemistry, bioavailability and toxicity of aluminium in the freshwater snail, Lymnaea stagnalis, at neutral pH

The influence of humic acid on the water chemistry of environmentally relevant concentrations of Al at neutral pH was studied, together with its effect on the bioavailability and toxicity of Al in Lymnaea stagnalis. Humic acid significantly reduced the loss of Al from the water and increased the fraction of filterable Al, although this was a relatively small fraction of total Al. Filterable Al concentration in the presence or absence of humic acid was independent of initial Al concentration. Humic acid only partly reduced toxicity, as observed by a reduction in behavioural suppression, and had no effect on the level of Al accumulated in tissues. These results suggest that humic acid maintains Al in a colloidal form that is bioavailable to L. stagnalis. However, these colloidal Al-humic acid species were less toxic since behavioural toxicity was reduced. Humic acid may play an important role in limiting the toxicity of Al to freshwater organisms.     

Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent

A nanocrystalline TiO₂-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L^?1 As(III), 246 μg L^?1 As(V), 151 μg L^?1 MMA, and 202 μg L^?1 DMA was continuously passed through a TiO₂ filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L^?1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).     

Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.