Humic Colloids Research Articles

Metal dissociation from humic colloids: Kinetics with time-dependent rate constants

The mobility of contaminant metals in aqueous subsurface environments is largely controlled by their interaction with humic substances as colloidal constituents of Dissolved Organic Matter. Transport models for predicting carrier-bound migration are based on a competitive partitioning process between solid surface and colloids. However, it has been observed that dissociation of multivalent metals from humic complexes is a slow kinetic process, which is even more impeded with increasing time of contact. Based on findings obtained in isotope exchange experiments, the convoluted time dependence of dissociation was fully described by a complex two-site approach, integrating rate “constants” that are in turn time-dependent. Thus, this study presents the treatment of a particular phenomenon: kinetics within kinetics. The analysis showed that the inertization process does not lead to irreversible binding. Consequently, thermodynamic concepts using equilibrium constants remain applicable in speciation and transport modeling if long time frames are appropriate.

Formation of Humic Colloids in Aqueous Solutions at Different pH Values

The effect the mechanochemical modification of humic acids has on their surface-active and acid–base properties is studied. The dependence of the surface activity of humic acids on structural changes, concentration, and the pH of the medium are determined. It is shown that in an alkaline medium, associates of humic acids are characterized by the minimum average particle radius, an increased degree of dissociation of acidic groups, and enhanced surface activity at the gas–liquid interface. A neutral or acidic medium facilitates aggregation and an increase in the size of macromolecules of humic acids.

Are nanoplastics able to bind significant amount of metals? The lead example

The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log Kadsfreundlich=8.36 against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

Alteration of the Copper-Binding Capacity of Iron-Rich Humic Colloids during Transport from Peatland to Marine Waters.

Blanket bogs contain vast amounts of Sphagnum-derived organic substances which can act as powerful chelators for dissolved iron and thus enhance its export to the coastal ocean. To investigate the variations in quantity and quality of these exports, adsorptive cathodic stripping voltammetry (CSV) was used to characterize the metal binding properties of molecular weight-fractionated dissolved organic matter (MW-fractionated DOM) in the catchment and coastal plume of a small peat-draining river over a seasonal cycle. Within the plume, both iron- and copper-binding organic ligands showed a linear, conservative distribution with increasing salinity, illustrating the high stability of peatland-derived humic substances (HS). Within the catchment, humic colloids lost up to 50% of their copper-binding capacity, expressed as a molar ratio to organic carbon, after residing for 1 week or more in the main reservoir of the catchment. Immediately downstream of the reservoir, the molar ratio [L2]/[Corg], where L2 was the second strongest copper-binding ligand, was 0.75 × 10-4 when the reservoir residence time was 5 h but 0.34 × 10-4 when it was 25 days. Residence time did not affect the carbon specific iron-binding capacity of the humic substances which was [L]/[Corg] = (0.80 ± 0.20) × 10-2. Our results suggest that the loss of copper-binding capacity with increasing residence time is caused by intracolloidal interactions between iron and HS during transit from peat soil to river mouth.

Influence of heteroaggregation processes between intrinsic colloids and carrier colloids on cerium(III) mobility through fractured carbonate rocks

Colloid facilitated transport of radionuclides has been implicated as a major transport vector for leaked nuclear waste in the subsurface. Sorption of radionuclides onto mobile carrier colloids such as bentonite and humic acid often accelerates their transport through saturated rock fractures. Here, we employ column studies to investigate the impact of intrinsic, bentonite and humic acid colloids on the transport and recovery of Ce(III) through a fractured chalk core. Ce(III) recovery where either bentonite or humic colloids were added was 7.7–26.9% Ce for all experiments. Greater Ce(III) recovery was observed when both types of carrier colloids were present (25.4–37.4%). When only bentonite colloids were present, Ce(III) appeared to be fractionated between chemical sorption to the bentonite colloid surfaces and heteroaggregation of bentonite colloids with intrinsic carbonate colloids, precipitated naturally in solution. However, scanning electron microscope (SEM) images and colloid stability experiments reveal that in suspensions of humic acid colloids, colloid-facilitated Ce(III) migration results only from the latter attachment mechanism rather than from chemical sorption. This observed heteroaggregation of different colloid types may be an important factor to consider when predicting potential mobility of leaked radionuclides from geological repositories for spent fuel located in carbonate rocks.

Influence of Humic Acid Colloid on Adsorption of DDT in the Riverbed Sediments

Influence of Humic Acid Colloid on Adsorption of DDT in the Riverbed Sediments

Influence of Humic Acid Colloid on Adsorption of Oxytetracycline in Sediment

Influence of Humic Acid Colloid on Adsorption of Oxytetracycline in Sediment

Phenanthrene removal from aqueous solutions using well-characterized, raw, chemically treated, and charred malt spent rootlets, a food industry by-product

Malt spent rootlets (MSR) are biomaterials produced in big quantities by beer industry as by-products. A sustainable solution is required for their management. In the present study, MSR are examined as sorbents of a hydrophobic organic compound, phenanthrene, from aqueous solutions. Raw MSR sorb phenanthrene but their sorptive properties are not competitive with the respective properties of commercial sorbents (e.g., activated carbons). Organic petrography is used as a tool to characterize MSR after treatment in order to produce an effective sorbent for phenanthrene. Chemical and thermal (at low temperature under nitrogen atmosphere) treatments of MSR did not result in highly effective sorbents. Based on organic petrography characterization, the pores of the treated materials were filled with humic colloids. When pyrolysis at 800 °C was used to treat MSR, a sorbent with new and empty pores was produced. Phenanthrene sorption capacity was 2 orders of magnitude higher for the pyrolized MSR than for raw MSR.

The effects of carbonates removal on adsorption, immobilization and activity of cellulase in a calcareous soil

Enzymes are able to be sorbed and immobilized by clay minerals and humic colloids in soil environments. The present study was done to elucidate the effects of soil innate carbonates on the sorption, immobilization and activity of cellulase in a calcareous soil by treating it with different levels of acetic acid. The study of adsorption isotherm revealed that soil carbonates removal with acetic acid increased the intensity of cellulase adsorption (1/n) estimated by the Freundlich model. Based on the Freundlich isotherm model it is predicted that cellulase molecules will be increasingly adsorbed on acetic acid treated soil with increasing cellulase concentration. However, practically the amounts of cellulase protein adsorbed and immobilized on untreated soil with high levels of ECC were significantly higher than those on acetic acid treated soils. The immobilized cellulase activity and particularly its specific activity decreased considerably with increasing carbonate contents in soil.

Diffusion, degradation or on-site stabilisation – Identifying causes of kinetic processes involved in metal–humate complexation

The applicability of equilibrium models for humic-bound transport of toxic or radioactive metals is affected by kinetic processes leading to an increasing inertness of metal–humic complexes. The chemical background is not yet understood. It is widely believed that bound metals undergo an in-diffusion process within the humic colloids, changing from weaker to stronger binding sites. This work is focussed on the competition effect of Al(III) on complexation of Tb(III) or Eu(III) as analogues of trivalent actinides. By using ion exchange and spectroscopic methods, their bound fractions were determined for solutions of Al and humic acid that had been pre-equilibrated for different periods of time. Whilst the amount of bound Al remained unchanged, its blocking effect was found to increase over a time frame of 2 days, which corresponds to the kinetics of the increase in complex inertness reported in most pertinent studies. Thus, the derived “diffusion theory” turned out to be inapplicable, since it cannot explain an increase in competition for the “initial” sites. A delayed degradation of polynuclear species (as found for Fe) does not occur. Consequently, the temporal changes must be based on structural rearrangements in the vicinity of bound Al, complicating the exchange or access. Time-dependent studies by laser fluorescence spectroscopy (steady-state and time-resolved) yielded evidence of substantial alterations, which were, however, immediately induced and did not show any significant trend on the time scale of interest, suggesting that the stabilisation process is based on comparatively moderate changes.

Modeling of the pseudo-colloids migration for multi-member decay chains with a arbitrary flux boundary condition in a fractured porous medium

A deep geologic disposal is the prime option for the long-term isolation of high-level radioactive waste (HLW) in many countries. For deeply located repositories, a radionuclide released from a failed waste container moves through the engineered and natural barriers before it reaches a biosphere. The pseudo-colloid which a radionuclide is adsorbed on a moving natural humic or fulvic colloid can be generated in a fractured porous medium. The size of a colloid is in general in the order of a hundred nanometer so that its migration velocity in a fracture is higher than that of a radionuclide due to the hydrochromatic effect. A large colloid cannot diffuse easily into a surrounding rock. Also, there are many kinds of actinides and these actinides have decay chains. In this analysis, the canonical form solution is derived for a pseudo-colloid and a solute in a fracture and a surrounding rock with a realistic inlet boundary condition with multi-member decay chains. It is used the Fortran based a computational code which uses a special subroutine for the inversion of Laplace transform. Consequently, the role of the pseudo-colloid in the fractured porous medium is important and also their decay chains aren’t neglected in the performance assessment of the HLW.

Application of different types of resins in the radiometric determination of uranium in waters

The aim of this study is to compare different resins regarding their separation and pre-concentration efficiency for uranium from aqueous solutions and its subsequent radiometric determination by liquid scintillation counting (LSC). The different types of the investigated resins include: (a) a pure cation-exchange resin (Dowex Marathon C), (b) a complex forming resin (Chelex 100) and (c) an impregnated resin (5% diethylene glycol succinate on Chromosorb W-H). The radiometric measurements were performed after mixing of the pre-concentrated aqueous phase with the liquid scintillation cocktail. The effect of experimental conditions such as pH, salinity (e.g. [NaCl]) and the presence of other chemical species (e.g. Ca2+ and Fe3+ ions or humic acid and silica colloids) on the separation recovery have been investigated at constant uranium/radioactivity concentration. According to the experimental results the maximum chemical recovery differs significantly from one resin to another as a function of either, pH or the other chemical parameters. The optimum pH is found to be 8, 4 and 8 for Marathon C, Chelex-100 and diethylene glycol succinate, respectively. On the other hand, generally Ca2+ and Fe3+ ions as well as the presence of colloidal species in solution (even at low concentrations) result in a significant decrease of the chemical recovery of uranium, particularly for Marathon C and the diethylene glycol succinate impregnated resins. Generally, among the studied resins Chelex 100 was superior regarding chemical recovery, selectivity, regeneration and reuse.

Uranium facilitated transport by water-dispersible colloids in field and soil columns

The transport of uranium through a sandy podzolic soil has been investigated in the field and in column experiments. Field monitoring, numerous years after surface contamination by depleted uranium deposits, revealed a 20 cm deep uranium migration in soil. Uranium retention in soil is controlled by the < 50 µm mixed humic and clayey coatings in the first 40 cm i.e. in the E horizon. Column experiments of uranium transport under various conditions were run using isotopic spiking. After 100 pore volumes elution, 60% of the total input uranium is retained in the first 2 cm of the column. Retardation factor of uranium on E horizon material ranges from 1300 (column) to 3000 (batch). In parallel to this slow uranium migration, we experimentally observed a fast elution related to humic colloids of about 1–5% of the total-uranium input, transferred at the mean porewater velocity through the soil column. In order to understand the effect of rain events, ionic strength of the input solution was sharply changed. Humic colloids are retarded when ionic strength increases, while a major mobilization of humic colloids and colloid-borne uranium occurs as ionic strength decreases. Isotopic spiking shows that both 238U initially present in the soil column and 233U brought by input solution are desorbed. The mobilization process observed experimentally after a drop of ionic strength may account for a rapid uranium migration in the field after a rainfall event, and for the significant uranium concentrations found in deep soil horizons and in groundwater, 1 km downstream from the pollution source.

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.

Direct-flow microfiltration of aquasols: II. On the role of colloidal natural organic matter

Natural organic matter (NOM) has been considered a major contributor to the fouling of microfiltration (MF) and ultrafiltration (UF) membranes employed in water treatment. However, the fouling potential of NOM has often been assessed in terms of its size or chemical composition. The colloid’s chemical properties have often been ignored. In this study, a chemical attachment-based (CAB) model established previously was used in conjunction with a variety of analytical techniques to investigate the existence of three major components of an aquatic NOM and their role in the fouling of a polyvinylidene fluoride MF membrane. The results suggest that colloidal NOM relevant to membrane fouling has a broader size distribution and variations in chemical properties than proposed previously. For the model aquatic NOM used in this research, fouling was primarily contributed by both non-humic and humic colloidal fractions. The non-humic colloids were larger in size and probably adhered to the membrane regardless of the solution chemistry, while humic colloids had variable size and stickiness depending on solution chemistry. The fouling caused by organic colloids was mostly hydraulically irreversible, as a consequence of favorable surface interactions. The CAB model provided a useful way to understand the role of organic colloids in membrane fouling.

An integrated colloid fractionation approach applied to the characterisation of porewater uranium–humic interactions at a depleted uranium contaminated site

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV–visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa–0.2 µm) and small (3–30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa–0.2 µm) iron (Fe)–aluminium (Al) colloids in addition to an association with small (3–30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.

Changes in humic acid conformation during coagulation with ferric chloride: Implications for drinking water treatment

Electrophoretic mobility, pyrene fluorescence, surface tension measurements, transmission electron microscopy on resin-embedded samples, and X-ray microscopy (XRM) were combined to characterize the aggregates formed from humic colloids and hydrolyzed-Fe species under various conditions of pH and mixing. We show that, at low coagulant concentration, the anionic humic network is reorganized upon association with cationic coagulant species to yield more compact structures. In particular, spheroids about 80 nm in size are evidenced by XRM at pH 6 and 8 just below the optimal coagulant concentration. Such reorganization of humic colloids does not yield surface-active species, and maintains negative functional groups on the outside of humic/hydrolyzed-Fe complex. We also observe that the humic network remains unaffected by the association with coagulant species up to the restabilization concentration. Upon increasing the coagulant concentration, restructuration becomes limited: indeed, the aggregation of humic acid with hydrolyzed-Fe species can be ascribed to a competition between humic network reconformation rate and collision rate of destabilized colloids. A decrease in stirring favors the shrinkage of humic/hydrolyzed-Fe complexes, which then yields a lower sediment volume. Elemental analyses also reveal that the iron coagulant species are poorly hydrolyzed in the destabilization range. This suggests that destabilization mechanisms such as sweep flocculation or adsorption onto a hydroxyde precipitate are not relevant to our case. A neutralization/complexation destabilization mechanism accompanied by a restructuration of flexible humic network is then proposed to occur in the range of pHs investigated.

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.

Total And Immobilized Enzymatic Activity Of Organic Materials Before And After Composting

The evaluation of residual organic materials as a source of enzymatic activities immobilized in the humus matrix is a little explored research area, particularly in the case of organic materials derived from municipal wastes. Enzymes catalyze most soil reactions essential for soil functionality. The advantage of humus enzyme-complexes (immobilized enzymes) with regards to free enzymes is that the former are protected in the humic colloid, being more resistant to denaturing agents and other adverse soil conditions. This explains the interest in use of organic wastes (which are produced in an increasingly amount and consequently are economical) as a source of immobilized enzymes, which could be concentrated and used to improve the quality of degraded or contaminated soils. The goal of this study was (i) to assess the potential of sewage sludge (SS) and the organic fraction of municipal solid waste (MSW), as well as their respective composts (CSS and CMSW) as sources of enzymes, (ii) to determine the proportion of such enzymes which are immobilized in the humic matrix of these organic materials, and (iii) to determine the effect of the composting process on the total and the immobilized enzymatic activities of the organic materials. Dehydrogenase (DHA), urease, protease-BAA, alkaline phosphatase (ALP), β-glucosidase (GLA) and o-diphenol oxidase (DPO) activities were determined both in the organic materials and in their humic extracts (except DHA). Sewage sludge had the highest total values of urease, protease-BAA, ALP and DHA activity (12.7 μol NH4+-N g−1 h−1, 40.6 μmol NH4+-N g−1 h−1, 75.7 μmol PNP g−1 h−1 and 0.3 μmol INTF g−1 h−1, respectively), which decreased with composting, but MSW had the highest total value of DPO activity. For both organic materials, a low percentage of total enzymatic activities were linked to humus (0.6-22%), except in the case of DPO activity. The SS and MSW composting process had a positive effect on the urease, protease-BAA, DPO and ALP immobilization in the humic matrix, as reflected by the higher immobilized activity/total activity ratios in the compost than in the fresh materials.

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.