Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon (char): attenuation of surface activity by humic and fulvic acids

Black carbon (BC) plays a potentially important role in the availability of pollutants in soils and sediments. Recent evidence points to the possible attenuation of the high surface activity of raw BC by natural substances. We studied the effects of soil humic (HA) and fulvic (FA) acids on the surface properties and affinity for organic compounds of synthesized wood charcoal. Char powder suspended in a solution of HA or FA was loaded with organic matter via adsorption, evaporation of the water, or coflocculation with Al3+. These treatments were chosen to simulate initial and more advanced stages of environmental exposure. Coevaporation dramatically reduced the N2 Brunauer-Emmett-Teller total surface area of the char, but only moderately the CO2 cumulative surface area up to 1.4 nm. Organic compound adsorption was suppressed in proportion to molecular size, benzene < naphthalene < phenanthrene and 1,2,4-trichlorobenzene < phenanthrene, for humics in the adsorbed and coflocculated states, respectively. Humic substances also increased the linearity of the isotherms. The model we propose assumes that humic substances are restricted to the external surface where they act as pore blocking agents or competitive adsorbates, depending on the temperature and adsorbate size. Nitrogen is blocked from the internal pore space due to stiffness at 77 K of humic strands extending into pore throats, giving an artificially low surface area. Together with previous results, this finding indicates that N2 may not detect BC microporosity in geosorbents. At higher temperatures (CO2, 273 K; organics, 293 K), humic strands are more flexible, allowing access to interior pores. The counterintuitive molecular size dependence of adsorption suppression by humics is due to a molecular sieving effect in pores in which the adsorption space available to the organic compound is more and more restricted to external sites.     

Study on the effects of humic and fulvic acids on quantum dot nanoparticles using capillary electrophoresis with laser-induced fluorescence detection

The increasing production and use of quantum dot (QD) nanoparticles have caused concerns on the possibility of contaminating the aquatic and terrestrial ecosystems with wastes that may contain QDs. Therefore, studies on the behavior of QDs upon interaction with components of the natural environment have become of interest. This study investigated the fluorescence and electrophoretic mobility of carboxylic or amine polyethylene glycol (PEG)-functionalized CdSe/ZnS QDs in the presence of two aquatic humic substances (HS), Suwannee River humic and fulvic acids, using capillary electrophoresis with laser-induced fluorescence detection. Results showed initial enhancement in fluorescence of QDs at the onset of the interaction with HS, followed by fluorescence quenching at longer exposure with HS (>30 min). It was also observed that the electrophoretic mobility of QDs increases with increasing concentration of HS, suggesting an increase in the ratio in charge to hydrodynamic size of the nanoparticles. To determine if the QDs degraded upon interaction with HS, the QD-HS mixtures were dialyzed to separate free Cd2+ from intact QDs, followed by analysis of the solutions using inductively coupled plasma-mass spectrometry. Results suggested that degradation of QDs in the presence of HS did not occur within the period of incubation.     

Research Watch: Aquatic humic substances

Assessment.     

Transport of humic and fulvic acids in relation to metal mobility in a copper-contaminated acid sandy soil

The transport of inorganic and organic pollutants in water and soil can be strongly influenced by the mobility of natural dissolved organic matter (DOM). In this paper, the transport of a humic acid (HA) and a fulvic acid (FA) in a copper-contaminated acid sandy soil was studied. The data showed that the transport behavior of HA differed from that of FA. The breakthrough curves (BTCs) of HA were characterized by a rapid relatively sharp front followed by a plateau at a lower HA concentration than in the influent solution. The increase of the Ca concentration decreased the HA concentration further. Compared to HA, the BTCs of FA were retarded and showed an extended tailing, approaching complete breakthrough. The increase of the Ca concentration decreased the FA concentration only temporarily. On the basis of our model calculation, the characterization of HA transport could be explained by the coagulation of HA largely upon the binding of Al. The increase of the Ca concentration resulted in further coagulation of HA because of the increased Ca adsorption, which occurred mainly in the Donnan phase. For FA, the adsorption to the soil matrix was more likely the process that controls its solubility and mobility. The mobility of Al and Cu in the soil column was closely related to the solubility and transport of the DOM in soil solution. The concentration of Ca in the effluent was lower than in the influent because Ca was retained in the soil due to the retardation of HA and FA and due to the compensation of the other cations released from the soil to the solution.     

Adsorption of glyphosate on goethite: molecular characterization of surface complexes

As a component of herbicides, the fate of glyphosate (PMG) in the environment is of significant interest. The nature of PMG adsorption on mineral surfaces plays a significant role in the degradation of PMG. The adsorption of PMG on goethite (alpha-FeOOH) has been studied as a function of pH and PMG concentration. Adsorption was investigated with batch experiments, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The N 1s line in XPS spectra showed deprotonation of the amine group of PMG (NH2+) with increasing pH. IR analyses showed no evidence for the interaction of PMG's carboxylate group with the goethite surface, while the phosphonate group formed inner-sphere complexes. There is evidence for intramolecular hydrogen bonding between NH2+ and both the carboxylate and the phosphonate groups at low pH. Intramolecular hydrogen bonding is lost when the amine group is deprotonated, and the trend in intramolecular hydrogen bonding between NH2+ and phosphonate shows that PMG adsorbs via predominantly monodentate complexation. A minor quantity of bidentate complexes is thought to form both at near-neutral pH and when the surface concentration of PMG is low. While the phosphonate group of PMG binds directly, the carboxylate group remains relatively "free" from complexation with goethite, leaving it subject to degradation and/or complexation with metal ions present in the environment.     

Elucidating differences in the sorption properties of 10 humic and fulvic acids for polar and nonpolar organic chemicals

In this work we present a dataset of more than 1000 natural organic matter (NOM)/air partition coefficients covering polar and nonpolar organic compounds measured in 10 different humic and fulvic acids (HAs/FAs) from terrestrial and aquatic origins. Differences of more than 1 order of magnitude in the sorption coefficients of a given compound measured in HAs and FAs from different origins were found. The terrestrial HAs exhibited substantially higher sorption coefficients compared to aquatic HAs and FAs. The difference between any two types of NOM is mainly reflected by a constant shift in the partition coefficients that applies to all compounds in the same way. This indicates that it is the number of available sorption sites per mass of sorbent rather than the types of intermolecular interactions between the sorbate and the sorbent that governs the major differences between the sorption properties of various types of NOM. The experimental partition coefficients measured in all HAs and FAs were successfully described by polyparameter linear free energy relationships (pp-LFERs) that explicitly account for van der Waals as well as H-donor/acceptor interactions between the sorbate and the sorbent. These pp-LFER equations provide for the first time a tool that allows including the variability of the sorption properties of NOM in environmental fate models.     

Binding of mercury(II) to aquatic humic substances: influence of pH and source of humic substances

Conditional distribution coefficients (K(DOM')) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that K(DOM') values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (10(22.5 +/-1.0)-10(23.5 +/- 1.0)) L kg(-1)), suggesting similar Hg(ll) binding environments, presumably involving thiol groups, for the different isolates. K(DOM') values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)-DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pK(a) = 10.3) and one other group (pK(a) = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)-DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).     

Nonideal binding between dissolved humic acids and polyaromatic hydrocarbons

Interactions between hydrophobic organic chemicals (HOCs) and dissolved organic matter (DOM) are of environmental significance due to their influence on mobility and bioavailability of HOCs. The linear dissolution concept has been widely used to describe the interactions between HOCs and DOM, but it may not be correct. To date there is no systematic evaluation of nonideal interactions between HOCs and DOM. Therefore, this study employed a dialysis method to investigate sorption, desorption, and competition of two polyaromatic hydrocarbons (PAHs), phenanthrene (PHE) and pyrene (PYR), by two DOMs at pHs of 4, 7, and 11. Nonlinear interactions between PAHs and DOM and desorption hysteresis were consistently observed. The isotherm nonlinearity factor, nvalue, increased significantly after the addition of cosolutes, indicating the occupation of specific binding sites by the cosolute molecules. Significant influence of pH on PAHs-DOM interaction was also observed (higher binding coefficients, stronger desorption hysteresis, and increased nonlinearity at lower pH). This study for the first time systematically showed the nonideal binding behavior of PAHs by DOM. A more complete model rather than linear distribution is required to describe the interactions between HOCs and DOM. Conformation changes of DOM molecules were proposed to explain the interactions between HOCs and DOM.     

Antioxidant properties of humic substances

Humic substances (HS) are heterogeneous, redox-active organic macromolecules. While electron transfer to and from HS under reducing conditions is well investigated, comparatively little is known on the electron donating (i.e., antioxidant) properties of HS under oxic conditions. In this work, the electron donating capacities (EDCs) of terrestrial and aquatic HS were quantified by mediated electrochemical oxidation over a wide range of pH values and applied redox potentials (E(h)) using 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) as an electron transfer mediator. Electrochemical oxidation of three model humic acids (HAs) was largely irreversible, and the EDCs of these HAs increased with increasing E(h) and pH. These results suggest that HS contain a wide variety of moieties that are oxidized at different potentials and that, upon oxidation, release protons and undergo irreversible follow-up reactions. At a given pH and E(h), the EDCs of the HS correlated well with their titrated phenol contents suggesting phenolic moieties as major electron donating groups in HS. Comparing the EDCs of 15 HS with their electron accepting capacities (EACs), aquatic HS had higher EDCs and lower EACs than terrestrial HS of comparable aromaticities. These results indicate that oxidative transformation of HS in the environment results in a depletion of electron donating phenolic moieties with antioxidant properties relative to the electron accepting quinone moieties.     

Involvement of humic substances in regrowth

There appear to be interactions in the distribution system that complicate the ability to use AOC/BDOC as an independent assessment of regrowth potential. Two such complications are the limitation of the assays themselves and the potential interaction between the organic carbon concentration with the presence of disinfectants and pipe materials. To address these interactions, a series of experiments spanning several years have been conducted in model distribution systems at the Center for Biofilm Engineering (CBE) using soil-derived humics. When compared to easily utilized organics, humic substances supported the same order of magnitude of biofilm organisms. As carbon concentration was increased from 500 to 1000 to 2000 ppb, there was no increase in growth rate of the organisms, suggesting zero-order kinetics. If the system was chlorinated, there was less biomass, but growth rates were higher. In the presence of corrosion products, humic-fed systems supported more organisms than a control system fed biologically treated water. When free chlorine was maintained at a residual of about 0.2 mg/l, biofilm numbers on the surfaces were reduced. Phosphate alone did not result in fewer bacteria, while a combination of chorine and phosphate had the best results (lowest biofilm numbers). Adjustment to pH 9 was not effective. Recently completed work compared increasing levels of humic substances in the presence of free chlorine and monochloramine on biofilm growth on a number of surfaces (PVC, epoxy, cement, ductile iron). As the concentration of humic substances was increased from 0, 0.5 to 2 mg/l, there was an increase in biofilm numbers on all surfaces. This effect was the most pronounced on iron surfaces. These results illustrate that carbon compounds not measured by the BDOC or AOC tests may profoundly influence biofilm numbers. In addition, iron surfaces are at much higher risk for elevated biofilm counts in the presence of humic substances, even if disinfection is practiced. However, corrosion control may mitigate this interaction.     

Effect of humic and fulvic acid concentrations and ionic strength on copper and lead binding

We investigated the influence of humic and fulvic acid concentration (in the range of 1-1000 mg/L) on the binding of the two trace metals Cu(II) and Pb(II). The ability of the non-ideal competitive adsorption (NICA)-Donnan model to correctly predict Cu and Pb binding at low humic or fulvic acid concentration and lower ionic strength (0.01 M NaNO3), based on model parameters obtained from experiments conducted at high humic or fulvic acid concentrations (approximately 1000 mg/L) and higher ionic strength (0.1 M NaNO3), was tested. The binding of Cu and Pb to humic and fulvic acid in 0.01 M NaNO3 was determined over wide ranges in proton and metal ion activities using three different methods: ligand exchange-adsorptive differential pulse cathodic stripping voltammetry at low humic or fulvic acid concentrations (1-3 mg/L), differential pulse anodic stripping voltammetry at intermediate humic or fulvic acid concentrations (10-20 mg/L), and ion-selective electrodes at high humic or fulvic acid concentrations (approximately 1000 mg/L). The results demonstrate that binding isotherms for Cu and Pb can be measured at low humic or fulvic acid concentration using suitable voltammetric techniques. The binding isotherms for Cu and Pb to humic and fulvic acid obtained at constant pH values in the range of pH 4-8 are shown to be independent of humic and fulvic acid concentration. The NICA-Donnan model, calibrated for Cu and Pb binding using data measured at high humic and fulvic acid concentrations and an ionic strength of 0.1 M, accurately predicts Cu and Pb binding at low humic and fulvic acid concentrations and lower ionic strength (0.01 M). We conclude that NICA-Donnan parameters obtained by fitting experimental data measured with ion-selective electrodes at high humic or fulvic acid concentrations can be used for geochemical modeling of soils and aquatic environments with much lower concentrations of humic or fulvic acids.     

Influence of humic substance adsorptive fractionation on pyrene partitioning to dissolved and mineral-associated humic substances

Changes in pyrene binding by dissolved and mineral-associated humic substances (HS) due to HS adsorptive fractionation processes were examined in model environmental systems using purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). For PAHA, carbon-normalized pyrene binding coefficients for nonadsorbed, residual fractions (Koc(res)) were different from the original dissolved PAHA Koc value (Koc(orig)) prior to contact with the mineral suspensions. A strong positive correlation between pyrene log Koc(res) and log weight-average molecular weight (MWw) for residual PAHA fractions was observed, which was relatively independent of the specific mineral adsorbent used and hypothesized fractionation processes. A strong positive correlation between log Koc(ads) and log MWw was also found for PAHA fractions adsorbed to kaolinite at low mass fraction organic carbon levels, although the relationship was statistically different from the one found with residual PAHA fractions. The same trends and correlations found for PAHA were not observed with SRFA, suggesting that the impacts of HS adsorptive fractionation on changes in hydrophobic organic contaminants binding are also influenced by the source and other biogeochemical characteristics of HS.     

Antimony(III) binding to humic substances: influence of pH and type of humic acid

Conditional distribution coefficients (Dom) for Sb(III) binding to three commercial humic acids (terrestrial, coal, and aquatic) were measured at environmentally relevant Sb(III)/DOC ratios and as a function of pH using an equilibrium dialysis method. Maximum binding of Sb(III) was observed around pH 6 for two of the humic acids. The third humic acid showed constant Dom values up to pH 6 and decreasing Dom values for pH > 6. Sb(III)/DOC ratio was found to be important for Dom (20 times higher Dom for 60 times lower Sb(III)/DOC ratio). Moreover, Dom depends on the individual humic acid, suggesting that different functional groups are involved and/or different degrees of stabilization by chelation or H-bridges. Chemical modeling of Sb(III)-humics binding at different pH values is consistent with two binding sites involving (i) a phenolic entity forming a neutral complex and (ii) a carboxylic entity forming a negatively charged complex. Under environmentally relevant conditions, over 30% of total Sb(III) may be bound to natural organic matter.