Influence of humic acid and dihydroxy benzoic acid on the agglomeration, adsorption, sedimentation and dissolution of copper, manganese, aluminum and silica nanoparticles - A tentative exposure scenario.

This work focuses on kinetic aspects of stability, mobility, and dissolution of bare Cu, Al and Mn, and SiO2 NPs in synthetic freshwater (FW) with and without the presence of natural organic matter (NOM). This includes elucidation of particle and surface interactions, metal dissolution kinetics, and speciation predictions of released metals in solution. Dihydroxy benzoic acid (DHBA) and humic acid adsorbed rapidly on all metal NPs (<1 min) via multiple surface coordinations, followed in general by rapid agglomeration and concomitant sedimentation for a large fraction of the particles. In contrast, NOM did not induce agglomeration of the SiO2 NPs during the test duration (21 days). DHBA in concentrations of 0.1 and 1 mM was unable to stabilize the metal NPs for time periods longer than 6 h, whereas humic acid, at certain concentrations (20 mg/L) was more efficient (>24 h). The presence of NOM increased the amount of released metals into solution, in particular for Al and Cu, whereas the effect for Mn was minor. At least 10% of the particle mass was dissolved within 24 h and remained in solution for the metal NPs in the presence of NOM. Speciation modeling revealed that released Al and Cu predominantly formed complexes with NOM, whereas less complexation was seen for Mn. The results imply that potentially dispersed NPs of Cu, Al and Mn readily dissolve or sediment close to the source in freshwater of low salinity, whereas SiO2 NPs are more stable and therefore more mobile in solution.

Influence of organic molecules on the aggregation of TiO2 nanoparticles in acidic conditions.

Engineered nanoparticles released into the environment may interact with natural organic matter (NOM). Surface complexation affects the surface potential, which in turn may lead to aggregation of the particles. Aggregation of synthetic TiO2 (anatase) nanoparticles in aqueous suspension was investigated at pH 2.8 as a function of time in the presence of various organic molecules and Suwannee River fulvic acid (SRFA), using dynamic light scattering (DLS) and high-resolution transmission electron microscopy (TEM). Results showed that the average hydrodynamic diameter and ζ-potential were dependent on both concentration and molecular structure of the organic molecule. Results were also compared with those of quantitative batch adsorption experiments. Further, a time study of the aggregation of TiO2 nanoparticles in the presence of 2,3-dihydroxybenzoic acid (2,3-DHBA) and SRFA, respectively, was performed in order to observe changes in ζ-potential and particle size over a time period of 9 months. In the 2,3-DHBA-TiO2 system, ζ-potentials decreased with time resulting in charge neutralization and/or inversion depending on ligand concentration. Aggregate sizes increased initially to the micrometer size range, followed by disaggregation after several months. No or very little interaction between SRFA and TiO2 occurred at the lowest concentrations tested. However, at the higher concentrations of SRFA, there was an increase in both aggregate size and the amount of SRFA adsorbed to the TiO2 surface. This was in correlation with the ζ-potential that decreased with increased SRFA concentration, leading to destabilization of the system. These results stress the importance of performing studies over both short and long time periods to better understand and predict the long-term effects of nanoparticles in the environment.

Adsorption and surface complexation study of L-DOPA on Rutile (α-TiO2) in NaCl solutions.

Dihydroxyphenylalanine (DOPA) and similar molecules are of considerable interest in studies of bioadhesion to minerals, solar cells involving titanium dioxide, and biomedical imaging. However, the extent and mechanisms of DOPA adsorption on oxides in salt solutions are unknown. We report measurements of DOPA adsorption on well-characterized rutile (α-TiO2) particles over a range of pH, ionic strength, and surface coverage as well as a surface complexation model analysis establishing the stoichiometry, model surface speciation, and thermodynamic equilibrium constants, which permits predictions in more complex systems. DOPA forms two surface species on rutile, the proportions of which vary strongly with pH but weakly with ionic strength and surface loading. At pH < 4.5 a species involving four attachment points ("lying down") is important, whereas at pH > 4.5 a species involving only two attachment points via the phenolic oxygens ("standing up") predominates. Based on evidence of strong attachment of DOPA to titanium dioxide from single molecule AFM (Lee, H. et al., Proc. Natl. Acad. Sci.2006, 103, 12999-12003) and studies of catechol adsorption, one or more of the DOPA attachments for each species is inner-sphere, the others are likely to be H-bonds.

The adsorption of short single-stranded DNA oligomers to mineral surfaces.

We studied the adsorption of short single-stranded deoxyribonucleic acid (ssDNA) oligomers, of approximately 30 nucleotides (nt) in length, of varying sequence, adenine+guanine+cytosine (AGC) content, and propensity to form secondary structure, to equal surface area samples of olivine, pyrite, calcite, hematite, and rutile in 0.1M NaCl, 0.05M pH 8.1 KHCO(3) buffer. Although the mineral surfaces have widely varying points of zero charge, under these conditions they show remarkably similar adsorption of ssDNA regardless of oligomer characteristics. Mineral surfaces appear to accommodate ssDNA comparably, or ssDNA oligomers of this length are able to find binding sites of comparable strength and density due to their flexibility, despite the disparate surface properties of the different minerals. This may partially be due charge shielding by the ionic strength of the solutions tested, which are typical of many natural environments. These results may have some bearing on the adsorption and accumulation of biologically derived nucleic acids in sediments as well as the abiotic synthesis of nucleic acids before the origin of life.

Evaluating glutamate and aspartate binding mechanisms to rutile (α-TiO2) via ATR-FTIR spectroscopy and quantum chemical calculations.

Attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy and quantum chemical calculations were used to elucidate the influence of solution chemistry (pH, amino acid concentration) on the binding mechanisms of glutamic and aspartic acid to rutile (α-TiO(2)). The amino acids, glutamate and aspartate, contain carboxyl and amine groups whose dissociation over a pH range results in changes of molecular charge and reactivity, including reactions with mineral surfaces. At pH 3, a decrease of IR bands corresponding to protonated carboxyl groups is observed upon reaction with TiO(2) and indicates involvement of distal carboxyl groups during sorption. In addition, decreased IR bands arising from carboxyl bonds at 1400 cm(-1), concomitant to shifts to higher wavenumbers for ν(as)(γ-COO(-)) and ν(as)(α-COO(-)) (particularly at low glutamate concentrations), are indicative of inner-sphere coordination of both carboxyl groups and therefore suggest a "lying down" surface species. IR spectra of aspartate reacted with rutile are similar to those of solution-phase samples, without peak shifts indicative of covalent bonding, and outer-sphere coordination is predicted. Quantum chemical calculations were carried out to assist in elucidating molecular mechanisms for glutamate binding to rutile and are in reasonable agreement with experimental data. The combined use of ATR-FTIR data and quantum calculations suggests three potential surface configurations, which include (1) bridging-bidentate where glutamate is "lying down" and binding occurs through inner-sphere coordination of both α- and γ-carboxyl groups; (2) chelating-monodentate in which glutamate binds through inner-sphere coordination with the γ-carboxyl group in a "standing up" configuration (with or without protonation of the α-carboxyl); and (3) another bridging-bidentate configuration where glutamate is binding to rutile via inner-sphere coordination of the α-carboxyl group and outer-sphere coordination with the γ-carboxyl ("lying down").

Adsorption of nucleic acid components on rutile (TiO(2)) surfaces.

Nucleic acids, the storage molecules of genetic information, are composed of repeating polymers of ribonucleotides (in RNA) or deoxyribonucleotides (in DNA), which are themselves composed of a phosphate moiety, a sugar moiety, and a nitrogenous base. The interactions between these components and mineral surfaces are important because there is a tremendous flux of nucleic acids in the environment due to cell death and horizontal gene transfer. The adsorption of mono-, oligo-, and polynucleotides and their components on mineral surfaces may have been important for the origin of life. We have studied here interactions of nucleic acid components with rutile (TiO(2)), a mineral common in many terrestrial crustal rocks. Our results suggest roles for several nucleic acid functional groups (including sugar hydroxyl groups, the phosphate group, and extracyclic functional groups on the bases) in binding, in agreement with results obtained from studies of other minerals. In contrast with recent studies of nucleotide adsorption on ZnO, aluminum oxides, and hematite, our results suggest a different preferred orientation for the monomers on rutile surfaces. The conformations of the molecules bound to rutile surfaces appear to favor specific interactions, which in turn may allow identification of the most favorable mineral surfaces for nucleic acid adsorption.

Attachment of L-glutamate to rutile (alpha-TiO(2)): a potentiometric, adsorption, and surface complexation study.

Interactions between aqueous amino acids and mineral surfaces influence the bioavailability of amino acids in the environment, the viability of Ti implants in humans, and the role of mineral surfaces in the origin of life on Earth. We studied the adsorption of l-glutamate on the surface of rutile (alpha-TiO(2), pH(PPZC) = 5.4) in NaCl solutions using potentiometric titrations and batch adsorption experiments over a wide range of pH values, ligand-to-solid ratios, and ionic strengths. Between pH 3 and 5, glutamate adsorbs strongly, up to 1.4 micromol m(-2), and the adsorption decreases with increasing ionic strength. Potentiometric titration measurements of proton consumption for the combined glutamate-rutile-aqueous solution system show a strong dependence on glutamate concentration. An extended triple-layer surface complexation model of all the experimental results required at least two reaction stoichiometries for glutamate adsorption, indicating the possible existence of at least two surface glutamate complexes. A possible mode of glutamate attachment involves a bridging-bidentate species binding through both carboxyl groups, which can be thought of as "lying down" on the surface (as found previously for amorphous titanium dioxide and hydrous ferric oxide). Another involves a chelating species which binds only through the gamma-carboxyl group, that is, "standing up" at the surface. The calculated proportions of these two surface glutamate species vary strongly, particularly with pH and glutamate concentration. Overall, our results serve as a basis for a better quantitative understanding of how and under what conditions acidic amino acids bind to oxide mineral surfaces.

Glyphosate complexation to aluminium(III). An equilibrium and structural study in solution using potentiometry, multinuclear NMR, ATR-FTIR, ESI-MS and DFT calculations.

The stoichiometries and stability constants of a series of Al(3+)-N-phosponomethyl glycine (PMG/H(3)L) complexes have been determined in acidic aqueous solution using a combination of precise potentiometric titration data, quantitative (27)Al and (31)P NMR spectra, ATR-FTIR spectrum and ESI-MS measurements (0.6M NaCl, 25 degrees C). Besides the mononuclear AlH(2)L(2+), Al(H(2)L)(HL), Al(HL)(2)(-) and Al(HL)L(2-), dimeric Al(2)(HL)L(+) and trinuclear Al(3)H(5)L(4)(2+) complexes have been postulated. (1)H and (31)P NMR data show that different isomers co-exist in solution and the isomerization reactions are slow on the (31)P NMR time scale. The geometries of monomeric and dimeric complexes likely double hydroxo bridged and double phosphonate bridged isomers have been optimized using DFT ab initio calculations starting from rational structural proposals. Energy calculations using the PCM solvation method also support the co-existence of isomers in solutions.

Glutamate surface speciation on amorphous titanium dioxide and hydrous ferric oxide.

Hydrous ferric oxide (HFO) and titanium dioxide exhibit similar strong attachment of many adsorbates including biomolecules. Using surface complexation modeling, we have integrated published adsorption data for glutamate on HFO over a range of pH and surface coverage with published in situ ATR-FTIR studies of glutamate speciation on amorphous titanium dioxide. The results indicate that glutamate adsorbs on HFO as a deprotonated divalent anion at pH 3-5 and 0.2 micromol x m(-2) in the form of chelating-monodentate and bridging-bidentate species attached to the surface through three or four of the carboxylate oxygens, respectively. The amine group may interact weakly with the surface. However, at similar pH values and higher surface coverages, glutamate adsorbs mainly as a monovalent or divalent anion chelated to the surface by the gamma-carboxylate group. In this configuration the alpha-carboxylate and amine groups might be free to interact above the surface with the free ends of adjacent glutamates, suggesting a possible mechanism for chiral self-organization and peptide bond formation.

Adsorption of glyphosate on goethite (alpha-FeOOH): surface complexation modeling combining spectroscopic and adsorption data.

N-(phosphonomethyl)glycine (glyphosate, PMG) is the most widely used herbicide, and its adsorption onto soil minerals plays a significant role in its mobility and rate of degradation. In this work, we present the results of the first serious effort to find a realistic surface complexation modelthatfits both adsorption and total proton concentration data for PMG on the common soil mineral, goethite. Special attention was focused on making sure that the final model was in good semiquantitative agreement with previously reported X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopic measurements. Electrostatic effects were accounted for using the Basic Stern model, and the charges of the PMG-containing surface complexes were assumed to be distributed across the 0- and beta-planes. The reactions for the protonation of the goethite surface were described using the 1 pK model. We optimized on the intrinsic formation constants and the charge distributions of the complexes, as well as the initial total proton concentration (I = 0.1 M Na(NO3), 25.0 degrees C), and the following model was obtained. triple bond FeOH(0.5-) + H3L <==> triple bond FeHL(1.5-) + H(+) + H2O Log10beta = 4.70 +/- 0.08, Q0 = -0.18 +/- 0.02 triple bond FeOH(0.5-) + H3L <==> FeL(2.5-) + 2H(+) + H2O Log10beta = -3.9 +/- 0.1, Q0 = -0.7 +/- 0.1 Here, beta is the intrinsic formation constant, Q0 is the charge at the 0-plane, and the errors are reported as one standard deviation. The charge distributions of the complexes are rationalized by considering intramolecular hydrogen bonding between the protons of the amine group and both the phosphonate and carboxylate groups.