Aluminosilicate Mineralogy and the Sorption of Organic Cations: Interplay between Electrostatic Barriers and Compound Structural Features.

Current predictive models of organic cation sorption assume that sorbates interact with all sites on aluminosilicate minerals in the same manner. To examine whether differences in aluminosilicate structure and the resultant changes in electrostatic potential influence the sorption of organic cations, seven smectites were chosen with different proportions of isomorphic substitutions (origin of clay charge) located in octahedral versus tetrahedral layers and with the presence or absence of aluminosilicate interlayers. Sorption coefficients for 14 benzylamine derivatives with systematic differences in compound structures were collected to understand the possible influence of aluminosilicate mineralogy. Benzylamine compounds with methyl group substitution on the charged amine or with electron-donating or -withdrawing ring substituents displayed decreases in cation exchange-normalized sorption coefficients (KCEC), by up to one order of magnitude, between hectorite (100% isomorphic substitution in the octahedral layer) and nontronite (100% isomorphic substitution in the tetrahedral layer). To understand this difference across aluminosilicates, stochastic molecular models of the various aluminosilicate minerals with interlayers were performed. These models showed that negative charge density associated with tetrahedral sites results in high positive electrostatic energy barriers within the interlayer, creating a penalty for compounds with positive charge spread over a larger compound surface area as occurs from primary to quaternary amines. Conversely, clays with charge originating from octahedral sites produce low electrostatic potential barriers within the interlayer, decreasing the penalty for quaternary amine sorption. Trends for nine cationic pharmaceutical compounds, which varied in size, group alkylation, and/or polar substituents, demonstrated similar decreases in KCEC values to aluminosilicate minerals with high electrostatic energy barriers. Overall, aluminosilicate mineralogy was found to exert a large influence (0.5-1 order of magnitude in sorption coefficients) on organic cation sorption. The application of atomistic electrostatic potential mapping of both sorbent and sorbate structures provided insights to explain trends in sorption coefficients that could not be described by the basic electrostatic potential theory or by assuming that sorbate structure moieties yielded additive sorption contributions.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (Kd). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (Kd) decreasing as follows: KdNa+ > KdNH4+ ≥ KdK+ > KdCa2+ ≥ KdMg2+ > KdAl3+. This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium Kd values, allowed for estimation of Kd values for more structurally complex organic cations to homoionic montmorillonites and to heteroionic soils (mean absolute error of 0.27 log unit). Accordingly, we concluded that the use of phenyltrimethylammonium as a probe compound was a promising means to account for the identity, affinity, and abundance of natural exchange ions in the prediction of organic cation sorption coefficients for environmental solids.

Column Chromatography To Obtain Organic Cation Sorption Isotherms.

Column chromatography was evaluated as a method to obtain organic cation sorption isotherms for environmental solids while using the peak skewness to identify the linear range of the sorption isotherm. Custom packed HPLC columns and standard batch sorption techniques were used to intercompare sorption isotherms and solid-water sorption coefficients (Kd) for four organic cations (benzylamine, 2,4-dichlorobenzylamine, phenyltrimethylammonium, oxytetracycline) with two aluminosilicate clay minerals and one soil. A comparison of Freundlich isotherm parameters revealed isotherm linearity or nonlinearity was not significantly different between column chromatography and traditional batch experiments. Importantly, skewness (a metric of eluting peak symmetry) analysis of eluting peaks can establish isotherm linearity, thereby enabling a less labor intensive means to generate the extensive data sets of linear Kd values required for the development of predictive sorption models. Our findings clearly show that column chromatography can reproduce sorption measures from conventional batch experiments with the benefit of lower labor-intensity, faster analysis times, and allow for consistent sorption measures across laboratories with distinct chromatography instrumentation.

Fate and transport of selected estrogen compounds in Hawaii soils: effect of soil type and macropores.

The fate and transport of estrogen compounds in the environment is of increasing concern due to their potential impact on freshwater organisms, ecosystems and human health. The behavior of these compounds in batch experiments suggests low mobility, while field studies indicate the persistence of estrogen compounds in the soil with the possibility of migration to surface water as well as groundwater. To better understand the movement of these chemicals through soils, we examined their transport in three different Hawaiian soils and two aqueous matrices. The three different soils used were an Oxisol, a Mollisol and a cinder, characterized by different mineralogical properties and collected at depths of 60-90 cm and 210-240 cm. Two liquid matrices were used; deionized (DI) water containing calcium chloride (CaCl2), and recycled water collected from a wastewater treatment facility. The experiments were conducted in packed and structured columns. Non-equilibrium conditions were observed during the study, especially in the structured soil. This is believed to be primarily related to the presence of macropores in the soil. The presence of macropores resulted in reduced contact time between soil and estrogens, which facilitated their transport. We found that the organic carbon content and mineralogical composition of the soils had a profound effect on the transport of the estrogens. The mobility of estrone (E1) and 17ß-estradiol (E2) was greater in cinder than in the other soils. In column experiments with recycled water, earlier breakthrough peaks and longer tails of estrogens were produced compared to those observed using DI water. The use of recycled water for agricultural purposes and the siting of septic tanks and cesspools should be critically reviewed in light of these findings, especially in areas where groundwater is the primary source of potable water, such as Hawaii.

Nonlinearity of cationic aromatic amine sorption to aluminosilicates and soils: role of intermolecular cation-π interactions.

Through the study of substituted anilines and benzylamines, we demonstrated that cooperative cation-π, π-π, and van der Waals interactions can increase aromatic cationic amine sorption to Na/Ca-montmorillonite well beyond the extent expected by cation exchange alone. Cationic amines exhibiting cooperative interactions displayed nonlinear S-shaped isotherms and increased affinity for the sorbent at low surface coverage; parallel cation exchange and cooperative interactions were noted above a sorption threshold of 0.3-2.3% of exchange sites occupied. Our experiments revealed the predominance of intermolecular cation-π interactions, which occurred between the π system of a compound retained on the surface via cation exchange and the cationic amine group of an adjacent molecule. Compounds with greater amine charge/area and electron-donating substituents that allowed for greater electron density at the center of the aromatic ring showed a greater potential for cation-π interactions on montmorillonite surfaces. However, benzylamine sorption to nine soils, at charge loadings comparable to the experiments with montmorillonite, revealed no significant cooperative interactions. It appears that cation-π interactions may be likely in soils with exceptionally high cation exchange capacities (>0.7 mol charge/kg) and low organic matter contents, abundant in montmorillonite and other expanding clay minerals.

Polyfunctional ionogenic compound sorption: challenges and new approaches to advance predictive models.

Polyfunctional ionogenic compounds are unique in that they sorb to environmental solids at multiple receptor sites via multiple interaction mechanisms. However, existing sorption models fail to accommodate: (i) sorption via a single mechanism (e.g., cation exchange) at one sorbent receptor site type (e.g., exchange site) distributed across multiple soil components (e.g., organic matter and aluminosilicates); and (ii) sorption at a specific sorbent receptor site (e.g., exchange site) involving distinct sorbate structural moieties (e.g., -NH(3)(+) and -COOH) and distinct interaction mechanisms (e.g., cation exchange and cation bridging). In response, this study offers a mechanism-based framework for conceptualizing the equilibrium solid-water sorption coefficient, K(d), with particular emphasis on the mechanisms of cation exchange and surface complexation/cation bridging. The unique mapping of sorbate structural moieties, sorbent receptor sites, and sorption mechanisms is used to advance mechanism-specific probe compounds for cation exchange and surface complexation/cation bridging for quantifying the relevant site abundance and baseline sorption free energy. Existing literature studies point to the feasibility of developing mechanism-specific structural corrections to "adjust" mechanism-specific probe sorption measures to estimate the magnitude of sorption for any polyfunctional ionogenic compound of interest. Advancement of our conceptual framework to a quantitative K(d) model requires more extensive evaluation of ionogenic compound sorption under consistent experimental conditions.

Trends in soil sorption coefficients within common antimicrobial families.

Sorption coefficients (K(d)) of fluoroquinolone, tetracycline, and sulfonamide antimicrobial compounds were measured for seven soils between pH 4.5 and 8.5 using batch sorption techniques. Soils were chosen to encompass a range of cation exchange capacity (CEC), iron and aluminum oxide and organic matter contents. For most soil-pH pairs, enrofloxacin, norfloxacin, and ciprofloxacin K(d) values were within a factor of 2 (0.3 log units) of each other. Lower enrofloxacin sorption than norfloxacin or ciprofloxacin sorption was observed at pH 8.5 for the two most aluminosilicate clay-rich soils, likely due to compound differences in acid dissociation constants, yielding greater anion species abundance for enrofloxacin. Tetracycline, oxytetracycline and chlortetracycline K(d) values also were within a factor of 2 for each soil-pH pair. Measured tetracycline and fluoroquinolone compound K(d) values could be estimated within a factor of 2 using published empirical multi-linear regression models. In contrast, sulfonamide K(d) values varied among compounds, as expected for sorbates that interact primarily with soil organic matter. Results of this research indicate that substituent groups have little effect on sorption interactions of compounds from the tetracycline and fluoroquinolone family that interact with soils primarily through cation exchange, surface complexation and cation bridging sorption mechanisms.

Hydroxynaphthoic acid isomer sorption onto goethite.

This study used batch and attenuated total reflectance-Fourier-transform infrared (ATR-FTIR) flow-through techniques, along with computational chemistry, to probe the sorption of hydroxynaphthoic acid (HNA) isomers at the goethite-water interface. The HNA isomers employed in this study, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid, possessed an intramolecular hydrogen bond (IHB) between their carboxyl and hydroxyl groups, which resulted in coupled vibrational modes. Complimentary information from batch and ATR-FTIR studies suggested surface complexation via a bidentate structure, involving both the carboxylate and phenolate groups, as the dominant mode of sorption. A secondary HNA surfaces species noted only at pH 4 appeared to sorb via the carboxylate group, with the phenolic group involved in IHB or H-bonded to the solvent or surface hydroxyl groups. Despite the lack of unique vibrational modes for the key functional groups our experimental approach was successful in proposing interfacial structures, while acknowledging the limitations with respect to differentiating mono- vs. binuclear complexes. Finally, the spectral similarity of HNA sorbed onto goethite and onto the clay fraction of an iron oxide-rich soil suggested analogous solute interaction in pure phase minerals and soils.

Sorption of ciprofloxacin and oxytetracycline zwitterions to soils and soil minerals: influence of compound structure.

Oxytetracycline (OTC) zwitterions sorbed to a greater extent than ciprofloxacin (CIP) zwitterions onto goethite and soils with moderate-to-low effective cation exchange capacities (ECEC < 10 cmol(c)/kg) because adjacent pairs of hydroxyl groups on the OTC molecule (absent in CIP) facilitated greater surface complexation to soil metal oxides and aluminosilicate edge sites. CIP sorbed to a higher extentthan OTC onto aluminosilicates and onto soils with "high" ECEC values (>10 cmol(c)/kg). The sorption of heterocyclic compounds structurally similar to CIP indicated that both positive charge localization on the cationic amine and the extent of charge delocalization to the heterocyclic ring influenced molecular orientation within the montmorillonite interlayers, van der Waals interactions, and the potential for sorption. The sorption of compounds structurally similar to OTC revealed that greater positive charge localization on the cationic amine facilitated sorption to montmorillonite, whereas ortho substituted anionic and cationic groups on a zwitterionic molecule resulted in unfavorable Coulombic interactions between the anionic moiety and the negatively charged surface and hindered sorption. Thus, greater CIP zwitterion sorption to aluminosilicates and "high" ECEC soils resulted from greater distance between the anionic and cationic groups, which maximized Coulombic attraction to the surface.

Improved speciation of dissolved organic nitrogen in natural waters: amide hydrolysis with fluorescence derivatization.

The objective of this study was to improve primary-amine nitrogen (1 degree-N) quantification in dissolved organic matter (DOM) originating from natural waters where inorganic forms of N, which may cause analytical interference, are commonly encountered. Efforts were targeted at elucidating organic-N structural criteria influencing the response of organic amines to known colorimetric and fluorescent reagents and exploring the use of divalent metal-assisted amide hydrolysis in combination with fluorescence analyses. We found that reaction of o-phthaldialdehyde (OPA) with primary amines is significantly influenced by steric factors, whereas fluorescamine (FLU) lacks sensitivity to steric factors and allows for the detection of a larger suite of organic amines, including di- and tri-peptides and sterically hindered 1degree-N. Due to the near quantitative recovery of dissolved peptides with the FLU reagent and lack of analytical response to inorganic nitrogen, we proposed that FLU be utilized for the quantification of primary amine nitrogen. In exploring the application of divalent metal promoted peptide hydrolysis to the analysis of organic forms of nitrogen in DOM, we found that Zn(II) reaction increased the total fraction of organic-N detectable by both OPA and FLU reagents. Zn-hydrolysis improved recovery of organic-N in natural waters from < 5% to 35%. The above method, coupled with standard inorganic-N analyses, allows for enhanced resolution of dissolved organic nitrogen (DON) speciation in natural waters.

Spectroscopic investigation of ciprofloxacin speciation at the goethite-water interface.

We investigated ciprofloxacin (a fluoroquinolone antibiotic) speciation as a function of pH in aqueous solution and in the presence of dissolved ferric ions and goethite using ATR-FTIR and UV-vis spectroscopy. The presence of dissolved and surface bound ferric species induced the deprotonation of the ciprofloxacin carboxylic acid group at pH < pKa1. The resultant ciprofloxacin zwitterions appeared to interact via both carboxylate oxygens to form bidentate chelate and bridging bidentate complexes within colloidal iron oxide-ciprofloxacin precipitates and bidentate chelates on the goethite surface. However, the structure of the aqueous ferric-ciprofloxacin complexes remains unclear. Our evidence for bidentate chelates (involving only the carboxylate oxygens) on the goethite surface was distinct from previous IR studies of fluoroquinolone sorption to metal oxides that have proposed surface complexes involving both the keto and the carboxylate groups. We find that the distinct ciprofloxacin surface complex proposed at the goethite-water interface may be a result of differences in metal oxide mineralogy or assignment of the carboxylate antisymmetric stretch in the metal oxide-fluoroquinolone spectra.

Factors influencing the sorption of oxytetracycline to soils.

Veterinary antibiotics such as oxytetracycline (OTC) increasingly are found in the environment and often come into direct contact with soils via the release of animal wastes. Oxytetracycline is known to sorb strongly to soils by interaction with soil organic matter, clay minerals, and metal oxides. However, current knowledge of the influence of soil properties on OTC sorption is limited, as is our ability to predict OTC sorption to soils. This work was aimed at identifying properties that most influence the extent of OTC sorption in a suite of soils from the eastern United States representing a wide range in soil properties. Thirty soils were well characterized, an OTC soil-water distribution coefficient (Kd) was determined for each soil, and statistical analyses were employed to determine appropriate soil descriptors of OTC sorption. Soil texture, cation exchange capacity, and iron oxide content seemed to most influence the extent of OTC sorption in soils with organic carbon (OC) content between 0 and 4%. Thus, the knowledge of these three soil properties would be key to anticipating the extent of OTC sorption and gaining insight into OTC fate within a given soil system. Notably, OC content appeared to influence OTC sorption only in a soil with 9% OC.

2,4-D sorption in iron oxide-rich soils: role of soil phosphate and exchangeable Al.

This study examined herbicide retention in iron oxide-rich variable charge soils (Ultisols) under no cultivation (forest), agriculture (farm), and turf maintenance (golf course) to explore the following hypothesis: inorganic phosphate accumulation from soil fertilization and liming to decrease exchangeable aluminum (Al) content will influence carboxylic acid herbicide sorption onto soils and leaching into groundwater. A suite of soil properties, including mineralogy (particularly soil iron and aluminum oxide content), exchangeable Al content, and soil phosphate content, influenced sorption of the anionic, 2,4-D. In general, 2,4-D sorption was lower in the presence of phosphate, possibly due to competition between phosphate and 2,4-D for surface sites or increase in surface negative charge resulting from phosphate sorption. Additionally, 2,4-D sorption was greater in the presence of exchangeable Al. It appears that 2,4-D may form surface complexes with or be electrostatically attracted to exchangeable aluminum in the soil. Our results suggest that carboxylic acid herbicides may be more easily leached in intensively managed Ultisols subject to continued phosphate fertilization and liming.

Fluoride sorption and associated aluminum release in variable charge soils.

Fluoride sorption and related aluminum (Al) release are evaluated in two iron-oxide-rich soils as a function of soil depth, composition, and physical-chemical properties and potential mechanisms of fluoride-surface interaction are suggested. Measured Al concentrations at equilibrium fluoride sorption, reflective of the net balance between Al dissolution and sequestration of the released Al by the solid phase, suggest net fluoride-assisted dissolution of Al-bearing amorphous and crystalline soil minerals. Strikingly, soils of similar depth and horizonation from the same soil order but of distinct soil series exhibited markedly different susceptibility to Al loss in the presence of fluoride, possibly a combined result of differences in the mechanism of fluoride sorption, soil mineralogy, reactivity of the surficial Al and Fe, and soil solution chemistry. Fluoride sorption is strongly correlated with soil Al and Fe present as high-surface-area amorphous and crystalline oxide phases. Fluoride complexation to surficial Al and Fe ions via ligand exchange with surficial OH groups and water molecules appears to be the dominant sorption mechanism. At high dissolved fluoride concentrations (>7 mM), other mechanisms of fluoride retention including adsorption of AlF solution complexes, entrapment in the interparticle pore fluid, and precipitation into solution and/or onto the soil surface are also likely.

Sorption-desorption of ionogenic compounds at the mineral-water interface: study of metal oxide-rich soils and pure-phase minerals.

Sorption of the ionic compounds 2,4-D and quinmerac onto iron oxide-rich, variable charged soils was strongly influenced by mineralogy, particularly soil iron and aluminum oxides, whereas sorption of the neutral norflurazon was only related to total soil C. An appreciable fraction of the mass sorbed in stirred-flow studies was easily desorbed by deionized water, and desorption of ionic compounds was initially more rapid than sorption. This sorption-desorption behavior, although contrary to desorption hysteresis commonly observed in batch studies, suggests that the reversibly sorbed fraction is weakly bound to the soil surface. 2,4-D sorption to iron oxide-rich soils and pure-phase metal oxides appears to be driven by nonspecific electrostatic attraction, with specific electrostatic attraction and van der Waals interactions being secondary. Both the carboxylate and the heterocyclic N groups may participate in sorption of quinmerac, facilitated by specific and nonspecific electrostatic attraction and surface complexation. The heterocyclic N, amine, and carbonyl groups of norflurazon do not appear to interact with soil minerals.