Resolution of Adsorption and Partition Components of Organic Compounds on Black Carbons.

Black carbons (BCs) may sequester non-ionic organic compounds by adsorption and/or partition to varying extents. Up to now, no experimental method has been developed to accurately resolve the combined adsorption and partition capacity of a compound on a BC. In this study, a unique "adsorptive displacement method" is introduced to reliably resolve the adsorption and partition components for a solute-BC system. It estimates the solute adsorption on a BC by the use of an adsorptive displacer to displace the adsorbed target solute into the solution phase. The method is validated by tests with uses of activated carbon as the model carbonaceous adsorbent, soil organic matter as the model carbonaceous partition phase, o-xylene and 1,2,3-trichlorobenzene as the reference solutes, and p-nitrophenol as the adsorptive displacer. Thereafter, the adsorption-partition resolution was completed for the two solutes on selected model BCs: four biochars and two National Institute of Standards and Technology (NIST) standard soots (SRM-2975 and SRM-1650b). The adsorption and partition components resolved for selected solutes with given BCs and their dependences upon solute properties enable one to cross-check the sorption data of other solutes on the same BCs. The resolved components also provide a theoretical basis for exploring the potential modes and extents of different solute uptakes by given BCs in natural systems.

Fast and slow rates of naphthalene sorption to biochars produced at different temperatures.

This study investigated the sorption kinetics of a model solute (naphthalene) with a series of biochars prepared from a pine wood at 150-700 °C (referred as PW100-PW700) to probe the effect of the degree of carbonization of a biochar. The samples were characterized by the elemental compositions, thermal gravimetric analyses, Fourier transform IR spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller-N(2) surface areas (SA), and pore size distributions. Naphthalene exhibited a fast rate of sorption to PW150 owning a high oxygen content and a small SA, due supposedly to the solute partition into a swollen well-hydrated uncarbonized organic matter of PW150. The partial removal of polar-group contents in PW250/PW350, which increased the compactness of the partition medium, decreased the diffusion of the solute into the partition phase to result in a slow sorption rate. With PW500 and PW700 displaying low oxygen contents and high SA, the solute sorption rates were fast, attributed to the near exhaustion of a partition phase in the sample and to the fast solute adsorption on the carbonized biochar component. The results illustrate that the sorption rate of a solute with biochars is controlled largely by the solute's diffusivity in the biochar's partition phase, in which the medium compactness affects directly the solute diffusivity.

Selected veterinary pharmaceuticals in agricultural water and soil from land application of animal manure.

Veterinary pharmaceuticals are commonly administered to animals for disease control, and added into feeds at subtherapeutic levels to improve feeding efficiency. As a result of these practices, a certain fraction of the pharmaceuticals are excreted into animal manures. Land application of these manures contaminates soils with the veterinary pharmaceuticals, which can subsequently lead to contamination of surface and groundwaters. Information on the occurrence and fate of pharmaceuticals in soil and water is needed to assess the potential for exposure of at-risk populations and the impacts on agricultural ecosystems. In this study, we investigated the occurrence and fate of four commonly used veterinary pharmaceuticals (amprolium, carbadox, monensin, and tylosin) in a farm in Michigan. Amprolium and monensin were frequently detected in nearby surface water, with concentrations ranging from several to hundreds of nanograms per liter, whereas tylosin or carbadox was rarely found. These pharmaceuticals were more frequently detected in surface runoff during nongrowing season (October to April) than during growing season (May to September). Pharmaceuticals resulting from postharvest manure application appeared to be more persistent than those from spring application. High concentrations of pharmaceuticals in soils were generally observed at the sites where the respective concentrations in surface water were also high. For monensin, the ratios of soil-sorbed to aqueous concentrations obtained from field samples were within the order of the distribution coefficients obtained from laboratory studies. These results suggest that soil is a reservoir for veterinary pharmaceuticals that can be disseminated to nearby surface water via desorption from soil, surface runoff, and soil erosion.

Improved prediction of the bioconcentration factors of organic contaminants from soils into plant/crop roots by related physicochemical parameters.

There has been an on-going pursuit for relations between the levels of chemicals in plants/crops and the source levels in soil or water in order to address impacts of toxic substances on human health and ecological quality. In this research, we applied the quasi-equilibrium partition model to analyze the relations for nonionic organic contaminants between plant/crop roots and external soil/water media. The model relates the in-situ root concentration factors of chemicals from external water into plant/crop roots (RCF(water)) with the system physicochemical parameters and the chemical quasi-equilibrium states with plant/crop roots (αpt, ≤1). With known RCF(water) values, root lipid contents (flip), and octanol-water Kow's, the chemical-plant αpt values and their ranges of variation at given flipKow could be calculated. Because of the inherent relation between αpt and flipKow, a highly distinct correlation emerges between log RCF(water) and log flipKow (R2 = 0.825; n = 368), with the supporting data drawn from 19 disparate soil-plant studies covering some 6 orders of magnitude in flipKow and 4 orders of magnitude in RCF(water). This correlation performs far better than any relationship previously developed for predicting the contamination levels of pesticides and toxic organic chemicals in plant/crop roots for assessing risks on food safety.

Determination of the Henry's law constants of low-volatility compounds via the measured air-phase transfer coefficients.

Accurate Henry's law constants (H) are unavailable for the majority of organic pollutants, especially those having a low volatility. A novel kinetics-based experimental method is introduced to determine H for a wide range of low-H compounds. The method consists of measuring independently the water-to-air transfer coefficient (KL) and the associated air-phase transfer coefficient (kG) of a low-H chemical (solute) in water when KL ≅ kGH prevails according to the two-film theory. The kG for a solute is obtained via a developed gas-dynamic equation that relates kG to the solute molecular weight and the solute-vapor escaping efficiency (ß) through a boundary air layer. The value of ß is only a function of the in situ air turbulence level, independent of the chemical species. Thus, the required ß for solutes can be estimated from the evaporative rates of pure volatile liquids under the same ambient setting. By relating the estimated kG with the measured KL of a low-H solute, the solute H is established. The H values of 45 low-H chemicals, including many complex pesticides, in the range of ∼10-7 to ∼10-3 have thus been determined. The accountability of the method is underscored by the consistency of the measured and credible literature H values for a number of the low-H compounds studied.

Evaluating phenanthrene sorption on various wood chars.

A certain amount of wood char or soot in a soil or sediment sample may cause the sorption of organic compounds to deviate significantly from the linear partitioning commonly observed with soil organic matter (SOM). Laboratory produced and field wood chars have been obtained and analyzed for their sorption isotherms of a model solute (phenanthrene) from water solution. The uptake capacities and nonlinear sorption effects with the laboratory wood chars are similar to those with the field wood chars. For phenanthrene aqueous concentrations of 1 microg l(-1), the organic carbon-normalized sorption coefficients (log K(oc)) ranging from 5.0 to 6.4 for field chars and 5.4-7.3 for laboratory wood chars, which is consistent with literature values (5.6-7.1). Data with artificial chars suggest that the variation in sorption potential can be attributed to heating temperature and starting material, and both the quantity and heterogeneity of surface-area impacts the sorption capacity. These results thus help to corroborate and explain the range of logK(oc) values reported in previous research for aquifer materials containing wood chars.

Clay-catalyzed reactions of coagulant polymers during water chlorination.

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence.

Lipid-water partition coefficients and correlations with uptakes by algae of organic compounds.

In view of the scarcity of the lipid-water partition coefficients (Ktw) for organic compounds, the logKtw values for many environmental contaminants were measured using ultra-pure triolein as the model lipid. Classes of compounds studied include alkyl benzenes, halogenated benzenes, short-chain chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides. In addition to logKtw determination, the uptakes of these compounds from water by a dry algal species were measured to evaluate the lipid effect on the algal uptake. The measured logKtw are closely related to their respective logKow (octanol-water), with logKow=1.9 to 6.5. A significant difference is observed between the present and early measured logKtw for compounds with logKow>∼5, which is attributed to the presence and absence of a triolein microemulsion in water affecting the solute partitioning. The observed lipid-normalized algae-water distribution coefficients (logKaw/lipid) are virtually identical to the respective logKtw values, which manifests the dominant lipid-partition effect of the compounds with algae.

On the use of a freeze-dried versus an air-dried soil humic acid as a surrogate of soil organic matter for contaminant sorption.

The sorption of phenanthrene (PHN) to relatively pure soil humic acids (HAs) was investigated to assess the suitability of the soil HA as a surrogate sorbent for the soil organic matter (SOM). The HAs were prepared in both freeze-dried and air-dried forms. The two forms of HAs from the same source are similar in composition but the freeze-dried HAs exhibit a significantly higher initial surface area (SA) (3.86-4.59 m(2)/g); the SAs of air-dried HAs are below 0.1 m(2)/g. However, the SAs of freeze-dried HAs are not stable upon contact with water; the samples lose practically all the SA after 4 days of immersion in water. The PHN sorption to both forms of HAs is practically linear, whether a co-solute is present or not. The sorption linearity observed with the present freeze-dried HAs is in sharp contrast with the allegedly nonlinear PHN sorption on similar freeze-dried HAs as presented by others.

Partition coefficients of organic contaminants with carbohydrates.

In view of the current lack of reliable partition coefficients for organic compounds with carbohydrates (K(ch)), carefully measured values with cellulose and starch, the two major forms of carbohydrates, are provided for a wide range of compounds: short-chain chlorinated hydrocarbons, halogenated benzenes, alkyl benzenes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and organochlorine pesticides. To ensure the accuracy of the K(ch) data, solute concentrations in both water and carbohydrate phases are measured by direct solvent extraction of the samples. For a given compound, the observed partition coefficient with cellulose (K(cl)) is virtually the same as that with starch (K(st)). This finding expedites the evaluation of organic contamination with different forms of carbohydrates. The presently determined K(ch) values of 13 PAHs are substantially lower (by 3-66 times) than the literature data; the latter are suspect as they were obtained with (i) presumably impure carbohydrate samples or (ii) indirectly measured equilibrium solute concentrations in carbohydrate and water phases. Although the K(ch) values are generally considerably lower than the respective K(ow) (octanol-water) or K(lipid) (lipid-water), accurate K(ch) data are duly required to accurately estimate the contamination of carbohydrates by organic compounds because of the abundance of carbohydrates over lipids in crops and plants. To overcome the current lack of reliable K(ch) data for organic compounds, a close correlation of log K(ch) with log K(ow) has been established for predicting the unavailable K(ch) data for low-polarity compounds.

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD).

UNLABELLED: PURPOSES AND AIMS: Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water. MATERIALS AND METHODS: An industrial-grade diatomite was used as the iron oxide support. The diatomite was first acidified and dried and then coated with iron oxide up to five times. The prepared IOCD samples were characterized for their morphology, composition, elemental content, and crystal properties by various instruments. Experiments of equilibrium and kinetic adsorption of As(V) on IOCD were conducted using 0.1- and 2-L polyethylene bottles, respectively, at different pH and temperatures. RESULTS: Iron oxide (alpha-Fe(2)O(3) hematite) coated onto diatomite greatly improves (by about 30 times) the adsorption of As(V) from water by IOCD as compared to using raw diatomite. This improvement was attributed to increases in both surface affinity and surface area of the IOCD. The surface area of IOCD increased to an optimal value. However, as the IOCD surface area (93 m(2)/g) was only 45% higher than that of raw diatomite (51 m(2)/g), the enhanced As(V) adsorption resulted primarily from the enhanced association of negatively charged As(V) ions with the partial positive surface charge of the iron oxide. The As(V) adsorption decreased when the solution pH was increased from 3.5 to 9.5, as expected from the partial charge interaction between As(V) and IOCD. The adsorption data at pH 5.5 and 7.5 could be well fitted to the Freundlich equation. A moderately high exothermic heat was observed for the As(V) adsorption, with the calculated molar isosteric heat ranging from -4 to -9 kcal/mol. The observed heats fall between those for physical adsorption and chemisorption and are indicative of the formation of a series of ion-pair complexes of As(V) ions with iron oxide surface groups. CONCLUSIONS: This study demonstrated that the granular IOCD was successfully developed and employed to remove the As(V) in aqueous solution. The Freundlich isotherm well fitted the equilibrium adsorption data of As(V) onto IOCD, and both the pseudo-second-order model and the pore diffusion model simulated well the adsorption kinetics. Compared to other iron-oxide-based adsorbents reported in the literatures, the adsorption capacity of IOCD is relatively high and its kinetics is fast.

The organic contamination level based on the total soil mass is not a proper index of the soil contamination intensity.

Concentrations of organic contaminants in common productive soils based on the total soil mass give a misleading account of actual contamination effects. This is attributed to the fact that productive soils are essentially water-saturated, with the result that the soil uptake of organic compounds occurs principally by partition into the soil organic matter (SOM). This report illustrates that the soil contamination intensity of a compound is governed by the concentration in the SOM (C(om)) rather than by the concentration in whole soil (C(s)). Supporting data consist of the measured levels and toxicities of many pesticides in soils of widely differing SOM contents and the related levels in in-situ crops that defy explanation by the C(s) values. This SOM-based index is timely needed for evaluating the contamination effects of food crops grown in different soils and for establishing a dependable priority ranking for intended remediation of numerous contamination sites.

Linear adsorption of nonionic organic compounds from water onto hydrophilic minerals: silica and alumina.

To characterize the linear adsorption phenomena in aqueous nonionic organic solute-mineral systems, the adsorption isotherms of some low-molecular-weight nonpolar nonionic solutes (1,2,3-trichlorobenzene, lindane, phenanthrene, and pyrene) and polar nonionic solutes (1,3-dinitrobenzene and 2,4-dinitrotoluene) from single- and binary-solute solutions on hydrophilic silica and alumina were established. Toward this objective, the influences of temperature, ionic strength, and pH on adsorption were also determined. It is found that linear adsorption exhibits low exothermic heats and practically no adsorptive competition. The solute-solid configuration and the adsorptive force consistent with these effects were hypothesized. For nonpolar solutes, the adsorption occurs presumably by London (dispersion) forces onto a water film above the mineral surface. For polar solutes, the adsorption is also assisted by polar-group interactions. The reduced adsorptive forces of solutes with hydrophilic minerals due to physical separation by the water film and the low fractions of the water-film surface covered by solutes offer a theoretical basis for linear solute adsorption, low exothermic heats, and no adsorptive competition. The postulated adsorptive forces are supported by observations that ionic strength or pH poses no effect on the adsorption of nonpolar solutes while it exhibits a significant effect on the uptake of polar solutes.

Relation of organic contaminant equilibrium sorption and kinetic uptake in plants.

Plant uptake is one of the environmental processes that influence contaminant fate. Understanding the magnitude and rate of plant uptake is critical to assessing potential crop contamination and the development of phytoremediation technologies. We determined (1) the partition-dominated equilibrium sorption of lindane (LDN) and hexachlorobenzene (HCB) by roots and shoots of wheat seedlings, (2) the kinetic uptake of LDN and HCB by roots and shoots of wheat seedlings, (3)the kinetic uptake of HCB,tetrachloroethylene (PCE), and trichloroethylene (TCE) by roots and shoots of ryegrass seedlings, and (4) the lipid, carbohydrate, and water contents of the plants. Although the determined sorption and the plant composition together suggest the predominant role of plant lipids for the sorption of LDN and HCB, the predicted partition with lipids of LDN and HCB using the octanol-water partition coefficients is notably lower than the measured sorption, due presumably to underestimation of the plant lipid contents and to the fact that octanol is less effective as a partition medium than plant lipids. The equilibrium sorption orthe estimated partition can be viewed as the kinetic uptake limits. The uptakes of LDN, PCE, and TCE from water at fixed concentrations increased with exposure time in approach to steady states. The uptake of HCB did not reach a plateau within the tested time because of its exceptionally high partition coefficient. In all of the cases, the observed uptakes were lower than their respective limits, due presumably to contaminant dissipation in and limited water transpiration by the plants.

Improved prediction of octanol-water partition coefficients from liquid-solute water solubilities and molar volumes.

A volume-fraction-based solvent-water partition model for dilute solutes, in which the partition coefficient shows a dependence on solute molar volume (V), is adapted to predict the octanol-water partition coefficient (K(ow)) from the liquid or supercooled-liquid solute water solubility (Sw), or vice versa. The established correlation is tested for a wide range of industrial compounds and pesticides (e.g., halogenated aliphatic hydrocarbons, alkylbenzenes, halogenated benzenes, ethers, esters, PAHs, PCBs, organochlorines, organophosphates, carbamates, and amides-ureas-triazines), which comprise a total of 215 test compounds spanning about 10 orders of magnitude in Sw and 8.5 orders of magnitude in K(ow). Except for phenols and alcohols, which require special considerations of the K(ow) data, the correlation predicts the K(ow) within 0.1 log units for most compounds, much independent of the compound type or the magnitude in K(ow). With reliable Sw and V data for compounds of interest, the correlation provides an effective means for either predicting the unavailable log K(ow) values or verifying the reliability of the reported log K(ow) data.

Sorption of aromatic organic pollutants to grasses from water.

The influence of plant lipids on the equilibrium sorption of three aromatic solutes from water was studied. The plant-water sorption isotherms of benzene, 1,2-dichlorobenzene, and phenanthrene were measured over a large range of solute concentrations using sealed vessels containing water, dried plant material, and solute. The plant materials studied include the shoots of annual rye, tall fescue, red fescue, and spinach as well as the roots of annual rye. Seven out of eight sorption isotherms were linear with no evidence of competitive effects between the solutes. For a given plant type, the sorption coefficient increased with decreasing solute water solubility. For a given solute, sorption increased with increasing plant lipid content. The estimated lipid-water partition coefficients of individual solutes were found to be significantly greater than the corresponding octanol-water partition coefficients. This indicates that plant lipids are a more effective partition solvent than octanol for the studied aromatic compounds. As expected, the solute lipid-water partition coefficients were log-linearly related to the respective water solubilities. For the compounds studied, partitioning into the lipids is believed to be the primary sorption mechanism.

Interactions of organic contaminants with mineral-adsorbed surfactants.

Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insightto interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

Compositions and sorptive properties of crop residue-derived chars.

Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption, a series of char samples were generated by pyrolyzing a wheat residue (Triticum aestivum L.) for 6 h at temperatures between 300 degrees C and 700 degrees C and analyzed for their elemental compositions, surface areas, and surface functional groups. The samples were then studied for their abilities to sorb benzene and nitrobenzene from water. A commercial activated carbon was used as a reference carbonaceous sample. The char samples produced at high pyrolytic temperatures (500-700 degrees C) were well carbonized and exhibited a relatively high surface area (>300 m2/g), little organic matter (<3%), and low oxygen content (< or = 10%). By contrast, the chars formed at low temperatures (300-400 degrees C) were only partially carbonized, showing significantly different properties (<200 m2/g surface area, 40-50% organic carbon, and >20% oxygen). The char samples exhibited a significant range of surface acidity/basicity because of their different surface polar-group contents, as characterized by the Boehm titration data and the NMR and FTIR spectra. The NOC sorption by high-temperature chars occurred almost exclusively by surface adsorption on carbonized surfaces, whereas the sorption by low-temperature chars resulted from the surface adsorption and the concurrent smaller partition into the residual organic-matter phase. The chars appeared to have a higher surface affinity for a polar solute (nitrobenzene) than for a nonpolar solute (benzene), the difference being related to the surface acidity/basicity of the char samples.

Evaluation of current techniques for isolation of chars as natural adsorbents.

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O7 2- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O7 2- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to non-oxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr2O7 2-oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.