Stephen A. Boyd

Clay-organic complexes as adsorbents for phenol and chlorophenols

Several clay-organic complexes were synthesized by placing quaternary ammonium cations on smectite by cation exchange. They were then examined for their ability to adsorb phenol and several of its chlorinated congeners. The organic cations used were: hexadecylpyridinium (HDPY+), hexadecyltri-methyl ammonium (HDTMA+), trimethylphenyl ammonium (TMPA), and tetramethylammonium (TMA+). The complexes containing long-chain alkyl (hexadecyl) groups were the most hydrophobic and adsorbed the phenols from water in proportion to their hydrophobicities, which increase with chlorine addition (phenol < chlorophenol < dichloropohenol < trichlorophenol). With n-hexane as the solvent, different adsorption was found which depended on the type and degree of solvent interactions with the compound and the clay-organic complex. Thus, the amount of adsorption of these phenols on clay-organic complexes was dependent on the relative energies of adsorbent-adsorbate and adsorbate-solvent interactions.

Pentachlorophenol sorption by organo-clays

Several clay organic complexes were prepared by placing organic cations on the exchange sites of smectite clays and studied as sorbents for pentachlorophenol (PCP). The organic cations used ranged from very hydrophobic in nature (e.g., dioctadecyldimethyl+ (DODMA+)- and hexadecyltrimethyl+ (HDTMA+)-ammonium) to those having minimal hydrophobic properties, such as tetramethylammonium+ (TMA+). In general, the more hydrophobic the cation on the smectite the greater the uptake of PCP from water. For the very hydrophobic clays (DODMA+- and HDTMA+-smectite) the uptake of PCP was via non-polar interactions between the alkyl (e.g., -C18) groups on the organic cation and PCP. In a mechanistic sense, this interaction appeared to be similar to a partitioning process between water and the organic phase of the clay-organic complex. The organic phases of DODMA+-smectite were about 10 times more effective than the organic matter of natural sediments for removing PCP from water. For those organo-clays containing small organic cations (e.g., TMA+), the organic phase consisted of separate small organic moieties, such as the methyl group. This phase did not act as an effective partitioning medium despite a significant carbon content, and very little PCP was taken up. Results from this study suggest the possibility of treating soils and subsurface materials with large hydrophobic organic cations to enhance the sorptive properties of these natural materials.

Reductive Dechlorination of Polychlorinated Biphenyls by Anaerobic Microorganisms from Sediments

Microorganisms from Hudson River sediments reductively dechlorinated most polychlorinated biphenyls (PCBs) in Aroclor 1242 under anaerobic conditions, thus demonstrating PCB dechlorination by anaerobic bacteria in the laboratory. The most rapid dechlorination was observed at the highest PCB concentration used; at 700 parts per million Aroclor, 53 percent of the total chlorine was removed in 16 weeks, and the proportion of mono- and dichlorobiphenyls increased from 9 to 88 percent. Dechlorination occurred primarily from the meta and para positions; congeners that were substituted only in the ortho position (or positions) accumulated. These dechlorination products are both less toxic and more readily degraded by aerobic bacteria. These results indicate that reductive dechlorination may be an important environmental fate of PCBs, and suggest that a sequential anaerobic-aerobic biological treatment system for PCBs may be feasible.

HYDROPHOBICITY OF SILOXANE SURFACES IN SMECTITES AS REVEALED BY AROMATIC HYDROCARBON ADSORPTION FROM WATER

The nature of the siloxane surface in smectites was investigated by measuring the adsorption of aromatic hydrocarbons from water by organo-clays. The organo-clays were prepared by replacing the hydrophilic, inorganic exchange cations of a series of smectites with the small, hydrophobic organic cation, trimethylphenylammonium (TMPA). Smectites with a range in charge densities were used that resulted in different TMPA contents in the organo-clays. Adsorption isotherms of benzene, alkylbenzenes, and naphthalene from water by the TMPA-smectites indicated that sorption was inversely related to TMPA content. The Langmuir form of the isotherms suggests that the aromatic compounds adsorb to the clay surface. Possible adsorptive sites in TMPA-smectites are limited to the TMPA cations and the siloxane oxygen surfaces. Because sorption increased as layer charge and TMPA content decreased, the organic compounds must adsorb to the siloxane surfaces.Calculations based on an adsorbed compound monolayer, which was estimated by fitting adsorption data to the Langmuir equation, and the N2 specific surface area of each TMPA-clay, indicate that the surface area occupied by each adsorbed molecule increases as the planar area of the molecule increases. This strongly indicates that the planar surfaces of the compounds adsorb directly to the clay surface. Apparently, the TMPA cations function to keep the smectite interlayers open. Interactions between the phenyl groups of TMPA cations on opposing interlayer clay surfaces may act to increase the size of the adsorptive regions. These results show that the siloxane surfaces of smectites can effectively adsorb aromatic hydrocarbons from water if the hydrophilic, inorganic exchange cations are replaced with small, hydrophobic organic cations. The strong adsorption of hydrophobic organic molecules from water demonstrates the hydrophobicity of the siloxane surfaces in smectites.

Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities

A high-charge smectite from Arizona [cation-exchange capacity (CEC) = 120 meq/100 g] and a low-charge smectite from Wyoming (CEC = 90 meq/100 g) were used to prepare homoionic tetra-methylammonium (TMA)-clay complexes. The adsorption of benzene, toluene, and o-xylene as vapors by the dry TMA-clays and as solutes from water by the wet TMA-clays was studied. The adsorption of the organic vapors by the dry TMA-smectite samples was strong and apparently consisted of interactions with both the aluminosilicate mineral surfaces and the TMA exchange ions in the interlayers. In the adsorption of organic vapors, the closer packing of TMA ions in the dry high-charge TMA-smectite, compared with the dry low-charge TMA-smectite, resulted in a somewhat higher degree of shape-selective adsorption of benzene, toluene, and xylene. In the presence of water, the adsorption capacities of both samples for the aromatic compounds were significantly reduced, although the uptake of benzene from water by the low-charge TMA-smectite was still substantial. This lower sorption capacity was accompanied by increased shape-selectivity for the aromatic compounds. The reduction in uptake and increased selectivity was much more pronounced for the water-saturated, high-charge TMA-smectite than for the low-charge TMA-smectite. Hydration of the TMA exchange ions and/or the mineral surfaces apparently reduced the accessibility of the aromatic molecules to interlamellar regions. The resulting water-induced sieving effect was greater for the high-charge TMA-smectite due to the higher density of exchanged TMA-ions. The low-charge Wyoming TMA-smectite was a highly effective adsorbent for removing benzene from water and may be useful for purifying benzene-contaminated water.

Sorption of nonionic organic compounds in soil-water systems containing a micelle-forming surfactant

The solubility enhancement of nonionic organic compounds (NOCs) by surfactants may represent an important tool in chemical and biological remediation of contaminated soils. In aqueous systems, the presence of dissolved surfactant emulsions or micelles may enhance the solubility of NOCs by acting as a hydrophobic partitioning phase for the NOCs. However, most environmental remediation efforts involve soil-water or sediment-water systems, where surfactant molecules may also interact with the solid phase. An understanding of the effect of surfactants on the sorption and distribution of NOCs in soil or sediment environments will provide an essential basis for utilizing surfactants in environmental remediation. In this study, the authors examined the effect of a micelle-forming surfactant (Triton X-100) on the sorption of 2,2{prime},4,4{prime},5,5{prime}-PCB, 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p{prime}-DDT) and 1,2,4-trichlorobenzene (1,2,4-TCB). A conceptual model, which accurately describes the functional dependence of K* on Triton X-100 concentration, was developed based on the partition coefficients of these NOCs by soil, soil-surfactant, surfactant monomer and surfactant micelle phases. This model can be further modified to provide quantitative prediction of K* of a given NOC at different surfactant concentrations.

Cationic surfactant sorption to a vermiculitic subsoil via hydrophobic bonding

Organoclays formed in soil from the addition of the cationic surfactant hexadecyltrimethylammonium (HDTMA) can effectively immobilize organic contaminants dissolved in water. The adsorption and desorption of HDTMA in a subsoil was studied to determine the stability of surfactant-soil clay complexes as affected by surfactant retention mechanism. We found that HDTMA was initially adsorbed by cation exchange in the interlayer, causing extensive clay aggregation. As the loading increased, HDTMA adsorbed to the external surfaces of aggregates via both cation exchange and hydrophobic bonding, the latter causing positive charge development on surfaces and ultimately clay dispersion. When the equilibrium concentration of HDTMA reached the critical micelle concentration, no further HDTMA adsorption occurred. Desorption of HDTMA was more significant when the HDTMA retention mechanism was hydrophobic bonding. HDTMA adsorption can be affected by cation type as well as the type and concentration of electrolytes, and these factors can be used to minimize the undesirable effects of hydrophobic bonding such as clay dispersion and HDTMA desorption.

Microbial reductive dechlorination of PCBs

Reductive dechlorination is an advantageous process to microorganisms under anaerobic conditions because it is an electron sink, thereby allowing reoxidation of metabolic intermediates. In some organisms this has been demonstrated to support growth. Many chlorinated compounds have now been shown to be reductively dechlorinated under anaerobic conditions, including many of the congeners in commercial PCB mixtures. Anaerobic microbial communities in sediments dechlorinate Aroclor at rates of 3 µg Cl/g sediment × week. PCB dechlorination occurs at 12° C, a temperature relevant for remediation at temperate sites, and at concentrations of 100 to 1000 ppm. The positions dechlorinated are usually meta > para > ortho. The biphenyl rings, and the mono-ortho- and diorthochlorobiphenyls were not degraded after a one year incubation. Hence subsequent aerobic treatment may be necessary to meet regulatory standards. Reductive dechlorination of Arochlors does reduce their dioxin-like toxicity as measured by bioassay and by analysis of the co-planar congeners. The most important limitation to using PCB dechlorination as a remediation technology is the slower than desired dechlorination rates and no means yet discovered to substantially enhance these rates. Long term enrichments using PCBs as the only electron acceptor resulted in an initial enhancement in dechlorination rate. This rate was sustained but did not increase in serial transfers. Bioremediation of soil contaminated with Aroclor 1254 from a transformer spill was dechlorinated by greater than 50% following mixing of the soil with dechlorinating organisms and river sediment. It is now reasonable to field test reductive dechlorination of PCBs in cases where the PCB concentration is in the range where regulatory standards may be directly achieved by dechlorination, where a subsequent aerobic treatment is feasible, where any co-contaminants do not pose an inhibitory problem, and where anaerobic conditions can be established.

Adsorption of phenol and chlorinated phenols from aqueous solution by tetramethylammonium- and tetramethylphosphonium-exchanged montmorillonite

Sorption of phenol and 2-, 3- and 4-chlorophenol from water by tetramethylammonium (TMA)-smectite and tetramethylphosphonium (TMP)-smectite was studied. Sorption of the phenolic compounds appeared to occur on the aluminosilicate mineral surfaces between neighboring organic cations (TMA or TMP). TMP-smectite was a better sorbent than TMA-smectite, which did not measurably adsorb any of the phenolic compounds. This disparity in sorption efficiency was attributed to differences in hydration of the interlayer cations. Apparently, hydration occurred to a greater extent in TMA-smectite that in TMP-smectite, causing the interlayer pore size to be smaller for TMA-smectite than for TMP-smectite. TMP-smectite showed selective sorption within the group of chlorinated phenols studied. Phenol and 4-chlorophenol were effectively sorbed by TMP-smectite, whereas 2-and 3-chlorophenol were not sorbed. The selectivity appeared to be size- and shape-dependent, and not strongly influenced by water solubility.

Shape-selective adsorption of aromatic molecules from water by tetramethylammonium–smectite

The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA–smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA–smectite were influenced strongly by the presence of water. The dry TMA–smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA–smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.