Influence of rhamnolipids and triton X-100 on the desorption of pesticides from soils

A rhamnolipid biosurfactant mixture produced by P. aeruginosa UG2 and the surfactant Triton X-100 were tested for their effectiveness of enhancing the desorption of trifluralin, atrazine, and coumaphos from soils. Sorption of both surfactants by the soils was significant and adequately described by the Langmuir-type isotherm. Values of maximum sorption capacity (Qmax) and Langmuir constant (Klang) did not correlate with the amount of soil organic matter. Our results indicate that clay surfaces play an important role in the sorption of surfactants. When surfactant dosages were high enough to reach soil saturation and maintain an aqueous micellar phase, pesticide desorption was only enhanced. At dosages below soil saturation, surfactants sorbed onto soil, increasing its hydrophobicity and enhancing the sorption of the pesticides by a factor of 2. Similar values of water-soil partition coefficients (Ksol*) for aged and fresh added pesticides to soils indicate that the aging process used did not significantly after the capability of either surfactant to desorb the pesticides. A model able to estimate equilibrium distributions of organic compounds in soil-aqueous-micellar systems was tested against experimental results. The determined organic carbon partition coefficients, Koc values, indicate that, on a carbon normalized basis, sorbed Rh-mix is a much better sorbent of pesticides than TX-100 or soil organic matter. These results have significant implications on determining the effectiveness of surfactants to aid soil remediation technologies.     

Configurations of the bentonite-sorbed myristylpyridinium cation and their influences on the uptake of organic compounds

Variations in the configuration of a sorbed myristylpyridinium (MP+) surfactant cation with a loading level in bentonite were examined by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR); the attractive force from the clay basal surfaces to the sorbed MP+ and water molecule in the interlayers was estimated by thermogravimetric analysis (TG-DTG). At low loading levels (i.e., < CEC), MP+ sorbed mainly by cation exchange to clay basal surfaces to form tightly-adhered "organic films" (i.e., flat-layer). With increasing MP+ loading, sorbed MP+ gradually changed into a less confined "phase-like medium" (i.e., paraffin-type structures) via London attraction forces. Attractive forces between the mineral basal surfaces and the sorbed MP+ varied with the interlayer spacing and the stacking of MP+. Sorption of phenol and naphthalene to the resultant MP(+)--clay was a function of the configuration of MP+ aggregates on clay surfaces. At low MP+ densities, the sorbed MP+ film acted as an effective adsorbent for organic compounds. The carbon-normalized solute distribution coefficients (K(sf)) were exceptionally large and increased with MP+ densities up to approximately 340 (phenol) and approximattely 15000 mL g(-1) (naphthalene). At high MP+ loadings, the MP+ aggregates transformed into a partition-like medium, and the K(sf) values decreased sharply and leveled off. Nonetheless, because of the enhanced MP+ packing density within the clay interlayer, the solute K(sf) with a confined sorbed MP+ phase exceeded the corresponding aqueous micelle-water partition coefficients (k(mc)).     

Enhanced soil washing of phenanthrene by mixed solutions of TX100 and SDBS

Increased desorption of hydrophobic organic compounds (HOCs) from soils and sediments is a key to the remediation of contaminated soils and groundwater. In this study, phenanthrene desorption from a contaminated soil by mixed solutions of a nonionic surfactant(octylphenol polyethoxylate, TX100) and an anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) was investigated. Phenanthrene desorption depended on not only aqueous surfactant concentrations and phenanthrene solubility enhancement but also the soil-sorbed surfactant amount and the corresponding sorption capacity of sorbed surfactants. The added surfactant critical desorption concentrations (CDCs) for phenanthrene from soil depended on both sorbed concentrations of surfactants and their critical micelle concentrations (CMCs). Phenanthrene desorption by mixed solutions was more efficient than individual surfactants due to the low sorption loss of mixed surfactants to soil. Among the tested surfactant systems, mixed TX100 and SDBS with a 1:9 mass ratio exhibited the highest phenanthrene desorption. Mixed micelle formation, showing negative deviation of CMCs from the ones predicted by the ideal mixing theory, was primarily responsible for the significant reduction of soil-sorbed amounts of TX100 and SDBS in their mixed systems. Therefore, mixed anionic-nonionic surfactants had great potential in the area of enhanced soil and groundwater remediation.     

Micellar partitioning and its effects on Henry's law constants of chlorinated solvents in anionic and nonionic surfactant solutions

Micellar partitioning of volatile chlorinated hydrocarbons in surfactant solutions and its effects on vapor-liquid equilibrium is fundamental to the overall design and implementation of surfactant-enhanced aquifer remediation. Surfactant micelles greatly enhance contaminant recovery from the subsurface; however, the reduced volatility of organic compounds compromises the aboveground treatment of surfactant-laden wastewaters using air-stripping process. Batch equilibrium tests were performed to acquire micellar partition coefficients (Km) and apparent Henry's law constants (H*) of three prominent groundwater contaminants (tetrachloroethylene, trichloroethylene, cis-dichlorethylene) in the presence of two anionic surfactants (sodium dodecyl sulfate, SDS; sodium dodecylbenzene sulfonate, SDBS) and two nonionic surfactants (Triton X-100 and Tween 80). The H* values were significantly reduced in the presence of all four surfactants over their critical micelle concentrations (cmc's). On a cmc basis, the anionic surfactant SDS had the greatest effect on H*, followed by SDBS, Triton X-100, and Tween 80. Anionic surfactants decreased H* to an order of magnitude lower than nonionic surfactants, although nonionic surfactants decreased the H* at concentrations significantly lower than the anionic surfactants due to their lower cmc's. Nonionic surfactants present higher Km and molar solubilization ratio than anionic surfactants. Tetrachloroethylene has the highest Km values among three chlorinated solvents, which agrees well with the hydrophobicity (Kow) of these chemicals. An empirical correlation between log Km and log Kow is developed on the basis of data from this study and the Km values reported for a number of chlorinated and nonchlorinated hydrocarbons. Equilibrium data were also tested against three sets of models that describe the partitioning of volatile compounds in vapor-water-micelle phases. Applications of these models in experimentally determining Km from batch vapor-water equilibrium data are discussed.     

A partition-limited model for the plant uptake of organic contaminants from soil and water

In dealing with the passive transport of organic contaminants from soils to plants (including crops), a partition-limited model is proposed in which (i) the maximum (equilibrium) concentration of a contaminant in any location in the plant is determined by partition equilibrium with its concentration in the soil interstitial water, which in turn is determined essentially by the concentration in the soil organic matter (SOM) and (ii) the extent of approach to partition equilibrium, as measured by the ratio of the contaminant concentrations in plantwater and soil interstitial water, alphapt (< or = 1), depends on the transport rate of the contaminant in soil water into the plant and the volume of soil water solution that is required for the plant contaminant level to reach equilibrium with the external soil-water phase. Through reasonable estimates of plant organic-water compositions and of contaminant partition coefficients with various plant components, the model accounts for calculated values of alphapt in several published crop-contamination studies, including near-equilibrium values (i.e., alphapt approximately equals 1) for relatively water-soluble contaminants and lower values for much less soluble contaminants; the differences are attributed to the much higher partition coefficients of the less soluble compounds between plant lipids and plant water, which necessitates much larger volumes of the plant water transport for achieving the equilibrium capacities. The model analysis indicates that for plants with high water contents the plant-water phase acts as the major reservoir for highly water-soluble contaminants. By contrast, the lipid in a plant, even at small amounts, is usually the major reservoir for highly water-insoluble contaminants.     

Measuring hydrophobic micropore volumes in geosorbents from trichloroethylene desorption data

Hydrophobic micropores can play a significant role in controlling the long-term release of organic contaminants from geosorbents. We describe a technique for quantifying the total and the hydrophobic mineral micropore volumes based on the mass of trichloroethylene (TCE) sorbed in the slow-releasing pores under dry and wet conditions, respectively. Micropore desorption models were used to differentiate the fast- and slow-desorbing fractions in desorption profiles. The micropore environment in which organic molecules were sorbed in the presence of water was probed by studying the transformation of a water-reactive compound (2,2-dichloropropane or 2,2-DCP). For sediment from an alluvial aquifer, the total and hydrophobic micropore volumes estimated using this technique were 4.65 microL/g and 0.027 microL/g (0.58% of total), respectively. In microporous silica gel A, a hydrophobic micropore volume of 0.038 microL/g (0.035% of reported total) was measured. The dehydrohalogenation rate of 2,2-DCP sorbed in hydrophobic micropores of the sediment was slower than that reported in bulk water, indicating an environment of low water activity. The results suggest that hydrolyzable organic contaminants sorbed in hydrophobic micropores react slower than in bulk water, consistent with the reported persistence of reactive contaminants in natural soils.     

Evaluation of component characteristics of soil-surfactant-herbicide system that affect enhanced desorption of linuron and atrazine preadsorbed by soils

The aim of the present work was to evaluate the surfactant-enhanced desorption of atrazine and linuron preadsorbed by soils and to study the effect of different characteristics of the components of soil-surfactant-herbicide systems on the efficiency of desorption. Two soils with organic matter contents of 3.16% and 7.28% and 11 surfactants, three of them anionic (SDS, LAS, and SDOSS) and 8 of them nonionic (Tween 80, Tween 20, Triton X-100, Triton X-114, Brij 35, Brij 30, Tergitol NP-10, and Tergitol 15S12), at concentrations 1.5 and 10 times the critical micellar concentration (cmc) were used. Adsorption-desorption studies were performed using a batch system, and the Freundlich model was applied to the isotherms except for some cases in which this was not possible. The desorption isotherms of both pesticides in aqueous medium pointed to the existence of hysteresis. The values of the hysteresis coefficients of the adsorption isotherms in water decreased in some cases while in others they increased in the presence of the surfactants, depending on the structure of these and on their concentration in water, on the organic matter content of the soil, and on the K(ow) of the herbicide. Parallel to the decrease in hysteresis, the percentage of herbicide desorption and desorption efficiency coefficient (E; ratio between the percentages of herbicide desorption in the presence of surfactant and those found in aqueous medium) increased. For a 10 cmc surfactant concentration, a linear relationship was seen between the E values and the absolute values of the cmc of the surfactants. Also, for the same surfactant, a linear relationship was seen between log E and the log of the absolute concentrations of surfactant in solution. The results obtained are of practical interest for the choice of surfactants for concrete problems involved in the recovery of pesticide-polluted waters using the surfactant-enhanced desorption pumping technique.     

Sorption behavior of nonylphenol in terrestrial soils

Nonylphenol (NP) as an intermediate from anaerobic degradation of widely used nonionic surfactants occurs widespread in the environment. Partition behavior of this toxic and endocrine-disrupting chemical between soil and water was not examined until yet. The objective of this investigation was to quantify sorption and desorption behavior of 4-nonyl[14C]phenol in a set of 51 soils using the batch equilibrium approach. Kinetic studies indicated apparent equilibrium within 20 h. Sorption was influenced by sorbate structure as could be shown with branched 4-nonyl[14C]phenol and the linear 4-n-NP, respectively. Linear 4-n-NP behaves differently from the branched isomers of 4-NP. Sorption of 4-nonyl[14C]phenol tested with five different initial concentrations resulted in linearly fitted isotherms that provided calculation of sorption partition coefficients (KP). Desorption partition coefficients (KP-des) revealed hysteresis independent of soil properties but decreasing with decreasing initial NP concentrations. KP values were correlated with organic carbon content of the soils yielding a log KOC of 3.97.     

Sorption of perfluorinated surfactants on sediments

The sorption of anionic perfluorochemical (PFC) surfactants of varying chain lengths to sediments was investigated using natural sediments of varying iron oxide and organic carbon content. Three classes of PFC surfactants were evaluated for sorptive potential: perfluorocarboxylates, perfluorosulfonates, and perfluorooctyl sulfonamide acetic acids. PFC surfactant sorption was influenced by both sediment-specific and solution-specific parameters. Sediment organic carbon, rather than sediment iron oxide content, was the dominant sediment-parameter affecting sorption, indicating the importance of hydrophobic interactions. However, sorption also increased with increasing solution [Ca2+] and decreasing pH, suggesting that electrostatic interactions play a role. Perfluorocarbon chain length was the dominant structural feature influencing sorption, with each CF2 moiety contributing 0.50-0.60 log units to the measured distribution coefficients. The sulfonate moiety contributed an additional 0.23 log units to the measured distribution coefficient, when compared to carboxylate analogs. In addition, the perfluorooctyl sulfonamide acetic acids demonstrated substantially stronger sorption than perfluorooctane sulfonate (PFOS). These data should prove useful for modeling the environmental fate of this class of contaminants.     

The rate of 2,2-dichloropropane transformation in mineral micropores: implications of sorptive preservation for fate and transport of organic contaminants in the subsurface

Nanometer scale pores are ubiquitous in porous geologic media (soils and sediments). Sorption of organic contaminants in micropores (< or = 2 nm) can inhibittheir hydrolytic transformation due to the limited availability of reactive water within hydrophobic micropore spaces. As a test case, we studied the dehydrohalogenation of 2,2-dichloropropane (2,2-DCP) sorbed in the micropores of several model mineral solids. In the micropores of a hydrophobic dealuminated Y zeolite, CBV-780, 2,2-DCP dehydrohalogenation proceeded significantly slower than in bulk aqueous solution and eventually stopped. This was attributed to the depletion of reactive water molecules in the micropore spaces. The 2,2-DCP sorbed in the micropores of more hydrophilic solids (aquifer sediment, aquifer sand, and silica gel) also transformed slower than in aqueous solution, and the reaction no longer followed first-order kinetics. Results of transport modeling support that reactive contaminants sorbed in microporous minerals can be preserved over geological time scales under conditions that limit desorption. This study shows that hydrophobic micropores in geological media may act as an important sink for anthropogenic organic contaminants in the subsurface, and that sorption in micropores may significantly increase the persistence of the sorbed contaminants.     

Quantification of solute-solute interactions using negligible-depletion solid-phase microextraction: measuring the affinity of estradiol to bulk organic matter

The interaction of trace organic contaminants with bulk organic matter has implications for the transport and behavior of organic trace contaminants within the aquatic environment as well as water and wastewater treatment processes. Partition coefficients (K(OM)) of the steroidal trace organic contaminant estradiol were quantified for environmentally relevant concentrations of bulk organic matter (12.5 mg C/L) using a full mass balance form of solid-phase microextraction (SPME). The results indicated that the method is successful and can be used at environmental concentrations. Estradiol had the greatest affinity for bulk organic matter that contained phenolic and benzoic acid ester groups, namely tannic acid, compared to organics containing predominately carboxylic functional groups. The solution chemistry (pH) was found to influence the interaction, as estradiol had a lower affinity for negatively charged and hydrophilic bulk organic matter. The partition coefficients determined using SPMEwere consistentwith partition coefficients derived using solubility enhancement and fluorescence quenching measurements, confirming that SPME is a powerful technique to quantify the affinity of estradiol for low concentrations of bulk organic matter and trace contaminants. Further, this novel method can be applied to a range of trace contaminants.     

Effects of linear alkylbenzene sulfonate on the sorption of Brij 30 and Brij 35 onto aquifer sand

Surfactant sorption is of considerable importance to environmental applications, including surfactant flushing to mobilize hydrophobic contaminants; effects of surfactants on the transport of dissolved contaminants, microorganisms, and colloids through porous media; and bioremediation of hydrophobic organic compounds, as well as understanding the fate and transport of surfactants as environmental contaminants themselves. Although most sorption studies consider pure surfactants, commercial detergent formulations typically consist of mixtures of nonionic and anionic surfactants. In this study, the effects of varying concentrations of the anionic surfactant linear alkylbenzene sulfonate (LAS) on micelle formation and sorption behavior of the two commonly used nonionic surfactants Brij 30 and Brij 35 onto aquifer sand were examined. A strong linear relationship was observed between the critical micelle concentration (CMC) of the Brij surfactants and the concentration of LAS in the mixture, with the CMC decreasing with increasing concentration of LAS. The relative change in CMC as a function of the LAS concentration was identical forthe two Brij surfactants, indicating that LAS interacted with their common alkyl chains. Sorption isotherms were developed for Brij 30 and Brij 35 present as single surfactants in an aqueous solution as well as when present with LAS. Although LAS had minor effects on the maximum sorption plateaus of the Brij surfactants, Brij sorption at was significantly enhanced as a function of the LAS concentration for Brij aqueous concentrations below the CMC. Application of a multi-interaction isotherm model indicated that the formation of surface aggregates (e.g., hemimicelles) decreased with increasing LAS concentration. Overall, these results provide insight into the complex sorption behavior of surfactant mixtures.     

Protection of mesopore-adsorbed organic matter from enzymatic degradation

Synthetic mesoporous alumina and silica minerals with uniform pore geometries, and their nonporous analogues, were used to test the role of mineral mesopores (2-50 nm diameter) in protecting organic matter from enzymatic degradation in soils and sediments. Dihydroxyphenylalanine (L-DOPA), a model humic compound, was irreversibly sorbed to both mineral types. The surface area-normalized adsorption capacity was greater for the mesoporous minerals relative to their nonporous analogues. The degradation kinetics of free and mineral-sorbed L-DOPA by the enzyme laccase was monitored in a closed cell via oxygen electrode. Relative to freely dissolved L-DOPA, nonporous alumina-sorbed substrate was degraded, on average, 90% more slowly and to a lesser extent (93%), likely due to laccase adsorption to alumina. In contrast, relative to free L-DOPA, degradation of nonporous silica-sorbed L-DOPA was enhanced by 20% on average. In the case of mesoporous alumina and silica-sorbed L-DOPA, the enzyme activity was 3-40 times lower than that observed for externally sorbed substrate (i.e., L-DOPA sorbed to nonporous minerals). These results provide strong evidence to support the viability of the mesopore protection mechanism for sequestration and preservation of sedimentary organic matter and organic contaminants. Nanopore adsorption/desorption phenomena may aid in explaining the slow degradation of organic contaminants in certain soils and sediments and may have implications for environmental remediation and biotechnological applications.     

Preferential surfactant utilization by a PAH-degrading strain: effects on micellar solubilization phenomena

Biodegradable nonionic Tween series surfactants were employed to assess the effects of synthetic surfactants on the bioavailability of a target polycyclic aromatic hydrocarbon (PAH), phenanthrene, in soil/sediment-free micellar solutions. Dosages of surfactants in excess of their respective critical micelle concentrations (CMCs) dramatically enhanced solubilization of phenanthrene, but the micellar-solubilized phenanthrene was neither directly nor readily bioavailable to the PAH-degrading strain, Sphingomonas paucimobilis EPA 505, used in these bioavailability experiments. The microorganism preferred instead to utilize hydrophobic fractions of the Tween surfactants as a carbon source, resulting in an imbalance of amphiphilic moieties in surfactant molecules and associated destabilization of micelles. This effect was assessed by measurements of surface tension, CMCs, weight-based PAH solubilization ratios, and by characterizations of the surfactants via HPLC separation and emulsification behavior. The observations and analyses lead to a conclusion that preferential biological destabilization of surfactant micelles effects an associated release of phenanthrene to the aqueous phase. The phenanthrene so released then apparently reverts to a crystallized form that appears to be bioavailable only through normal re-dissolution to the aqueous phase. This is, to our knowledge, the first attempt to characterize and quantify changes in the properties and solubilization behaviors of surfactant micelles resulting from their partial and preferential biodegradation. The associated re-deposition of previously micellar-solubilized PAHs observed and the loss of solubilization capacity of recovered surfactants have significant implications for applications of surfactant-enhanced bioremediation of contaminated soils and sediments.     

Development of engineered natural organic sorbents for environmental applications. 4. Effects on biodegradation and distribution of pyrene in soils

The effects of engineered natural organic amendments on the biodegradation and distribution of pyrene in soils were assessed. Pyrene was aged for 105 days in soils amended with either raw or superheated water (SHW)-processed MI peat or soybean stalks, and then subjected to biodegradation with specifically selected microorganisms for 130 days. Initial rates of pyrene mineralization in the soils were increased by addition of raw MI peat, but markedly decreased by additions of SHW-processed MI peat and both processed and raw soybean stalks. Pyrene sorbed by the processed organic sorbents was, however, slowly but steadily degraded by microorganisms over a greater than 4-month test period. Pyrene distributions in the soils were examined by sequential extractions of samples before and after biodegradation. Fractions of pyrene extracted readilywith water or water/methanol mixtures were decreased substantially in both soils bythe addition of processed amendments, while the nonextractable fractions associated with humic and fulvic acids and humin were increased markedly. The results demonstrate that SHW-processed amendments effectively reduce the ecological and human availability and aqueous phase extractability of organic contaminants while facilitating their steady microbial degradation and eventually complete remediation.     

Occurrence and fate of perfluorochemicals in soil following the land application of municipal biosolids

The recent implementation of soil and drinking water screening guidance values for two perfluorochemicals (PFCs), perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) by the U.S. Environmental Protection Agency (EPA), reflects the growing concerns regarding the presence of these persistent and bioaccumulative chemicals in the natural environment. Previous work has established the potential risk to the environment from the land application of industrially contaminated biosolids, but studies focusing on environmental risk from land application of typical municipal biosolids are lacking. Thus, the present study investigated the occurrence and fate of PFCs from land-applied municipal biosolids by evaluating the levels, mass balance, desorption, and transport of PFCs in soils receiving application of municipal biosolids at various loading rates. This study is the first to report levels of PFCs in agricultural soils amended with typical municipal biosolids. PFOS was the dominant PFC in both biosolids (80-219 ng/g) and biosolids-amended soil (2-483 ng/g). Concentrations of all PFCs in soil increased linearly with increasing biosolids loading rate. These data were used to develop a model for predicting PFC soil concentrations in soils amended with typical municipal biosolids using cumulative biosolids loading rates. Mass balance calculations comparing PFCs applied vs those recovered in the surface soil interval indicated the potential transformation of PFC precursors. Laboratory desorption experiments indicated that the leaching potential of PFCs decreases with increasing chain length and that previously derived organic-carbon normalized partition coefficients may not be accurate predictors of the desorption of long-chain PFCs from biosolids-amended soils. Trace levels of PFCs were also detected in soil cores from biosolids-amended soils to depths of 120 cm, suggesting potential movement of these compounds within the soil profile over time and confirming the higher transport potential for short-chain PFCs in soils amended with municipal biosolids.     

Assessing sequestration of selected polycyclic aromatic hydrocarbons by use of adsorption modeling and temperature-programmed desorption

Sequestration of phenanthrene and pyrene was investigated in two soils--a sandy soil designated SBS and a silt-loam designated LHS--by combining long-term batch sorption studies with thermal desorption and pyrolysis of amended soil samples. The Polanyi-based adsorption volume and the adsorbed solute mass increased with aging for both soils, thus demonstrating the mechanism for observed sequestration. Despite rigorous thermal analysis, 30-62% (SBS sand) and 8-30% (LHS silt-loam) of phenanthrene could not be recovered after 30-270 days of sorption, with the increase in desorption resistance showing greater significance in SBS sand. For both soils, these values were 20-65% of adsorbed phenanthrene mass. Activation energies estimated from the temperature-programmed desorption (TPD) of sorbed phenanthrene at < or = 375 degrees C were 51-53 kJ/mol, consistent with values derived for desorption of organic compounds from humic materials. The activated first-order model fitting of observed TPD data supports the conclusion that the desorption-resistant fraction of phenanthrene has become sequestered onto condensed organic domains and requires temperatures exceeding 600 degrees C to be released. The work demonstrates the use of thermal analysis in complementing the Polanyi-based adsorption modeling approach for assessing the mechanistic basis for sequestration of organic contaminants in soils.     

Sorption and dissipation of testosterone, estrogens, and their primary transformation products in soils and sediment

Concern over the potential negative ecological effects of steroid hormones from human- and animal-derived wastes has resulted in an increased interest regarding the mobility and persistence of these compounds in the environment. Batch experiments were conducted to examine the simultaneous sorption and dissipation of three reproductive hormones (testosterone, 17beta-estradiol, and 17alpha-ethynyl estradiol) in four midwestern U.S. soils and one freshwater sediment. Sorption isotherms were generated by measuring aqueous concentrations and by extracting the sorbed parent chemical or transformation products (e.g., estrone, androstenedione). Apparent sorption equilibrium is reached within a few hours. Measured sorption isotherms for the three parent chemicals and their principal transformation products were generally linear. Average organic carbon normalized sorption coefficients (K(oc)) resulted in standard deviations of less than 0.2 log units and were consistent with reported aqueous solubilites and octanol-water partition coefficients, indicating hydrophobic partitioning as the dominant sorption mechanism. Large log K(oc) values (approximately 3-4) suggest that leaching from soils will be limited, runoff of soil- and land-applied biosolids are the most likely inputs into surface waters, and that a significant fraction of these compounds will be associated with sediments. Half-lives for hormone dissipation in the aerobic soil and sediment slurries estimated assuming pseudo first-order processes ranged from a few hours to a few days with testosterone having the shortest half-life.     

Photosensitized oxidation of substituted phenols on aluminum phthalocyanine-intercalated organoclay

Bentonite modified with cationic surfactant, cetyltri-methylammonium bromide (CTMA), was an effective sorbent for organic pollutants in water. To make the sorbent recyclable, aluminum phthalocyanine (AIPc), a representative photosensitizer for generation of singlet oxygen, was inserted successfully into the interlamellar space of CTMA-modified bentonite. Under visible light (lambda > 450 nm) irradiation, the composite catalyst exhibited a remarkable activity for degradation of the recalcitrant pollutants phenol, 4-chlorophenol, 4-nitrophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in an aerated aqueous medium. The initial rate of the heterogeneous photoreaction was found to increase with the initial amount of the substrate sorption onto the catalyst, the kinetics following the Langmuir-Hinshelwood equation. Loading of AIPc into the organoclay led to slight expansion of the clay basal spacings from 1.82 to 2.15 nm, but the sorption capacity was decreased notably. The optimal loading of AIPc was about 0.25 wt %. The result demonstrates thatthe surfactant-modified bentonite not only offers a hydrophobic zone for enrichment of organic contaminants but also provides a flexible environment for destruction of the sorbed pollutants by singlet oxygen generated in situ. It was noted, however, that during four repeated experiments, both the sorption and the degradation rate of 2,4,6-trichlorophenol were gradually decreased, due to some intermediates formed and sorbed onto the catalyst surface.     

Particle-size dependent sorption and desorption of pesticides within a water-soil-nonionic surfactant system

Although nonionic surfactants have been considered in surfactant-aided soil washing systems, there is little information on the particle-size dependence of these processes, and this may have significant implications for the design of these systems. In this study, Triton-100 (TX) was selected to study its effect on the sorption and desorption of two pesticides (Atrazine and Diuron) from different primary soil size fractions (clay, silt, and sand fractions) under equilibrium sorption and sequential desorption. Soil properties, TX sorption, and pesticide sorption and desorption all exhibited significant particle-size dependence. The cation exchange capacity (CEC) of the bulk soils and the soil fractions determined TX sorption capacity, which in turn determined the desorption efficiency. Desorption of pesticide out of the clay raction is the limiting factor in a surfactant-aided washing system. The solubilization efficiency of the individual surfactant micelles decreased as the amount of surfactant added to the systems increased. Thus, instead of attempting to wash the bulk soil, a better strategy might be to either (1) use only the amount of surfactant that is sufficient to clean the coarse fraction, then separate the fine fraction, and dispose or treat it separately, or (2) to separate the coarse fractions mechanically and then treatthe coarse and fine fractions separately. These results may be applicable to many other hydrophobic organic compounds such as polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) strongly sorbed onto soils and sediments.