Shonali Laha

Surfactant-soil interactions during surfactant-amended remediation of contaminated soils by hydrophobic organic compounds : A review

Surfactants are amphiphilic molecules that reduce aqueous surface tension and increase the solubility of hydrophobic organic compounds (HOCs). Surfactant-amended remediation of HOC-contaminated soils and aquifers has received significant attention as an effective treatment strategy - similar in concept to using soaps and detergents as washing agents to remove grease from soiled fabrics. The proposed mechanisms involved in surfactant-amended remediation include: lowering of interfacial tension, surfactant solubilization of HOCs, and the phase transfer of HOC from soil-sorbed to pseudo-aqueous phase. However, as with any proposed chemical countermeasures, there is a concern regarding the fate of the added surfactant. This review summarizes the current state of knowledge regarding nonionic micelle-forming surfactant sorption onto soil, and serves as an introduction to research on that topic. Surfactant sorption onto soil appears to increase with increasing surfactant concentration until the onset of micellization. Sorbed-phase surfactant may account for the majority of added surfactant in surfactant-amended remediation applications, and this may result in increased HOC partitioning onto soil until HOC solubilization by micellar phase surfactant successfully competes with increased HOC sorption on surfactant-modified soil. This review provides discussion of equilibrium partitioning theory to account for the distribution of HOCs between soil, aqueous phase, sorbed surfactant, and micellar surfactant phases, as well as recently developed models for surfactant sorption onto soil. HOC partitioning is characterized by apparent soil-water distribution coefficients in the presence of surfactant.

Effects of surfactant addition on the biomineralization and microbial toxicity of phenanthrene

Surfactants are known to increase the apparent aqueous solubility of polycyclic aromatic hydrocarbons and may thereby enhance their bioavailability. In this study the effects of four surfactants on the mineralization of phenanthrene by Pseudomonas aeruginosa in liquid culture and in soil-water suspensions was studied in batch reactors over a 15-week study period. In the absence of surfactant, liquid cultures mineralized approximately 50% of the phenanthrene added within seven weeks following a one-week lag period and an initial mineralization rate of 0.04 mg/d. Mineralization in soil-water suspensions proceeded without any measurable lag period. The initial mineralization rate was lower (0.006 mg/d), but mineralization continued to >70% over the fifteen week period. In general, the addition of very low concentrations of surfactant (≤0.001%) to liquid cultures did not impact mineralization significantly. At higher surfactant concentrations (≥CMC) all surfactants were seen to be inhibitory. In soil-water systems, the rate of phenanthrene mineralization was decreased even at surfactant doses that did not produce significant solubilization. In summary, none of the surfactants enhanced the mineralization of phenanthrene by P. aeruginosa in liquid culture or in soil-water suspensions. In order to rank surfactant toxicity, microbial toxicity tests were performed measuring the light output of bioluminescent bacteria as affected by the presence of surfactants. Additional toxicity testing indicated that the presence of solubilized phenanthrene increased the toxicity of the surfactant by a 100-fold suggesting that the toxicity of solubilized substrate needs also to be considered in the application of surfactant-amended remediation.

Biodegradation of 4-nitrophenol by indigenous microbial populations in Everglades soils.

The Everglades in South Florida are a unique ecologicalsystem. As a result of the widespread use of pesticides andherbicides in agricultural areas upstream from these wetlands,there is a serious potential for pollution problems in theEverglades. The purpose of this study was to evaluate theability of indigenous microbial populations to degradexenobiotic organic compounds introduced by agricultural andother activities. Such biodegradation may facilitate theremediation of contaminated soils and water in the Everglades.The model compound selected in this study is 4-nitrophenol, achemical commonly used in the manufacture of pesticides. Themineralization of 4-nitrophenol at various concentrations wasstudied in soils collected from the Everglades. Atconcentrations of 10 and 100 µg/g soil, considerablemineralization occurred within a week. At a higherconcentration, i.e., 10 mg/g soil, however, no mineralizationof 4-nitrophenol occurred over a 4-month period; such a highconcentration apparently produced an inhibitory effect. Therate and extent of 4-nitrophenol mineralization was enhancedon inoculation with previously isolated nitrophenol-degradingmicroorganisms. The maximum mineralization extent measured,however, was less than 30% suggesting conversion to biomassand/or unidentified intermediate products. These resultsindicate the potential for natural mechanisms to mitigate theadverse effects of xenobiotic pollutants in a complex systemsuch as the Everglades.

Color removal in groundwater through the enhanced softening process

The source of water for Miami-Dade County, Florida is groundwater derived from the Biscayne aquifer. The raw water is rich in natural organic material producing correspondingly high color levels. Currently, breakpoint chlorination is used at the water treatment plant to control the color problem. However, this results in the formation of disinfection by-products. Proposed alternatives to reduce color and avoid by-product formation include the addition of coagulants such as ferric chloride and organic polymers, and the operation of the existing lime softening process at a higher pH. This study uses jar tests to evaluate the relative effectiveness of the proposed alternatives. Results indicate that significant color reduction is achieved using the existing lime softening process with activated silica coagulant by increasing the softening pH to 11 or more. Elevated pH also produced a > 30% reduction in total organic carbon. In the presence of higher raw water color (> or = 80 units), the addition of ferric chloride as coagulant at dosages of 80 mg/L is recommended.

Highly organic natural media as permeable reactive barriers: TCE partitioning and anaerobic degradation profile in eucalyptus mulch and compost

Batch and column experiments were conducted with eucalyptus mulch and commercial compost to evaluate suitability of highly organic natural media to support anaerobic decomposition of trichloroethylene (TCE) in groundwater. Experimental data for TCE and its dechlorination byproducts were analyzed with Hydrus-1D model to estimate the partitioning and kinetic parameters for the sequential dechlorination reactions during TCE decomposition. The highly organic natural media allowed development of a bioactive zone capable of decomposing TCE under anaerobic conditions. The first order TCE biodecomposition reaction rates were 0.23 and 1.2d(-1) in eucalyptus mulch and compost media, respectively. The retardation factors in the eucalyptus mulch and compost columns for TCE were 35 and 301, respectively. The results showed that natural organic soil amendments can effectively support the anaerobic bioactive zone for remediation of TCE contaminated groundwater. The natural organic media are effective environmentally sustainable materials for use in permeable reactive barriers.

Enhancement of TCE Attenuation in Soils by Natural Amendments

The objective of this study was to identify low-cost natural amendments that could be used as carbon sources and sustain a bioactive zone to promote biodegradation of TCE in contaminated shallow groundwater. The natural amendments were compared based on their geophysical characteristics as well as TCE adsorption capacities. The amendments studied included low-cost natural and agricultural materials such as eucalyptus tree mulch, pine bark mulch, muck from the Florida Everglades, SRS wetland peat, commercial compost, and peat humus. These natural substrates have relatively high organic fractions that can retard the movement of TCE while serving as carbon sources. Batch sorption studies were conducted to determine the sorption and retardation characteristics of the amendments for TCE. The experimental results were analyzed in relation to the geophysical characteristics of the amendments and compared with those of natural soils.

Synergistic Effects of Organic Contaminants and Soil Organic Matter on the Soil-Water Partitioning and Effectiveness of a Nonionic Surfactant (Triton X-100)

ABSTRACT Napthalene- and decane-contaminated soils were treated with Triton X-100 (a nonionic surfactant) to characterize the soil-water partitioning behavior of the surfactant in soils with different organic content. Soil samples with different organic content were prepared by mixing sand-mulch mixtures at different proportions. The experimental results indicated that the amount of surfactant sorbed onto soil increased with increasing soil organic content and increasing surfactant concentration. The effective critical micelle concentration (CMC) also increased with increasing organic content in soil. The CMC of Triton X-100 in aqueous systems without soil was about 0.3 mM and the effective CMC values measured for soil-water-surfactant systems (approximately 1:19 soil/water ratio) with 25%, 50%, and 75% mulch content were 0.9, 1.0, and 1.7 mM, respectively. Sub-CMC surfactant sorption was modeled accurately with both the Freundlich and the linear isotherm. The maximum surfactant sorption onto soil varied from 66% to 82% of added surfactant in the absence of contaminant. The effective CMC values for Triton X-100 increased to some extent in the presence of contaminants, as did the maximum surfactant sorption. The maximum surfactant sorbed onto the soil with 75% mulch content increased from 82% for clean soils, to 95% and 96% for soils samples contaminated with naphthalene and decane, respectively.