Sorption, degradation and transport phenomena of alcohol ethoxysulfates in agricultural soils. Laboratory studies.

In the present work, laboratory studies were conducted in order to determine and model the sorption, degradation and transport processes of alcohol ethoxysulfates (AES), one of the most important groups of anionic surfactants. Adsorption/desorption isotherms were obtained for several structurally related AES ethoxymers (homologue AES-C12En with n = 0-10 ethoxymer units and homologue AES-C14En with n = 0-7 ethoxymer units) using a batch equilibrium method. Data were fitted to a linear and a Freundlich isotherm models. Additionally, experiments in continuous-flow soil columns were also carried out and the breakthrough curves observed for each compound were studied. Breakthrough curves were used to determine the fundamental parameters of the transport model (hydrodynamic dispersion coefficient, degradation rate constant and adsorption/desorption isotherm slope), that is the main phenomena that take place simultaneously when AES move through agricultural soil. When the results obtained for the AES ethoxymers are combined, they reveal a clear and consistent trend towards a sorption increase with the number of ethoxylated units and with the length of the alkyl chain that opens the possibility to estimate the values of the transport parameters for other structurally related ethoxymers.

Wide-range and accurate modeling of linear alkylbenzene sulfonate (LAS) adsorption/desorption on agricultural soil.

In this paper, rigorous data and adequate models about linear alkylbenzene sulfonate (LAS) adsorption/desorption on agricultural soil are presented, contributing with a substantial improvement over available adsorption works. The kinetics of the adsorption/desorption phenomenon and the adsorption/desorption equilibrium isotherms were determined through batch studies for total LAS amount and also for each homologue series: C10, C11, C12 and C13. The proposed multiple pseudo-first order kinetic model provides the best fit to the kinetic data, indicating the presence of two adsorption/desorption processes in the general phenomenon. Equilibrium adsorption and desorption data have been properly fitted by a model consisting of a Langmuir plus quadratic term, which provides a good integrated description of the experimental data over a wide range of concentrations. At low concentrations, the Langmuir term explains the adsorption of LAS on soil sites which are highly selective of the n-alkyl groups and cover a very small fraction of the soil surface area, whereas the quadratic term describes adsorption on the much larger part of the soil surface and on LAS retained at moderate to high concentrations. Since adsorption/desorption phenomenon plays a major role in the LAS behavior in soils, relevant conclusions can be drawn from the obtained results.

Evaluation of Linear Alkylbenzene Sulfonate (LAS) behaviour in agricultural soil through laboratory continuous studies.

The behaviour of Linear Alkylbenzene Sulfonate (LAS) in agricultural soil is investigated in the laboratory using continuous-flow soil column studies in order to simultaneously analyze the three main underlying phenomena (adsorption/desorption, degradation and transport). The continuous-flow soil column experiments generated the breakthrough curves for each LAS homologue, C10, C11, C12 and C13, and by adding them up, for total LAS, from which the relevant retention, degradation and transport parameters could be estimated, after proposing adequate models. Several transport equations were considered, including the degradation of the sorbate in solution and its retention by soil, under equilibrium and non-equilibrium conditions between the sorbent and the sorbate. In general, the results obtained for the estimates of those parameters that were common to the various models studied (such as the isotherm slope, first order degradation rate coefficient and the hydrodynamic dispersion coefficient) were rather consistent, meaning that mass transfer limitations are not playing a major role in the experiments. These three parameters increase with the length of the LAS homologue chain. The study will provide the underlying conceptual framework and fundamental parameters to understand, simulate and predict the environmental behaviour of LAS compounds in agricultural soils.

Improved sample treatment for the determination of insoluble soap in sewage sludge samples by liquid chromatography with fluorescence detection.

A new selective and sensitive method for the determination of insoluble fatty acid salts (soap) in sewage sludge samples is proposed. The method involves a clean up of sample with petroleum ether, the conversion of calcium and magnesium insoluble salts into soluble potassium salts, potassium salts extraction with methanol, and a derivatization procedure previous to the liquid chromatography with fluorescence detection (LC-FLD) analysis. Three different extraction techniques (Soxhlet, microwave-assisted extraction and ultrasounds) were compared and microwave-assisted extraction (MAE) was selected as appropriate for our purpose. This allowed to reduce the extraction time and solvent waste (50 mL of methanol in contrast with 250 mL for Soxhlet procedure). The absence of matrix effect was demonstrated with two standards (C(13:0) and C(17:0)) that are not commercials and neither of them has been detected in sewage sludge samples. Therefore, it was possible to evaluate the matrix effect since both standards have similar environmental behaviour (adsorption and precipitation) to commercial soaps (C(10:0)-C(18:0)). The method was successfully applied to samples from different sources and consequently, with different composition.

New sample treatment for the determination of alkylphenols and alkylphenol ethoxylates in agricultural soils.

A new sample treatment for alkylphenols (AP) and alkylphenol ethoxylates (APEO) determination in agricultural soil samples has been developed. In a first stage these compounds were isolated from soil by pressurized liquid extraction (PLE) using methanol. In a second stage the extracts were cleaned up and pre-concentrated by solid-phase extraction (SPE) using ENV+cartridges. The effect of different variables on PLE and SPE was also studied. In the last place, separation and quantification of analytes were performed by liquid chromatography with fluorescence detection (LC-FD) and gas chromatography coupled to mass spectrometry (GC-MS). Quantification limits (QL) ranged from 20 to 200 ng g(-1) for LC-FD and from 3 to 126 ng g(-1) for GC-MS. This method was satisfactorily applied in a study field designed to evaluate the environmental behaviour of APEOs in agricultural soils.