Determination of insoluble soap in agricultural soil and sewage sludge samples by liquid chromatography with ultraviolet detection.

We have developed a new analytical procedure for determining insoluble Ca and Mg fatty acid salts (soaps) in agricultural soil and sewage sludge samples. The number of analytical methodologies that focus in the determination of insoluble soap salts in different environmental compartments is very limited. In this work, we propose a methodology that involves a sample clean-up step with petroleum ether to remove soluble salts and a conversion of Ca and Mg insoluble salts into soluble potassium salts using tripotassium ethylenediaminetetraacetate salt and potassium carbonate, followed by the extraction of analytes from the samples using microwave-assisted extraction with methanol. An improved esterification procedure using 2,4-dibromoacetophenone before the liquid chromatography with ultraviolet detection analysis also has been developed. The absence of matrix effect was demonstrated with two fatty acid Ca salts that are not commercial and are never detected in natural samples (C13:0 and C17:0). Therefore, it was possible to evaluate the matrix effect because both standards have similar environmental behavior (adsorption and precipitation) to commercial soaps (C10:0) to C18:0). We also studied the effect of the different variables on the clean-up, the conversion of Ca soap, and the extraction and derivatization procedures. The quantification limits found ranged from 0.4 to 0.8 mg/kg. The proposed method was satisfactorily applied for the development of a study on soap behavior in agricultural soil and sewage sludge samples.

Mobility and fate of carbetamide in an agricultural soil.

The objective of this work is to gain a better understanding of the fate of carbetamide, as a representative herbicide, after its soil application. To reach this goal, batch and column laboratory experiments were performed and a transport model was proposed consistent with these results. Then field-scale experiments were carried out for two years and the results compared with those that would be obtained from the transport model, once the degradation terms were introduced. All this is done for four different scenarios: first, considering that the soil is under its natural condition; second, the soil is amended with organic carbon by the addition of stabilized sewage sludge; third, considering that the percolating aqueous phase contains a significant quantity of surfactant [Linear Alkyl Benzene Sulfonate, (LAS)]; and fourth, the scenario in which the sewage sludge and the surfactant are present simultaneously. The Freundlich model yields a good fit to the data of the sorption isotherms obtained from batch equilibrium experiments, but the isotherms are close to linear. The batch sorption/desorption kinetic data together with the column and field results indicate that the retention kinetics are quite fast and local equilibrium can be assumed for the description of the sorption phenomenon. Results also prove that carbetamide is moderately retained in the original soil with a mean value of the partition coefficient of carbetamide about 0.46 (L kg(-1)). When the soil is amended with sewage sludge, this coefficient is somewhat lower, about 0.40 (L kg(-1)). A further decrease is observed 0.32 L kg(-1)) when the surfactant (LAS) at critical micelle concentration (CMC) is used. The two-region model yields a good reproduction of the results of carbetamide mobility in the soil, both at the laboratory scale and at the field scale.

Sampling and identification of natural dyes in historical maps and drawings by liquid chromatography with diode-array detection.

A simple and rapid liquid chromatographic with diode-array UV-vis spectrophotometric detection (HPLC-DAD) method for identification of natural dyes has been developed. Chromatographic retention of carminic acid, indigotin, crocetin, gambogic acid, alizarin and purpurin has been studied. The mobile phase consisted of 40 mM SDS-10 mM phosphate buffer solution (pH 2.3)-0.1% TFA (eluent A) and acetonitrile (eluent B) using a programmed gradient (5% B to 95% B). Analyses were carried out on a Phenomenex, Luna 5u NH2 100(a) column (250 mm x 4.60 mm i.d., 5 microm particle) and the operating conditions were: 0.6 ml min(-1) flow rate, 20 microl volume injection and 35 degrees C column temperature. Extracts of samples of natural dyes taken from historical maps belonging to The Royal Chancellery Archives in Granada were successfully analyzed using the proposed method including a new technique for sampling.