Column experiment on activation aids and biosurfactant application to the persulphate treatment of chlorophene-contaminated soil.

An innovative strategy integrating the use of biosurfactant (BS) and persulphate activated by chelated iron for the decontamination of soil from an emerging pollutant chlorophene was studied in laboratory down-flow columns along with other persulphate activation aids including combined application of persulphate and hydrogen peroxide, and persulphate activation with sodium hydroxide. Although BS addition improved chlorophene removal by the persulphate treatment, the addition of chelated iron did not have a significant influence. Combined application of persulphate with hydrogen peroxide resulted in a significant (p≤.05) overall improvement of chlorophene removal compared with treatment with persulphate only. The highest removal rate (71%) of chlorophene was achieved with the base-activated persulphate, but only in the upper part (of 0.0-3.5 cm in depth) of the column. The chemicals at the applied dosages did not substantially influence the Daphnia magna toxicity of the effluent. Dehydrogenase activity (DHA) measurements indicated no substantial changes in the microbial activity during the persulphate treatment. The highest oxygen consumption and a slight increase in DHA were observed with the BS addition. The combined application of persulphate and BS at natural soil pH is a promising method for chlorophene-contaminated soil remediation. Hydroquinone was identified among the by-products of chlorophene degradation.

Targeted three-dimensional liquid chromatography: a versatile tool for quantitative trace analysis in complex matrices.

Targeted multidimensional liquid chromatography (MDLC), commonly referred to as 'coupled-column' or 'heartcutting', has been used extensively since the 1970s for analysis of low concentration constituents in complex biological and environmental samples. A primary benefit of adding additional dimensions of separation to conventional HPLC separations is that the additional resolving power provided by the added dimensions can greatly simplify method development for complex samples. Despite the long history of targeted MDLC, nearly all published reports involve two-dimensional methods, and very few have explored the benefits of adding a third dimension of separation. In this work we capitalize on recent advances in reversed-phase HPLC to construct a three-dimensional HPLC system for targeted analysis built on three very different reversed-phase columns. Using statistical peak overlap theory and one of the most recent models of reversed-phase selectivity we use simulations to show the potential benefit of adding a third dimension to a MDLC system. We then demonstrate this advantage experimentally by developing targeted methods for the analysis of a variety of broadly relevant molecules in different sample matrices including urban wastewater treatment effluent, human urine, and river water. We find in each case that excellent separations of the target compounds from the sample matrix are obtained using one set of very similar separation conditions for all of the target compound/sample matrix combinations, thereby significantly reducing the normally tedious method development process. A rigorous quantitative comparison of this approach to conventional 1DLC-MS/MS also shows that targeted 3DLC with UV detection is quantitatively accurate for the target compounds studied, with method detection limits in the low parts-per-trillion range of concentrations. We believe this work represents a first step toward the development of a targeted 3D analysis system that will be more effective than previous 2D separations as a tool for the rapid development of robust methods for quantitation of low concentration constituents in complex mixtures.