Joint influence of surfactants and humic matter on PAH solubility. Are mixed micelles formed?

Mobilization of polycyclic aromatic hydrocarbons (PAH) by surfactants, present at contaminated sites or deliberately introduced for remediation purposes, is inevitably associated with the influence of humic substances, which are ubiquitous in natural systems. Therefore, the solubilizing effects of anthropogenic and natural amphiphiles must be considered in their combined action since synergistic or antagonistic effects may be expected, for instance, as a consequence of mixed micellization.

In this paper, solubilization of ¹⁴C-labeled pyrene in single-component and mixed solutions of surfactants and humic acid (coal-derived) was investigated up to the micellar concentration range. At low concentrations, antagonistic effects were observed for systems with cationic as well as anionic surfactants. Solubility enhancements in the presence of humic acid were canceled on addition of a cationic surfactant (DTAB) since charge compensation at humic colloids entailed precipitation. Solubility was also found to be decreased in the presence of an anionic surfactant (SDS), which was attributed to a competitive effect in respect of pyrene–humic interaction. This explanation is based on octanol–water partitioning experiments with radiolabeled humic acid, yielding evidence of different interaction modes between humic colloids and cationic/anionic surfactants. At higher concentrations, the effects of humic acid and SDS were found to be additive. Thus, a formation of mixed micelles is very unlikely, which was confirmed by size exclusion chromatography of mixed systems. It can be concluded that remediation measures on the basis of micellar solubilization are not significantly affected by the presence of natural amphiphilic compounds.     

Empirical relationship between precision and ultra-trace concentrations of PCDD/Fs and dioxin-like PCBs in biological matrices

Dioxin analysis in food and feed can be characterized as an analytical application where very high accuracy is required at very low levels of contamination. Gas chromatography (GC) in combination with 13C-label isotope dilution (ID) high resolution mass spectrometry (HRMS) is the reference congener-specific technique characterized by pronounced selectivity, precision and trueness at parts-per-trillion (ppt) and sub-parts-per-trillion (sub-ppt) levels. The quality of the analytical data produced routinely by a laboratory should be adequate for its intended purpose, i.e., one will seek a compromise between the cost and time needed and the consequences of incorrect decisions due to erroneous results. The requirements for reproducibility are usually dependent on the analyte concentrations and have been expressed in various empirical functions. While Horwitz or modified functions are widely useful for many purposes, it would be difficult to expect these functions to cover every analytical problem. This study reports on precision characteristics achieved by the GC-ID-HRMS reference method for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in food and feed in two interlaboratory method-performance studies among expert laboratories with long-standing experience in this field. Striking linear functions in log scale between reproducibility standard deviation and congener's level over a concentration range of 10(-8)-10(-14)g per g fresh weight are observed. The data fit very well to a Horwitz-type function of the form sR=0.153c0.904, where sR and c are dimensionless mass ratios expressed in pg g(-1) on fresh weight, regardless of the nature of the toxic congeners, food and feed matrices, or sample preparation methods. We demonstrate that the proposed function is suitable for use as a fitness-for-purpose criterion for proficiency assessment in interlaboratory comparisons on dioxins and related compounds in food.     

Photochemical production of methane in natural waters: implications for its present and past oceanic source

We conducted irradiation experiments with riverine, estuarine, and marine water samples to investigate the possibility of photochemical methane (CH4) formation. CH4 photoproduction was undetectable under oxic conditions or in the absence of methyl radical precursors indicating that its photochemical formation is negligible in the present ocean. Significant photochemical CH4 production was observed in the presence of a methyl radical precursor such as acetone under strictly anoxic conditions. Our results indicate an indirect formation mechanism with coloured dissolved organic matter acting as photosensitizer. We suggest that photochemical CH4 formation might have occurred in the anoxic ocean surface layer of the Archean prior to the onset of O2 accumulation in the atmosphere at around 2300 million years ago. Oceanic CH4 photoproduction via methyl radical (CH3) precursors and its subsequent release to the atmosphere may have contributed to high CH4 mixing ratios in the Archean atmosphere.