Hollow fiber liquid-phase microextraction combined with supercritical fluid chromatography coupled to mass spectrometry for multiclass emerging contaminant quantification in water samples.

The hollow fiber liquid-phase microextraction allows highly selective concentration of organic compounds that are at trace levels. The determination of those analytes through the supercritical fluid chromatography usage is associated with many analytical benefits, which are significantly increased when it is coupled to a mass spectrometry detector, thus providing an extremely sensitive analytical technique with minimal consumption of organic solvents. On account of this, a hollow fiber liquid-phase microextraction technique in two-phase mode combined with supercritical fluid chromatography coupled to mass spectrometry was developed for quantifying 19 multiclass emerging contaminants in water samples in a total chromatographic time of 5.5 min. The analytical method used 40 µL of 1-octanol placed in the porous-walled polypropylene fiber as the acceptor phase, and 1 L of water sample was the donor phase. After extraction and quantification techniques were optimized in detail, a good determination coefficient (r2 > 0.9905) in the range of 0.1 to 100 µg L-1, for most of the analytes, and an enrichment factor in the range of 7 to 28,985 were obtained. The recovery percentage (%R) and intraday precision (%RSD) were in the range of 80.80-123.40%, and from 0.48 to 16.89%, respectively. Limit of detection and quantification ranged from 1.90 to 35.66 ng L-1, and from 3.41 to 62.11 ng L-1, respectively. Finally, the developed method was successfully used for the determination of the 19 multiclass emerging contaminants in superficial and wastewater samples.

Temporal distribution and ecological risk assessment for pesticides in water from the north-central coastal zone of Sinaloa, Mexico.

Water contamination with pesticides is one of the major pollution problems in northwestern Mexico, and this is due to the extensive use of pesticides in agriculture. In this research, water samples of ten sampling sites (fishing grounds, beaches, and both) were analyzed in the search for 28 pesticides (organochlorines, organophosphates, pyrethroids, carbamates, among other chemical classes), supplemented with a calculation of the resulting potential environmental risk. Pesticides were separated from the matrix by liquid-liquid extraction and quantified by gas chromatography coupled to electron micro-capture (organohalogenated) and pulsed flame photometric detectors (organophosphates). In addition, the ecotoxicological risk of pesticides in algae, invertebrates, and fish was assessed, based on seawater pesticide concentrations using the Risk Quotient (RQ) and Toxic Units (TU) approach. The results showed 18 pesticides identified in the analyzed samples, where cypermethrin and chlorpyrifos were identified with the maximum concentrations of 1.223 and 0.994 µg L-1, respectively. In addition, these two pesticides have been associated with acute toxic effects on algae, invertebrates, and fish. It is important to pay particular attention to the search for long-term alternatives to the use of chlorpyrifos and cypermethrin due to their high detection rates and the risks associated with their toxic properties. However, the adoption of alternative measures to synthetic pesticide control should be a priority, moving towards sustainable practices such as the use of biopesticides, crop rotation and polycultures.

HPLC-DAD method development and validation for the quantification of hydroxymethylfurfural in corn chips by means of response surface optimisation.

In recent years, there has been an increased concern about the presence of toxic compounds derived from the Maillard reaction produced during food cooking at high temperatures. The main toxic compounds derived from this reaction are acrylamide and hydroxymethylfurfural (HMF). The majority of analytical methods require sample treatments using solvents which are highly polluting for the environment. The difficulty of quantifying HMF in complex fried food matrices encourages the development of new analytical methods. This paper provides a rapid, sensitive and environmentally-friendly analytical method for the quantification of HMF in corn chips using HPLC-DAD. Chromatographic separation resulted in a baseline separation for HMF in 3.7 min. Sample treatment for corn chip samples first involved a leaching process using water and afterwards a solid-phase extraction (SPE) using HLB-Oasis polymeric cartridges. Sample treatment optimisation was carried out by means of Box-Behnken fractional factorial design and Response Surface Methodolog y to examine the effects of four variables (sample weight, pH, sonication time and elution volume) on HMF extraction from corn chips. The SPE-HPLC-DAD method was validated. The limits of detection and quantification were 0.82 and 2.20 mg kg-1, respectively. Method precision was evaluated in terms of repeatability and reproducibility as relative standard deviations (RSDs) using three concentration levels. For repeatability, RSD values were 6.9, 3.6 and 2.0%; and for reproducibility 18.8, 7.9 and 2.9%. For a ruggedness study the Yuden test was applied and the result demonstrated the method as robust. The method was successfully applied to different corn chip samples.