An investigation of the utility of QuEChERS for extracting acid, base, neutral and amphiphilic species from example environmental and clinical matrices

Abstract

Accurate measurement of the composition of complex samples is key for the safety and efficacy of a range of products used in daily life, with sample preparation a critical step in this workflow. QuEChERS is one such method, however published protocols do not explicitly address acidic, basic, neutral, and amphiphilic species in a single protocol and often use extra steps or an alternative preparation to recover the breadth of chemical types. Our work addresses this need by investigating the use of QuEChERS for monitoring this wide range of chemistries within environmental solids and blood plasma, using a protocol that can accommodate both milliliter and microliter sample volumes. While published methods can require significant resource and time, our approach offers a reduction in preparation time (for environmental samples), with the "micro-QuEChERS" protocol offering a further reduction in cost. The analytical performance of these methods were assessed using reversed-phase LC-MS and showed good accuracy, precision, and sensitivity for the expected concentrations in the tested applications. Target analytes of variable lipophilicity/acidity were extracted and isolated from soil, with largely repeatable matrix effects < 15%RSD and recoveries of 39-100%. An initial "proof-of-concept" investigation using the "micro-QuEChERS" protocol showed reduced matrix enhancement (median value of 90%ME) for soil, and improved matrix effects and recovery (>65%) for blood plasma. This novel sample preparation method can therefore offer an improved approach with wider applicability providing "cleaner" extracts than other methods used for high-throughput clinical analysis.

Stochastic Dynamic Mass Spectrometric Quantitative and Structural Analyses of Pharmaceutics and Biocides in Biota and Sewage Sludge

“…The Savitzky–Golay smoothing function with baseline correction was used. The ICIS algorithm involves a trapezoidal integration approach [ 1 , 5 , 6 , 7 , 104 ]. In order to account for the effect of the smoothing function on chemometrics, herein, we examined the same relationships, but applying baseline correction and TIA ( Figure 4 and Figures S22–S24 ).…”

“…(mL) –1 show r 2 = 0.997. Quantification of BAC-C12 and BAC-C14 yields r 2 = 0.987 and 0.983 [ 1 , 6 , 7 ]. The analysis of the peak at m / z 211.75 ± 0.15 of BAC-C12 ions in biota using the [M+H] + cation at m / z 304 ( Tables S11 and S12 and Figure 6 ) produces |r| = 0.9972 1 and 0.9841 1 when employing the equation D″ SD = f(conc.)…”

“…The main biocidal disposal route is via sewage systems and drains. The potential risk for bioaccumulation carries toxicological effects on the ecosystem [ 1 , 5 , 6 , 7 , 8 ]. The major chemical compositions of cleaning substances, including disinfectants, cosmetics, and personal care products, are surfactants [ 9 , 10 , 11 , 12 ].…”

“…The ultra-high resolving power, selectivity, accuracy, precision, and sensitivity of tandem mass spectrometry are irreplaceable, being used for the analysis of environmental and biological samples. However, MS cannot be used as a universal method for determining mixtures of quaternary ammonium derivatives simultaneously [ 5 , 6 , 27 , 51 ].…”