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.
Highlights
Advances in the analytical workflow have largely concerned instrumentation accuracy and sensitivity[1]; there remains a need to develop sample preparation technology to meet the demands of “blue-sky” research and regulated industry.[2]
Chromatographic separation was carried out using a Thermo Scientific (Hemel Hempstead, UK) liquid chromatography (LC) system consisting of a Micro AS autosampler and MSPump Plus, with a reversed phase Waters (Elstree, UK) Xselect HSS T3 LC column (1 × 100 mm, 3.5 μm) and a Phenomenex KrudKatcher Ultra online filter (Macclesfield, UK)
The data showed repeatable chromatography for all analytes on both days (RSDs < 5%) and no significant difference determined between the 2 days; largely chromatographic stability improved for acidic/neutral/basic analytes with prolonged use indicating a further settling of chromatographic conditions with time
Summary
Advances in the analytical workflow have largely concerned instrumentation accuracy and sensitivity[1]; there remains a need to develop sample preparation technology to meet the demands of “blue-sky” research and regulated industry.[2]. With greater focus on links between environmental and public health, and increased regulation for pollution and waste management, the selection of environmental matrices, target chemistries and their (trace) amounts for analysis[3,4,5] make the analytical challenge more difficult to address without appropriate sample preparation solutions. The introduction of the Water Framework Directive[3] and Circular Economy legislation (waste and landfill6) has increased the types of matrices requiring molecular (pollutant) characterization to include organisms, wastewater, sludges, and receiving sediments.[3] These regulations are evidence-driven with substances of concern and their environmental limits[4,5] continually evolving to protect environmental and public health. These may cover a range of classes with high usage (and perceived disposal) rates (e.g. diphenhydramine, carbamazepine, erythromycin, etc) and lipophilicity (log Kow, log P, or Kd), with the latter enabling sorption to sludge and/or bioaccumulation within soil and biota, respectively.[9,10] Given the significant re-use of treated sewage sludge as agricultural fertilizer (80%)[11] and the proposed effects on agricultural soil (e.g. antimicrobial resistance12), it is essential that pollutants are accurately measured within these samples
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