A LC-MS/MS method with electrospray ionization and atmospheric pressure chemical ionization source for analysis of pesticides in hemp

Background Pesticide testing for hemp has traditionally focused on techniques like QuEChERS with dSPE and SPE which demand time-consuming sample preparation, typically resulting in poor recovery rates for some pesticides, and requires the use of both LC-MS/MS and GC-MS/MS based instruments to cover the analysis for all regulated pesticides. In this study, we describe a streamlined approach for working with LC-MS/MS featuring a dual electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) sources using solvent extraction for faster and easier sample preparation and with 80–120% recovery for the analysis of all of 66 pesticides (regulated by California state in cannabis) with low detection limits in hemp. Methods A simple solvent extraction with acetonitrile was used to extract pesticides from hemp. A LC-MS/MS system with dual ESI and APCI source was used to determine sensitivity for the analysis of 66 pesticides in hemp matrix, 62 pesticides were analyzed using an 18-min LC-MS/MS method with an ESI source and the other 4 pesticides were measured using a 6-min LC-MS/MS method with an APCI source. Results The limit of quantitation (LOQ) of all 66 pesticides in hemp was in the range of 0.0025–0.1 μg/g which was well below the California state action limits of these analytes in cannabis products. A simple, fast, and cost-effective solvent extraction method was used for sample preparation to get good recovery in the range of 80–120% with RSD less than 20%. The unique ionization mechanism of chlorinated pesticides such as pentachloronitrobenzene using the LC-MS/MS system with an APCI source was elucidated. The proficiency test report generated with the LC-MS/MS method showed acceptable results for all of 66 pesticides in hemp with all of th z scores less than 2 with no false positives and negatives. The stability data collected over 5 days showed RSD less than 20% for 66 pesticides in hemp, and this demonstrated the robustness of the LC-MS/MS system used in this work. Conclusions A LC-MS/MS method with dual ESI and APCI sources was developed for the analysis of 66 pesticides in hemp. The recovery of all pesticides from a hemp matrix was in the acceptable range of 80–120% with RSD less than 20%.

A Versatile Vacuum Ultraviolet Ion Source for Reduced Pressure Bipolar Chemical Ionization Mass Spectrometry

We present the development of a Chemical Ionization Mass Spectrometer (CIMS) ion source specifically designed for in situ measurements of trace gases in the upper troposphere and lower stratosphere. The ion source utilizes a commercially available photoionization krypton lamp, primarily emitting photons in the vacuum ultraviolet (VUV) region at wavelengths of 124 and 117 nm (corresponding to energies of 10 and 10.6 eV, respectively), coupled to a commercially available Vocus Proton Transfer Reaction Mass Spectrometer. The VUV ion source can produce both negative and positive reagent ions, however, here we primarily focus on generating iodide anions (I−). The instrument’s drift tube (also known as ion molecule reactor) operates at pressures between 2 and 10 mbar, which facilitates ambient sampling at atmospheric pressures as low as 50 mbar. The low operating pressure reduces secondary ion chemistry that can occur in iodide CIMS. It also allows the addition of water vapor to the drift tube to exceed typical ambient humidity by more than one order of magnitude, significantly reducing ambient humidity dependence of sensitivities. An additional benefit of this ion source and drift tube is a 10 to 100-fold reduction in nitrogen consumed during operation relative to standard I− ion sources, resulting in significantly reduced instrument weight and operational costs. In iodide mode, sensitivities of 76 cps/ppt for nitric acid, 35 cps/ppt for Br2, and 8.9 cps/ppt for Cl2 were achieved. Lastly, we demonstrate that this ion source can generate benzene (C6H6+) and ammonium (NH4+) reagent ions to expand the number of detected atmospheric trace gases.