Fast Extraction and Dilution Flow Injection Mass Spectrometry Method for Quantitative Chemical Residue Screening in Food

Abstract

A prototype multiresidue method based on fast extraction and dilution of samples followed by flow injection mass spectrometric analysis is proposed here for high-throughput chemical screening in complex matrices. The method was tested for sulfonylurea herbicides (triflusulfuron methyl, azimsulfuron, chlorimuron ethyl, sulfometuron methyl, chlorsulfuron, and flupyrsulfuron methyl), carbamate insecticides (oxamyl and methomyl), pyrimidine carboxylic acid herbicides (aminocyclopyrachlor and aminocyclopyrachlor methyl), and anthranilic diamide insecticides (chlorantraniliprole and cyantraniliprole). Lemon and pecan were used as representative high-water and low-water content matrices, respectively, and a sample extraction procedure was designed for each commodity type. Matrix-matched external standards were used for calibration, yielding linear responses with correlation coefficients (r) consistently >0.99. The limits of detection (LOD) were estimated to be between 0.01 and 0.03 mg/kg for all analytes, allowing execution of recovery tests with samples fortified at ≥0.05 mg/kg. Average analyte recoveries obtained during method validation for lemon and pecan ranged from 75 to 118% with standard deviations between 3 and 21%. Representative food processed fractions were also tested, that is, soybean oil and corn meal, yielding individual analyte average recoveries ranging from 62 to 114% with standard deviations between 4 and 18%. An intralaboratory blind test was also performed; the method excelled with 0 false positives and 0 false negatives in 240 residue measurements (20 samples × 12 analytes). The daily throughput of the fast extraction and dilution (FED) procedure is estimated at 72 samples/chemist, whereas the flow injection mass spectrometry (FI-MS) throughput could be as high as 4.3 sample injections/min, making very efficient use of mass spectrometers with negligible instrumental analysis time compared to the sample homogenization, preparation, and data processing steps.

Determination of Creatinine in Human Urine with Flow Injection Tandem Mass Spectrometry

“…Similar methods are now used in many nationwide neonatal screening programs [23,24]. In the fields of pesticide determination [25,26,27], therapeutic drug monitoring [28] and analysis of adulterated dietary supplements [29], FIA-MS/MS has recently been presented as an adequate alternative to LC-MS/MS. For FIA-MS/MS the mass spectrometer is directly coupled to a pump delivering a continuous flow of eluent solvents, whereas the LC column compartment is bypassed.…”

“…The two most important analytical challenges of FIA-MS/MS are: (1) assessment and exclusion of coelution bias, which is here addressed by qualifier ion monitoring [29,30], and (2) correct quantification in the presence of significant ion suppression, which is best achieved by using properly matched stable isotope-labeled internal standards (SIL-IS) [31]. If properly applied, FIA-MS/MS provides high precision, short run times and remarkable cost savings due to elimination of time-consuming and possibly error-prone procedures of sample cleanup and pre-separation [27]. …”

Electron ionization LC‐MS with supersonic molecular beams—the new concept, benefits and applications

“…Because EI‐LC‐MS with SMB has no matrix related ion suppression effects, it does not always require LC for sample separation from the matrix, and thus a new approach is enabled for achieving ultra‐fast flow injection (FI) EI‐MS‐MS with SMB analysis. Recently, the topic of flow injection MS‐MS as an alternative to lengthy LC‐MS analysis received significant attention in the world of pesticides analysis in agricultural products …”

Use of flow injection mass spectrometric fingerprinting and chemometrics for differentiation of three black cohosh species

“…The dominant groups of chemical constituents considered characteristic of black cohosh are the triterpene glycosides, such as 23-epi-26-deoxyactein and cimicifugoside H-1, and the polyphenols [18][19][20]. Recent pharmacological studies of black cohosh have shown that it has estrogen-like, dopaminergic, and serotonergic activity [21][22][23][24][25].…”