Douglas G. Hayward

Quadrupole ion storage tandem mass spectrometry and high-resolution mass spectrometry: complementary application in the measurement of 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans in US foods

The US Food and Drug Administration has simultaneously utilized both high-resolution mass spectrometry (HRMS) and quadrupole ion storage tandem mass spectrometry (QISTMS) in the measurement of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in 147 food samples collected in 1998 and 1999 in the US. In 1998, 20 egg samples, six scallop, 10 blue crab, eight American lobster, 10 pollack, 15 striped bass, five rockfish, 10 crawfish, seven aqua-cultured and 13 wild-caught salmon, along with 19 cream and 18 mozzarella cheese samples were measured for PCDD/Fs. QISTMS provided limits of detection (LODs) close to those produced using HRMS for many congeners in 56 samples analyzed by both techniques in 1998 and three salmon and three striped bass collected in 1999. The I-TEQs of the mean levels for measured congeners in 40 samples of fish and shellfish and 16 cheese and eggs from 1998 analyzed by HRMS and QISTMS were 0.99 and 1.1 ng/kg wet weight, respectively. The I-TEQ for mean congener levels in the 40 fish and shellfish measured by HRMS was 1.4 ng/kg wet weight. A higher sample throughput with greater data quality at a lower cost is achievable by using both QISTMS and HRMS.

Determination of polychlorinated dibenzo-p-dioxin and dibenzofuran background in milk and cheese by quadrupole ion storage collision induced dissociation MS/MS

Recent developments in quadrupole ion storage scanning techniques have made possible the acquisition of mass spectrometry/mass spectrometry (MS/MS) data with high sensitivity, selectivity and reproducibility. Retail dairy products were analyzed successfully for bioincurred or background contamination by all 17 of the 2,3,7,8 substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Analytes were measured by both full scan electron impact low resolution MS (EI-LRMS) and collision induced dissociation MS/MS (CID MS/MS). Results were comparable using either technique. MS/MS, however, provided higher sensitivity and selectivity on many congeners. Results for the MS/MS technique were reproducible, with little reduction in sensitivity or spectral quality during the analyses of all test samples. The MS/MS signal to noise ratio (S/N) was 10 to 100 times greater than low resolution electron impact performed with the same instrument in food matrices. Signal to noise ratios increased on most parent ions as well as for all daughter ions. Further development of this technique may provide a cost effective alternative to traditional HRMS analyses of PCDDs and PCDFs in food.

Application of a High-Resolution Quadrupole/Orbital Trapping Mass Spectrometer Coupled to a Gas Chromatograph for the Determination of Persistent Organic Pollutants in Cow’s and Human Milk

A quadrupole/orbital trapping mass spectrometer or Q-Exactive (QE) interfaced with a gas chromatograph (GC) was optimized for measuring polychlorinated dibenzo- p-dioxins, dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs) in foods. Figures of merit include (1) an instrument detection limit (IDL) for 2,3,7,8-tetrachlorodibenzo- p-dioxin (TCDD) of 9 femtograms (fg), (2) quantitative mass resolution from PCDD interferences (e.g., PCBs, methoxy-PCBs DDTs, polychlorodibenzylphenyl ethers, polychloroxanthenes, methyl-polychlorodibenzofuran, and polychlorodibenzothiophenes), and (3) mass accuracy <1 ppm at the IDL. The QE measured the concentrations of PCDD/Fs and PCBs in whole cows milk with no known source of contamination (e.g., TCDD 33 fg/g fat). A National Institute of Standards and Technology (NIST) unfortified human milk standard reference material (SRM) 1953 was measured determining 27 PCDD/F and PCB congeners with an average difference of 7.6% from the certified results. The QE-GC is a benchtop instrument, easy to service, easy to operate, and requires no lock masses, mass preselection, or chemical ionization conditions. The QE-GC demonstrated that it can be an alternative to the double focusing magnetic sector instruments (sector) for the high-resolution measurement of PCDD/Fs and PCBs in dairy products.