Optimization of Resolving Power, Fragmentation, and Mass Calibration in an Orbitrap Spectrometer for Analysis of 24 Pesticide Metabolites in Urine

Table 2

Average peak area and coefficient of variation (CV, %) obtained at 3 different Resolving Powers (R) for pesticide metabolites diagnostic and fragment ions (n = 6).

Metabolite	Peak area	Diagnostic ion			Fragment ion
		R=10,000	R=25,000	R=50,000	R=10,000	R=25,000	R=50,000
CMHC	Average	908337	839333	570456	12927	26726	39492
	CV (%)	1.51	2.91	7.49	24.38	21.36	52.87
DEAMPY	Average	994268	880944	834834	63190	161187	175626
	CV (%)	17.15	28.51	10.49	22.31	16.20	40.94
IMPY	Average	1447089	1425080	1663104	Not found	47097	116409
	CV (%)	0.36	7.92	13.22	Not found	1.23	41.28
PNP	Average	6388647	6280026	6007343	3938342	3858484	4005830
	CV (%)	1.70	2.06	1.92	7.36	4.40	6.67
TCPy	Average	1090750	1148221	943686	-	-	-
	CV (%)	1.73	7.04	8.08	-	-	-
MNP	Average	3938892	3813784	3650660	503016	474896	634023
	CV (%)	3.10	3.85	4.18	11.40	13.27	19.46
DMTP	Average	76340	68339	88833	2644	6361	9973
	CV (%)	39.41	5.74	16.55	57.74	37.34	57.74
DMDTP	Average	111502	321392	247711	2679	16962	53675
	CV (%)	36.39	10.13	30.71	57.74	110.51	11.56
DEP	Average	1719737	1870997	1556112	196269	272546	272666
	CV (%)	4.09	4.33	5.83	21.00	12.49	6.12
DETP	Average	2224008	2154624	1819644	50934	141703	169339
	CV (%)	0.08	6.97	6.56	63.42	24.47	24.00
AP	Average	58729	74307	90733	157684	157729	206069
	CV (%)	8.34	33.62	17.63	7.21	4.59	13.43
MMP	Average	69818	178190	112470	19869	169131	69306
	CV (%)	7.38	2.89	4.58	25.93	3.05	7.43
OMET	Average	45484	226016	149173	13032	25505	32670
	CV (%)	69.04	23.35	17.68	35.04	22.09	32.95
DIMET	Average	380660	399855	329466	60934	83874	87121
	CV (%)	8.48	11.44	14.44	6.51	10.55	31.27
PBA	Average	648211	571829	363693	121191	138365	166373
	CV (%)	8.82	15.34	16.11	11.30	20.44	23.68
FPBA	Average	612579	519635	405204	73743	82755	112916
	CV (%)	13.94	23.07	11.99	16.68	13.95	31.57
cis DCCA	Average	171464	273263	194626	-	-	-
	CV (%)	28.60	16.39	13.55	-	-	-
trans DCCA	Average	453810	436816	314120	-	-	-
	CV (%)	6.12	6.49	13.04	-	-	-
DBCA	Average	6904	32503	32185	-	-	-
	CV (%)	31.56	40.91	16.74	-	-	-
ATZM	Average	273078	1179224	756085	1314830	1421843	1252716
	CV (%)	71.21	3.96	2.01	3.57	4.46	9.05
ALAM	Average	67659	687712	511658	831200	1255816	1242225
	CV (%)	12.30	15.92	7.77	7.02	2.35	5.40
METM	Average	268530	644807	446473	2762	5381	6657
	CV (%)	8.80	4.93	9.49	57.74	57.74	57.74
2,4-D	Average	1234998	1225331	907979	1130961	1117200	1224757
	CV (%)	6.27	4.39	5.67	3.85	8.45	3.68
2,4,5-T	Average	731224	786035	477627	677796	718415	777837
	CV (%)	10.79	10.86	10.65	7.95	12.15	13.05

Acquisition conditions: ESI+/ESI- in separated injections, HCD fragmentation 20 eV, and external mass calibration.
-: no fragment ions monitored.
Irregular peak shape caused by isobaric interferences. The measured areas could be affected by the interferences.