ICP-MS: The Ultimate GC Detector

Mina Tanoshima, Steve Wilbur and Emmett Soffey , Agilent Technologies Inc.

Introduction Results and Discussion

Gas chromatography (GC) is widely used for the speciation and detection of volatile 1) Organo-tin analysis Table 2. Method parameters for the separation of PBDEs using the GC with ICP-MS detection
organic compounds in many applications and industries. There are many detectors The toxic effects of organo-tin compounds in the environment are well known
GC ICP-MS
for GC, such as PFPD/FPD ((pulsed) flame photometric detector) or SCD (Sulfur and research has begun to include matrices with human health implications,
chemiluminescence detector) for sulfur, NPD (nitrogen/phosphorus detector) for such as seafood, manufactured products, and human blood samples. In this Injection Splitless 1ul ICP-MS model 7700x

nitrogen and phosphorus and ECD (electron capture detector) for the halogens. GC study, a mixed organo-tin standard was analyzed. The analysis was completed Column DB-5MS (5m x 0.25 mm x
0.25um film thickness)
RF power 1250 W

is also combined with a mass spectrometer or mass selective detector (MS or MSD), in less than 12 minutes achieving detection limit of 5.9 ppt for tributyl tin (TBT). Oven program 80℃ (1min), 20℃/min -> 320℃ Sample depth 7 mm
both with single quadrupole or triple-quad (QQQ). However, none of these detectors (5min)
Carrier gas 0.61 L/min
is capable of providing universal, element specific quantification in the manner of Carrier gas He at 7mL/min
Full Time Range EIC (mass 120): Inlet temp 260 deg C
ICP-MS. ICP-MS provides a unique combination of rapid multi-element/isotope Aux gas 1.5 L/min

Transfer line temp 250 deg C

analysis, with very high sensitivity. Additional gas No

ICP injector temp 280 deg C Monitored mass (m/z) 79, 81

Count
Experimental
3) Sulfur analysis in diesel fuel
Sulfur in motor fuels has been implicated in global warming and acid rain. It is also
Instrumentation
a catalyst poison for automobile catalytic converters and refinery catalytic crackers.
An Agilent 7890A GC and Agilent 7700x ICP-MS were connected using the new
Reducing total sulfur in motor fuels has become a critical air pollution control goal
Agilent GC-ICP-MS interface (Figure 1) to evaluate these three analyses; 1)Organo- RT (min) worldwide. Figure 5 show the chromatogram for low sulfur in diesel samples
tin, 2) Polybrominated Diphenyl Ether (PBDE), and 3) Sulfur species in diesel. The
(NIST 2724B). GC and ICP-MS operating parameters are shown in Table 3.
interface connects the two instruments via a passivated, heated Sulfinert ® tube
Figure 3. Chromatogram of 10 ppb organo-tin standard. The samples was derivatized beforehand
between the GC column and the tip of the ICP injector using a special torch with a
heated injector to maintain constant high temperature and inertness. The schematic
Table 1. Method parameters for the separation of organo-tin using the GC with ICP-MS detection
is shown in Figure 2.
GC ICP-MS

Injection Splitless 1ul ICP-MS model 7700x

Column HP-5 (30m x 0.32mm i.d. x 0.25
RF power 1200 W

Count
um film thickness)

Oven program 70 deg(1min) ~ 30deg/min Sample depth 8 mm

~190deg (0min) ~ 15deg/min ~
270deg (4min) Carrier gas 0.80 L/min

Carrier gas He at 2mL/min Aux gas 1.5 L/min

Inlet temp 290 deg C
Additional gas No
Transfer line temp 250 deg C
Monitored mass (m/z) 118,120
ICP injector temp 250 deg C

RT (sec)

2) Polybrominated Diphenyl Ether (PBDE) analysis

Figure 5. Carbon and sulfur extracted ion chromatograms for NIST 2724B low sulfur
PBDEs are widely used flame retardants added to many common household
products, such as mattresses and furniture, and electronic devices. Table 3. GC and ICP-MS operating parameters
However their similarity in structure to PCBs and dioxins has raised GC ICP-MS

concerns about health risks associated with their use. For this study, a Injection Split 1:50 1ul ICP-MS model 7700x

PBDE mix(CIL Predominant Congener Mixture EO-5103) containing 14 Column HP-5 (30m x 0.32mm i.d. x 0.25
um film thickness)
RF power 1550 W

different PBDEs were analyzed. (Chromatogram is shown in Figure 4.) All Oven program 40deG(4min) ~ 20deG/min
Sample depth 8 mm
~250deG (1min)
Figure 1. Agilent 7700x ICP-MS coupled to an Agilent 7890A GC the PBDEs were separated successfully with good sensitivity, even for the Carrier gas 0.80 L/min
Carrier gas He at 2.5mL/min
difficult #209 (decaBDE) congener, which is thermally labile and Inlet temp 250 degC
Aux gas 1.5 L/min

decomposes easily during GC separation. The detection limit was150 ppt Transfer line temp 250 degC
Additional gas No

for Deca BDE . ICP injector temp 260 degC

Monitored mass (m/z) 118,120

Full Time Range EIC (mass 79)

(1) 2, 2’,4-TriBDE (BDE – 17)
(2) 2, 4’,4-TriBDE (BDE – 28)
(3) 2, 3’,4’,6-TetraBDE (BDE – 71)
(11) 2, 2’,3,4,4’,5’-HexaBDE (BDE – 138)
(12) 2, 2’,3,4,4’,5’,6-heptaBDE (BDE – 183)
(13) 2, 3,3’,4,4’,5’,6’-HeptaBDE (BDE – 190)
Conclusions
(4) 2, 2’,4,4’-TetraBDE (BDE – 47) (14) DecaBDE (BDE – 209)
(5) 2, 3’,4,4’-TetraBDE (BDE – 66)
Count

(6) 2, 2’,4,4’,6-PentaBDE (BDE – 100)

(7) 2, 2’,4,4’-5-PentaBDE (BDE – 99) The use of ICP-MS as a GC detector significantly extends GC capability and expands
(8) 2, 2’,3,4,4’-PentaBDE (BDE – 85)
(9) 2, 2’,4,4’,5,6’-HexaBDE (BDE – 154)
(10) 2, 2’,4,4’,5,5’-HexaBDE (BDE – 153)
its application. With a well-designed GC / ICP-MS interface featuring high
temperature and inertness, organo-tin , PBDE and sulfur compounds in diesel were
successfully analyzed. These results demonstrate the ultimate detection limits and
RT (min)
multi element analysis capability of ICP-MS.
Figure 4. Chromatogram of mixed PBDE standard: 25ppb each compound except #138 (37.5 ppb) and #209
(100 ppb)
Figure 2. Schematic diagram for the Agilent GC-ICP-MS interface for the 7890GC/7700 ICP-MS