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SSI-GCMS-1302
Instrument Configuration
The analyses were conducted using a Shimadzu columns were interfaced to a single MS by means of a
GCMS-QP2010 SE shown in Figure 1. The GCMS was special adaptor and a two-hole ferrule. The Twin Line MS
operated in full-scan mode according to the operational Kit column connection is shown in Figure 2. Volatile
parameters specified in USEPA Methods 8260C and analysis by USEPA Method 8260C was performed using an
8270D. The instrument was configured with the Shimadzu EST Encon Evolution purge-and- trap concentrator with
Twin Line MS Kit: two chromatographic columns were Centurion autosampler operated in the water mode.
connected to two split-splitless injectors, and both of the
Instrument conditions for the analyses were based on 0.25-mm columns is also possible. The capacity of the
those recommended for USEPA Methods 8260C and GCMS-QP2010 SE vacuum system allows a total flow of 4
8270D. Carrier gas flow was supplied to both analytical mL/min. Under the conditions specified below, total flow
columns at all times to prevent column degradation; the of both columns was slightly greater than 1 mL/min.
column not being used for the analyses was operated in Specific instrument conditions for the EPA Methods
the constant linear velocity mode at 30 cm/sec. 8260C and 8270D analyses are shown in the respective
Narrow-bore columns (0.18-mm) were chosen for this sections below.
application to minimize total column flow, but the use of
Table 1: Instrument Operating Conditions for Volatile Analysis by USEPA Method 8260C
Figure 3A: BFB Mass Spectrum Figure 3B: BFB Tune Evaluation
Calibration and Determination of Precision, Recovery, and MDLs for Volatile Organics
Calibration standards were prepared over the calibration analytes. For most of the target compounds, the %RSD of
range of 0.5-200 g/L (parts-per-billion, ppb) and the relative response factors was 10-15% for the 0.2-200
transferred to 40-mL VOA vials for sampling and analysis. g/L calibration range. For those target compounds
Internal standards were held constant at 25 g/L, and with %RSD >15%, the linear calibration was used. In all
were added automatically with the Centurion autosampler. cases, the correlation coefficient was greater than 0.99,
The initial calibration standards were analyzed using the demonstrating linear response for the target compounds.
instrument conditions outlined above. The detector The calibration data satisfied the USEPA Method 8260C
(electron multiplier) voltage was adjusted to provide calibration acceptance criteria. Calibration results are
adequate response at the lowest calibration level and summarized in Table 2, below.
avoid saturation at the highest calibration level. Figure 4A
shows the total ion chromatogram of a 10 g/L standard; Analytical precision, method detection limits (MDLs), and
Figure 4B illustrates the chromatography of the compound recoveries were determined following the
early-eluting compounds in the 1.0 g/L standard. procedures referenced in USEPA Method 8260C. Eight
aliquots of the 0.5 g/L calibration standard were
The data for the initial calibration were processed using analyzed, analyte concentrations determined, and the
GCMSsolution software. The calibration data were MDLs calculated. Statistically-derived MDLs for most of
evaluated both by examination of the %RSD of the the compounds were below 0.1 g/L. Method detection
relative response factors and by the linearity (correlation limit results are presented in Table 2, below.
coefficient) of the calibration curves for all of the target
2
3 1. Dichlorodifluoromethane
2. Chloromethane
3. Vinyl Chloride
4 5
4. Chloroethane
5. Bromomethane
6. Trichlorofluoromethane
1 6
Figure 4B: Mass Chromatograms of Early-eluting Compounds in 1.0 g/L Calibration Standard
Table 2: Calibration Results, and Determination of Precision, Recovery, and Method Detection Limits for Volatile Organics by
USEPA Method 8260C
Table 3: Instrument Operating Conditions for Semi-volatile Analysis by USEPA Method 8270D
Figure 5A: DFTPP mass spectrum Figure 5B: DFTPP spectrum check
No. SSI-GCMS-1302
Pentachlorophenol
Benzidine
Figure 5C: Tailing of pentachlorophenol and benzidine Figure 5D: Column performance check
DDT (expanded)
DDE DDD
Calibration and Determination of Precision, Recovery, and IDLs for Semi-volatile Organics
Calibration standards were prepared over the calibration response factors for the lowest calibration points are not
range of 0.4-160 g/mL and transferred to 2-mL included for all of the analytes. Most analytes showed %
autosampler vials for analysis. Internal standards were RSD less than 15%. Where specific analytes had % RSD
held constant at 40 g/mL. Data for the initial calibration greater than 15%, the linear calibration was used for
standards were acquired using the instrument conditions calculations, and the correlation coefficient (r) was used
outlined above. The detector (electron multiplier) voltage to evaluate the validity of the calibration.
was adjusted to provide adequate response at the lowest
calibration level and avoid saturation at the highest Replicate injections of the four low-level calibration
calibration level. Figure 6 shows the total ion standards (0.4, 1.0, 2.0, and 5.0 g/mL) were used to
chromatogram of a 50 g/mL standard. Selected assess analytical precision and calculate instrument
chromatograms of individual analytes which may be detection limits in a manner analogous to the procedure
subject to non-ideal chromatography, are shown in referenced in Method 8270D. (Sample extractions were
Figures 7A-7F. not performed, so the statistical values are presented as
instrument detection limits, expressed in g/mL). The
Response factors were tabulated and percent relative statistical values and determination of instrument
standard deviation (%RSD) of response factors were detection limits were based on data from injection of the
determined as described in USEPA Method 8270D; the standard concentration corresponding to the lowest
response factors for the initial calibration are presented point in the initial multi-point calibration for a given
in Table 4. Response of selected analytes varied analyte. Data for assessment of analytical precision are
considerably, especially at low concentrations, so summarized in Table 4.
No. SSI-GCMS-1302
Figure 7C: 2,4,5- and 2,4,6-Trichlorophenols (1 g/mL) Figure 7D: Pentachlorophenol (1 g/mL)
Table 4: Calibration Results, and Determination of Precision, Recovery, and Instrument Detection Limits for Semi-volatile Organics by
USEPA Method 8270D
*Statistically-derived instrument detection limits (IDLs) were determined by multiple injections of low level standards, and did not include the
sample preparation (extraction and clean-up) steps.
References
1. USEPA Method 8260C Volatile Organic Compounds by Gas Chromatography / Mass Spectrometry (GC/MS),
Revision 3, August, 2006.
2. USEPA Method 8270D Semi-volatile Organic Compounds by Gas Chromatography / Mass Spectrometry (GC/MS),
Revision 4, February, 2007.
3. 40 CFR Appendix B to Part 136 - Definition and Procedure for the Determination of the Method Detection Limit.
Acknowledgements
The authors wish to acknowledge EST Analytical, Fairfield, OH for use of purge-and-trap equipment used in this study
and for their continued technical support. We also acknowledge the support of Restek Corporation, Bellefonte, PA for
useful discussions and advice regarding column selection and for GC columns and standards used in this study.