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To cite this Article Wnorowski, Andrzej, Tardif, Mylaine, Harnish, David, Poole, Gary and Chiu, Chung H.(2006)'CORRECTION OF
ANALYTICAL RESULTS FOR RECOVERY: DETERMINATION OF PAH s IN AMBIENT AIR, SOIL, AND DIESEL EMISSION
CONTROL SAMPLES BY ISOTOPE DILUTION GAS CHROMATOGRAPHY-MASS SPECTROMETRY',Polycyclic Aromatic
Compounds,26:5,313 329
To link to this Article: DOI: 10.1080/10406630601028171
URL: http://dx.doi.org/10.1080/10406630601028171
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Polycyclic Aromatic Compounds, 26: 313329, 2006
Copyright c 2006 Taylor & Francis Group, LLC
ISSN: 1040-6638 print / 1563-5333 online
DOI: 10.1080/10406630601028171
Andrzej Wnorowski
Mylaine Tardif
David Harnish
Gary Poole
Chung H. Chiu
Environment Canada, Air Analysis and Quality Division,
Ottawa, Ontario, Canada
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314 A. Wnorowski et al.
INTRODUCTION
sis conditions, but rather evaluate and compare the output of the two
quantitation approaches. Consequently, we will demonstrate the ability
of surrogate recovery correction to improve quantitation of natives, re-
gardless of the method conditions or instrument used. The data used for
the study was generated in 2003 and 2004 in AAQD laboratories, as a
requirement of our Quality Control Program, and re-analyzed for the
needs of the current study. During the two-year time span, the analysis
was performed following the same methodology by numerous analysts
using various instruments, therefore, the data in a sense could be regarded
as interlaboratory generated. This fact should be taken into consideration
to understand the impact of analytical bias on the presented results and
its correction.
Standards
GC-MS Analysis
was made with an Agilent 7683 Autosampler. The cool on-column injec-
tor was set to track GC oven temperature. A DB-XLB capillary column
(30 m 0.25 mm ID, 0.25 m film thickness) from J&W Scientific
Inc. was used for the separation of PAHs. Helium was utilized as a
carrier gas with a constant flow of 2.0 mL/min. The GC oven initial
temperature was set at 90 C, after 4 minutes increased to 200 C with a
rate of 20 C/min, then increased to 250 C at 2.5 C/min, then increased
to 283 C with a rate of 1.5 C/min and held for 6 minutes. Spectro-
scopic analysis was performed using 70 eV electron impact ionization
and selected ion monitoring mode. All analytes with the same molecular
and fragment ions were chromatographically separated. A minimum of
three ions were monitored for all native analytes, two characteristic ions
for each of the surrogate analytes and one ion for the internal standard
(Tables 1 and 2).
Quantification
The target PAHs were quantified using both isotope dilution correc-
tion and uncorrected procedures. Quality control monitoring of surrogate
recoveries ensured accurate and reliable recovery-corrected quantitation
of the analytes. The acceptable range of surrogate recoveries was set
to contain within 50 and 120%, with no more than two surrogates out-
side of these limits. Target compound identification was confirmed by
the presence of the analytes characteristic ions in the right ratio at the
appropriate retention time. Daily Calibration Check and Performance
Sensitivity standards were analyzed with every sample set to monitor
system performance. Enhanced Data Analysis MSD ChemStation Soft-
ware, version D.01.00, was used for data processing. Statistical data
treatment was performed with ANOVA analysis using the Microsoft
Excel 2003 SP3. Outliers, standard deviation, mean, and significance
PAHs Quantitation by Isotope Dilution GC-MS 317
tests with confidence limits of 95% were estimated based on the meth-
ods of Miller and Miller (12). For the purposes of this study 17 deuter-
ated surrogates were chosen (Table 1) to represent 30 native analytes
(Table 2). A mean relative response factor of surrogates which are clos-
est in chemical properties (homologues) to the native analyte is used for
natives with no corresponding isotopic analogue (Table 2). Although 30
native PAHs were studied, to simplify the data presentation, quantitation
data presented herein shows only PAHs that are common to the three
studied matrices.
TABLE 2. Analyzed PAHs with Monitored Ions and their Corresponding Surrogates
318
Native PAH Quantitation ion Confirmation ions Relative intensities Recovery correction surrogate
Naphthalene 128 127, 102 100, 12, 7 d8 -Naphthalene
Acenaphthylene 152 151, 150 100, 20, 13 d8 -Acenapthylene
Acenaphthene 153 154, 152 100, 96, 48 d10 -Acenaphthene
2-Methylfluorene 165 180, 178 100, 90, 27 AVG (d10 -Fluorene + d10 -Phenanthrene
+ d10 -Anthracene)
Fluorene 166 165, 163 100, 91, 15 d10 -Fluorene
Anthracene 178 176, 179 100, 18, 16 d10 -Anthracene
Phenanthrene 178 176, 179 100, 19, 16 d10 -Phenanthrene
Fluoranthene 202 200, 101 100, 21, 13 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Pyrene 202 200, 101 100, 21, 13 d10 -Pyrene
1-Methylpyrene 216 215, 108 100, 68, 10 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Benzo[a]fluorene 216 215, 108 100, 72, 12 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Benzo[b]fluorene 216 215, 108 100, 89, 13 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Retene 219 234, 204 100, 70, 28 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Benzo[ghi]fluoranthene 226 224, 113 100, 22, 15 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Benz[a]anthracene 228 226, 114 100, 27, 11 d12 -Benz[a]anthracene
Chrysene 228 226, 114 100, 29, 9 d12 -Chrysene
Triphenylene 228 226, 114 100, 28, 10 d12 -Triphenylene
7-Methylbenz[a]anthracene 242 241, 239 100, 40, 28 AVG (d10 -Pyrene + d12 -Benz[a]anthracene
+ d12 -Triphenylene + d12 -Chrysene)
Downloaded By: [Sheffield Hallam University] At: 15:35 19 November 2008
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320 A. Wnorowski et al.
A) Surrogates Recoveries
Evaluation of surrogate recoveries spiked into control samples con-
firmed that the values were within the acceptable range of 50120%
(Figure 1). The data show that the analysis of ambient air samples pro-
vides results closest to the reference values, thus the highest analytical
recovery, probably due to the relatively inert matrix of the ambient air.
Soil and diesel matrices had on average a 10% lower accuracy compared
to air samples.
Furthermore, recoveries of the presented 17 PAH surrogates differed
not only among the three matrices, but also within each matrix. There
is an evident trend in recovery with regard to volatility of PAHs. As
expected, recovery is poorer for more volatile, low molecular weight
TABLE 3. Quantitation Assigned Value with Uncertainty Interval (95% CL) for PAHs in Ambient Air, Soil, and Diesel
Emission Control Samples
326
Ambient air Soil Diesel emission
Expanded Uncertainty = % RSD x k; k is coverage factor chosen from t distribution table at P = 0.05.
naCertified/Reference values not available in SRM.
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328 A. Wnorowski et al.
CONCLUSIONS
REFERENCES