Volatile Organic Compound Determinations Using Surrogate-Based Correction
for Method and Matrix Effects

Table 1. Experimental Relative
Volatility Values (a)

Compound Normalized ^a Derived ^b

benzene 0.60 ± 0.10

toluene 0.75 ± 0.01

chlorobenzene 0.78 ± 0.03

1,3-and 1,4-dichlorobenzene 0.78 ± 0.05

2-and 4-chlorotoluene 0.79 ± 0.03

styrene 0.80 ± 0.03

bromobenzene 0.81 ± 0.05

1,2,4-trimethylbenzene 0.82 ± 0.62

isopropyl benzene 0.84 ± 0.03

ortho-xylene 0.84 ± 0.03

acrolein 0.85 ± 0.16

1,2-dichlorobenzene 0.86 ± 0.05

tert-butylbenzene 0.91 ± 0.08

n-propyl benzene 0.92 ± 0.08

1,2,4-trichlorobenzene 1.10 ± 0.20

1,2,3-trichlorobenzene 1.30 ± 0.20

naphthalene 1.30 ± 0.10

acrylonitrile 1.51 ± 0.12

ethyl methacrylate 1.70 ± 0.40 1.55 ± 0.07

methacrylonitrile 1.67 ± 0.12

2-pentanone 2.10 ± 0.50 2.63 ± 0.05

4-methyl-2-pentanone 2.20 ± 0.50

acetonitrile 2.64 ± 0.08

acetone 3.26 ± 0.23

isobutyl alcohol 7.32 ± 0.24

pyridine 7.80 ± 3.10 8.54 ± 0.13

2-picoline 8.40 ± 3.60

n-butanol 10.10 ± 0.33

n-propanol 11.46 ± 0.44

1,4-dioxane 12.51 ± 0.55

^a Values (± one standard deviation) were generated by normalizing and averaging data from six vacuum distillation analyses.

^b Using 4-methyl-2-pentanone and 2-picoline as the two reference points, the derived 's were experimentally found. Derived 's (± one standard deviation) were calculated using determinations from ten vacuum distillations.

Table 2. Comparisons of Relative Volatility Values (a) presented in Table 1 to Literature References for Partition Coefficients (K)
	Average ± Standard Deviation
Analyte	a	K
benzene	0.60 ± 0.10	4.0 ± 1.0^7,8
toluene	0.75 ± 0.01	3.6 ± 0.2^7,8
ortho-xylene	0.84 ± 0.03	5.11⁹
isopropyl benzene	0.84 ± 0.03	2.25⁹
acrolein	0.85 ± 0.16	180.¹⁰
acetonitrile	2.64 ± 0.08	1200.¹⁰
acetone	3.26 ± 0.23	580. ± 45.⁷
isobutyl alcohol	7.32 ± 0.24	2500.¹⁰
n-propanol	11.46 ± 0.44	4090. ± 390.⁷
1,4-dioxane	12.51 ± 0.55	5750. ± 450.⁷

Table 3. Condenser Trapping Efficiencies
Compound	Boiling Point¹¹(°C)	Efficiency^a (%)
benzene	80	4.3 ± 1.8
2-pentanone	102	28.9 ± 14.6
toluene	111	4.8 ± 2.1
pyridine	115	82.5 ± 24.0
4-methyl-2-pentanone	116	20.7 ± 9.8
ethyl methacrylate	119	9.9 ± 6.2
2-picoline	129	84.5 ± 23.8
chlorobenzene	132	5.8 ± 2.1
ortho-xylene	144	6.4 ± 2.4
styrene	145	7.0 ± 2.7
isopropyl benzene	153	7.0 ± 2.9
bromobenzene	156	8.8 ± 3.4
n-propyl benzene	159	7.4 ± 4.1
2-and 4-chlorotoluene	162	9.6 ± 3.1
tert-butylbenzene	169	10.5 ± 4.2
1,2,4-trimethylbenzene	169	11.3 ± 4.4
1,3-and 1,4-dichloromethane	173	15.9 ± 5.5
1,2-dichlorobenzene	179	22.2 ± 6.8
1,2,4-trichlorobenzene	213	71.5 ± 7.5
naphthalene	218	76.4 ± 6.6
1,2,3-trichlorobenzene	219	83.3 ± 4.4

^a Calculated as the percent of compound vacuum distilled from the sample chamber and trapped on the condenser column. Six vacuum distillations of 5 mL water samples were used to generate the experimental data.

Table 4. Accuracy of Surrogate-Based Corrections^a
	Surrogate-Pair^c		Multi-Surrogate^d
Analyte^b	Water	Soil	Water	Soil
	ratio (%)	ratio (%)	ratio (%)	ratio (%)
benzene (a-surrogate)^e
toluene	95.4 ± 3.1	97.1 ± 2.3	92.6 ± 1.1	98.8 ± 4.2
1,3-and 1,4-dichlorobenzene	90.9 ± 1.8	92.8 ± 1.9	90.1 ± 1.9	90.9 ± 1.2
chlorobenzene (a-surrogate)
2-and 4-chlorotoluenes	95.6 ± 3.3	101.1 ± 2.9	93.1 ± 1.3	103.0 ± 3.3
styrene	101.9 ± 3.2	103.1 ± 1.9	99.8 ± 1.2	106.0 ± 2.8
bromobenzene	96.8 ± 2.3	102.6 ± 1.7	95.0 ± 0.3	105.5 ± 2.7
1,2,4-trimethylbenzene	94.2 ± 2.4	96.5 ± 2.9	94.8 ± 0.8	95.4 ± 1.0
isopropyl benzene	93.4 ± 2.7	102.0 ± 4.0	94.3 ± 0.8	104.4 ± 4.2
ortho-xylene (a-surrogate)
1,2-dichlorobenzene (b-surrogate)^f
tert-butylbenzene	95.1 ± 3.0	102.9 ± 2.9	98.0 ± 1.6	100.7 ± 1.5
n-propylbenzene	97.7 ± 4.7	99.1 ± 12.3	96.3 ± 0.6	100.8 ± 14.2
1,2,4-trichlorobenzene	113.7 ± 8.1	99.3 ± 5.2	113.5 ± 5.8	91.6 ± 14.9
1,2,3-trichlorobenzene	165.8 ± 29.9	147.2 ± 20.5	162.2 ± 14.2	134.6 ± 32.5
naphthalene (b-surrogate)
ethyl methacrylate	109.2 ± 2.4	101.3 ± 8.9	110.9 ± 0.2	101.2 ± 9.0
2-pentanone	84.2 ± 1.8	94.6 ± 6.5	85.6 ± 0.9	94.2 ± 7.4
4-methyl-2-pentanone (a-surrogate)
pyridine	109.2 ± 5.4	103.8 ± 5.7	102.7 ± 4.6	132.6 ± 14.9
2-picoline (a-surrogate)

^a Ratio (as a percent ± one standard deviation) of predicted recovery to the experimentally obtained analyte recovery using test samples. ^b Analyte list sorted by increasing .^c Percent comparison data generated using bracketing -surrogates and the two -surrogates. Averages reflect the same-day vacuum distillations of four water samples and three soil samples.^d Percent comparison data generated using all -surrogates and the two -surrogates. The same samples used to generate the surrogate-pair were used to generate multi-surrogate data.^e Compound selected to predict only effects.^f Compound selected to predict condenser column trapping efficiencies related to after compensating for effects.

National Exposure Research Laboratory
Author: Mike Hiatt / Email: Hiatt.Mike@epa.gov
Send questions or comments to the Information Desk
ESD Info Desk (contractor operated)
(Library-lv@epa.gov)

Table 1. Experimental Relative Volatility Values (a)
Compound	Normalized ^a	Derived ^b
benzene	0.60 ± 0.10
toluene	0.75 ± 0.01
chlorobenzene	0.78 ± 0.03
1,3-and 1,4-dichlorobenzene	0.78 ± 0.05
2-and 4-chlorotoluene	0.79 ± 0.03
styrene	0.80 ± 0.03
bromobenzene	0.81 ± 0.05
1,2,4-trimethylbenzene	0.82 ± 0.62
isopropyl benzene	0.84 ± 0.03
ortho-xylene	0.84 ± 0.03
acrolein		0.85 ± 0.16
1,2-dichlorobenzene	0.86 ± 0.05
tert-butylbenzene	0.91 ± 0.08
n-propyl benzene	0.92 ± 0.08
1,2,4-trichlorobenzene	1.10 ± 0.20
1,2,3-trichlorobenzene	1.30 ± 0.20
naphthalene	1.30 ± 0.10
acrylonitrile		1.51 ± 0.12
ethyl methacrylate	1.70 ± 0.40	1.55 ± 0.07
methacrylonitrile		1.67 ± 0.12
2-pentanone	2.10 ± 0.50	2.63 ± 0.05
4-methyl-2-pentanone	2.20 ± 0.50
acetonitrile		2.64 ± 0.08
acetone		3.26 ± 0.23
isobutyl alcohol		7.32 ± 0.24
pyridine	7.80 ± 3.10	8.54 ± 0.13
2-picoline	8.40 ± 3.60
n-butanol		10.10 ± 0.33
n-propanol		11.46 ± 0.44
1,4-dioxane		12.51 ± 0.55

Volatile Organic Compound Determinations Using Surrogate-Based Correction for Method and Matrix Effects

Local Navigation

Volatile Organic Compound Determinations Using Surrogate-Based Correction
for Method and Matrix Effects