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Aerostat Sampling of PCDD/PCDF Emissions from the 

Gulf Oil Spill In Situ Burns 

- Supporting information - 

Johanna Aurell1 and Brian K. Gullett2,*

U.S. Environmental Protection Agency, Office of Research and Development, National Risk 

Management Research Laboratory, Research Triangle Park, NC 27711, USA 

*Corresponding author e-mail: gullett.brian@epa.gov: phone (919) 541-1534; fax (919) 541-0554 

1National Research Council Post Doctoral Fellow to the U.S. Environmental Protection Agency 

2U.S. Environmental Protection Agency, Office of Research and Development, National Risk 

Management Research Laboratory 

The targeted sample size (carbon) in the initial quality assurance plan was twice as much as was 

collected. Accordingly, the PUF/XAD-2/PUF had been spiked with pre-sampling standards at higher 

concentrations than would be warranted by the actual sample obtained. The HRGC/HRMS calibration 

solutions for the 5-point calibration curve were tailored to the actual concentrations of the standards in 

the final extract volume of 20 μL. The concentrations of the calibration solutions are given in Table S1. The concentration of the surrogate (pre-sampling), internal (pre-extraction), and recovery (pre-
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injection) standards in the samples are given in Table S-2. This adjustment of the concentrations in the 

initial calibration resulted in the pre-sampling surrogates being up to ten times more concentrated than 

the pre-extraction spikes (Table S-2). The high ratio of pre-sampling to pre-extraction surrogate caused 

overlapping peaks for HxCDD/F on the DB-Dioxin column (the hexa-chlorinated pre-extractions spikes 

were a small peak on the trailing edge of the pre-sampling hexa-chlorinated spikes). The same 

phenomenon was observed on the DB-5 column that was tested to obtain better chromatographic 

separation of 13C12-1,2,3,4,7,8-HxCDD/F from 13C12-1,2,3,6,7,8 HxCDD/F . The hexa-chlorinated preextraction spikes were integrated tangentially instead of to baseline (both for the calibration solutions 

and samples). Due to the overlapping HxCDD/F peaks, elevated recoveries of hexachlorinated internal 

standards and consequent lower recoveries of hexachlorinated pre-sampling spikes were observed. 

Table S-1. Composition and Concentrations of the Calibration Solutions. 

Calibrati

on 

solution 

Native 

PCDDs/Fs 

Pre-sampling surrogates Pre-extraction surrogates Pre-injection surrogates 

 

TCDD/F to 

OCDD/F 

37Cl14-

TCDD 

13C12PeCDD/F to 

HpCDD/F 

13C12

TCDD/F 

13C12PeCDD/F to 

HpCDD/F 

13C12

OCDD 13C12 TCDD to HxCDD 

ICAL1 1 25 50 25 50 100 50 

ICAL2 2.5 100 200 25 50 100 50 

ICAL3 5 150 300 25 50 100 50 

ICAL4 25 200 400 25 50 100 50 

ICAL5 50 250 500 25 50 100 50 

 
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Table S-2. Concentrations and Recovery Criteria for the Surrogate (Pre-Sampling) and Internal (PreExtraction) Standards for the Plume Sample, Background Sample, Trip Blank, and Field Blank. 

Spiking 

Solution 

Analytes Std. Concen. in 

sample (pg/μL) 

Recovery (%) 

 Plume 

Sample 

Backgroun

d Sample 

Trip Blank Field Blank 

Surrogate 

standards 

(Presampling) 

37Cl14-2,3,7,8-TCDD 

13C12-2,3,4,7,8-PeCDF 

13C12-1,2,3,4,7,8-HxCDF 

13C12-1,2,3,4,7,8-HxCDD 

13C12-1,2,3,4,7,8,9-HpCDF 

250 

500 

500 

500 

500 

90 

87 

64 

84 

89 

85 

80. 

51 

77 

81 

86 

84 

53 

78 

82 

82 

81 

39 

75 

74 

Internal 

standards 

(Preextraction) 

13C12-2,3,7,8 TCDF 

13C12-2,3,7,8 TCDD 

13C12-1,2,3,7,8 PeCDF 

13C12-1,2,3,7,8 PeCDD 

13C12-1,2,3,6,7,8 HxCDF 

13C12-1,2,3,6,7,8 HxCDD 

13C12-1,2,3,4,6,7,8 HpCDF 

13C12-1,2,3,4,6,7,8 HpCDD 

13C12-1,2,3,4,6,7,8,9 OCDD 

25 

25 

50 

50 

50 

50 

50 

50 

100 

95 

89 

91 

44 

120 

88 

75 

83 

73 

99. 

92. 

94 

101 

141 

94 

76 

88 

76 

90 

92 

88 

96 

133 

94 

75 

82 

76 

92 

93 

84 

98 

171 

96 

72 

86 

76 

Recovery 

Standards 

13C12-1,2,3,4-TCDD 

13C12-1,2,3,7,8,9-HxCDD 

50 

50 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

Bold values fall outside the recovery criteria of U.S. EPA Method 23. 

All four samples met the recovery acceptance criterion recommended by U.S. EPA Method 23 (1) for 

surrogate standards (between 70% and 130%) except for the HxCDF standard. The internal standards 

all meet the recovery criteria for U.S. EPA Method 23 (between 40% and 130%) except for the HxCDF 

standard on the non-plume samples. 
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Table S-3 presents all of the analytical results for the four samples. The congener mass relationships, 

or patterns, have typically been used as source identifiers. The pattern in the last column of the table for 

the plume sample is similar to those found in this laboratory for a variety of biomass sources. 

The plume sample data suffer limitations of four non-detects for the 17 toxic congeners that comprise 

the PCDD/PCDF toxic equivalency (TEQ) measure. The range of the signal to noise ratios observed for 

the 13 detected congeners was 6/1 to 29/1, meeting the S/N detection criteria of 2.5/1 but was below the 

lowest point of the calibration curve (S/N of 31/1 to 115/1). This is an understandable outcome, as it is 

not possible a priori to know how much sample mass is sufficient to provide a quantifiable value for 

each congener and to avoid non-detect congeners. 

Table S-3. PCDD/PCDF Analytical Results for All Four Samples. 

 Trip blank Field blank Background 

Sample 

Plume Sample 

 pg/train pg/train pg/train pg/train 

2,3,7,8-TCDD ND (0.46) ND (0.46) ND (0.56) ND (0.50) 

1,2,3,7,8-PeCDD ND (0.74) ND (0.62) ND (0.80) ND (1.6) 

1,2,3,4,7,8-HxCDD ND (0.70) ND (0.64) ND (0.76) 1.8 (0.64) 

1,2,3,6,7,8-HxCDD ND (0.70) ND (0.64) ND (0.76) 1.2 (0.66) 

1,2,3,7,8,9-HxCDD ND (0.74) ND (0.68) ND (0.80) 2.4 (0.68) 

1,2,3,4,6,7,8-HpCDD ND (0.94) ND (0.86) ND (1.0) 4.0 (0.90) 

1,2,3,4,6,7,8,9-OCDD ND (2.0) ND (1.9) ND (2.2) 13 (1.6) 

 

2,3,7,8-TCDF ND (0.76) ND (0.78) ND (0.80) 4.8 (0.68) 

1,2,3,7,8-PeCDF ND (0.70) ND (0.78) ND (0.72) 3.0 (0.92) 

2,3,4,7,8-PeCDF ND (0.62) ND (0.70) ND (0.64) 3.6 (0.82) 

1,2,3,4,7,8-HxCDF 1.6 (0.32) 1.4 (0.24) 1.8 (0.32) 3.4 (0.36) 

1,2,3,6,7,8-HxCDF ND (0.30) ND (0.22) ND (0.30) 1.2 (0.34) 
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1,2,3,7,8,9-HxCDF ND (0.40) ND (0.30) ND (0.40) ND (0.44) 

2,3,4,6,7,8-HxCDF ND (0.36) ND (0.28) ND (0.36) 1.0 (0.40) 

1,2,3,4,6,7,8-HpCDF ND 0.74) ND (0.72) ND (0.78) 3.4 (0.66) 

1,2,3,4,7,8,9-HpCDF ND (0.96) ND (0.94) ND (1.0) 2.0 (0.86) 

1,2,3,4,6,7,8,9-OCDF ND (3.8) ND (3.4) ND (3.5) ND (2.4) 

 

Limit of detection in parentheses. 

REFERENCES 

(1) U.S. EPA. Method 23. Determination of Polychlorinated Dibenzo-p-dioxins and Polychlorinated 

Dibenzofurans from Municipal Waste Combustors. United States Environmental Protection 

Agency; http://www.epa.gov/ttn/emc/promgate/m-23.pdf (accessed, July 29, 2010).