PAH Presentation CONFIDENTIAL AGENDA Introduction PAH list from - - PowerPoint PPT Presentation

PAH Presentation

October 2012

CONFIDENTIAL

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AGENDA

• Introduction

– PAH list from WAC 173-340-708(8)(e)(v) – Objectives

• Experimental Design
• Experimental Observations
• Results
• Summary
• Conclusions
• Next Steps

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Introduction and Background

• Original compound list of most commonly tested PAHs
• Washington Administrative Code adds 18 PAHs and c-PAHs
• All additional PAHs/c-PAHs are IARC 2B or possibly

carcinogenic

• Six of the additional PAH/c-PAH compounds have assigned

TEFs that are ten times greater than benzo(a)pyrene

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Introduction Original PAH list

Naphthalene 2-Methylnaphthalene 1-Methylnaphthalene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Chrysene Benzo(a)anthracene Benzo(b,j)fluoranthene Benzo(k)fluoranthene Benzo(e)pyrene Benzo(a)pyrene Perylene Indeno(1,2,3-cd)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene Coronene

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Washington Administrative Code

4-Nitropyrene 1,6-Dinitropyrene 1,8-Dinitropyrene 6-Nitrochrysene 2-Nitrofluorene 7,12-Dimethylbenzo[a]anthracene 3-Methylcholanthrene 5-Nitroacenaphthene 1-Nitropyrene Benzo(j)fluoranthene Dibenz[a,j]acridine Dibenz[a,h]acridine 7H-Dibenzo[c,g]carbazole Dibenzo[a,e]pyrene Dibenzo[a,h]pyrene Dibenzo[a,i]pyrene Dibenzo[a,l]pyrene 5-Methylchrysene

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Toxicity TEF = 1

• 7H-dibenzo[c,g]carbazole
• Dibenzo(a,e)pyrene
• 5-methylchrysene
• 1,8-dinitropyrene
• 3-methylcholanthrene
• Benzo(a)pyrene

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Toxicity

TEFs 10x’s Greater than Benzo(a)pyrene

TEF = 10

• Dibenzo(a,h)pyrene
• Dibenzo(a,i)pyrene
• Dibenzo(a,l)pyrene
• 1,6-dinitropyrene
• 6-nitrochrysene
• 7,12-dimethylbenzanthracene

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Objectives

• Lower detection limits for the original 16 PAHs
• Increased specificity (HRMS)
• Expand the list of PAH analytes to include 18

additional compounds

• Method validation for water, soil and tissue

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Experimental Design

• Liquid/Liquid extracted using a tumbler with separatory

funnel

• Soils extracted by Soxhlet and cleaned up with alumina
• Tissue ( deveined shrimp) extracted by Soxhlet and cleaned up

with GPC and alumina

• HRMS with isotopic dilution
• Initial calibration ranges

– Water 5 – 250 ng/L – Soil 0.5 – 25 ng/g – Tissue 0.5 – 25 ng/g

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Experimental Observations Instrument Performance

• Mass Resolution >8000 RP
• Column Selection
• J&W Scientific DB-5
• Varian Select PAH

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J&W Scientific DB-5 Column

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Varian Select PAH Column

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Experimental Observations Average Background Tissues

ng/g 5-Methylchrysene 0.21 7,12-Dimethylbenzo[a]anthracene 1.15 Benzo(b)fluoranthene 0.03 Benzo(k)fluoranthene 0.01 Benzo(j)fluoranthene 0.005 3-Methylcholanthrene 0.01 Dibenzo[a,h]acridine 0.01 Dibenzo[a,i]acridine 0.08 7H-Dibenzo[c,g]carbazole 0.02 Dibenzo[a,l]pyrene 0.01 Dibenzo[a,e]pyrene 0.02 Dibenzo[a,i]pyrene 0.03 Dibenzo[a,h]pyrene 0.03

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Results Comparison of Water Method DLs

HRMS (ng/L) LRMS (ng/L) Anthracene 0.21 2.9 1-Methylphenanthrene 0.21 4.3 Fluoranthene 0.34 9.3 Pyrene 0.30 13.3 Benzo[a]anthracene 0.40 6.4 Chrysene 0.53 6.2 Benzo[b]fluoranthene 0.61 8.0 Benzo[k]fluoranthene 0.24 5.2 Benzo[j]fluoranthene 0.35 8.0 Benzo[e]pyrene 0.19 6.2 Benzo[a]pyrene 0.16 8.3 Perylene 0.36 4.2 Indeno[1,2,3-cd]pyrene 0.27 7.5 Dibenzo[a,h]anthracene 0.23 4.1 Benzo[g,h,I]perylene 0.32 9.4 Dibenzo[a,e]pyrene 0.22 3.3 Coronene 0.34 10.2

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Comparison of Soil Method DLs

HRMS (ng/g) LRMS (ng/g) Acenaphthene 0.05 0.2 Fluorene 0.02 0.1 Phenanthrene 0.05 0.2 Anthracene 0.03 0.1 1-Methylphenanthrene 0.02 1.1 Fluoranthene 0.02 0.1 Pyrene 0.05 0.3 Benzo[a]anthracene 0.02 0.2 Chrysene 0.03 0.2 Benzo[b]fluoranthene 0.08 0.2 Benzo[k]fluoranthene 0.04 0.3 Benzo[a]pyrene 0.01 0.8 Perylene 0.02 8.3 Indeno[1,2,3-cd]pyrene 0.03 0.7 Dibenzo[a,h]anthracene 0.02 0.8 Benzo[g,h,I]perylene 0.02 0.7 Dibenzo[a,e]pyrene 0.08 2.3

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Detection Limits for Additional PAHs

Water Soil Tissue (ng/L) (ng/g) (ng/g) 5-Methylchrysene 0.59 0.03 0.13 7,12-Dimethylbenzo[a]anthracene 2.88 1.09 1.19 Benzo[b]fluoranthene 0.61 0.08 0.11 Benzo[k]fluoranthene 0.24 0.04 0.06 Benzo[j]fluoranthene 0.35 0.03 0.09 3-Methylcholanthrene 0.84 N/A 0.12 Dibenzo[a,h]acridine 0.11 0.04 0.07 Dibenzo[a,j]acridine 0.24 N/A 0.10 7H-Dibenzo[c,g]carbazole 0.26 0.02 0.05 Dibenzo[a,l]pyrene 0.31 0.05 0.08 Dibenzo[a,e]pyrene 0.22 0.08 0.04 Dibenzo[a,i]pyrene 0.33 0.02 0.04 Dibenzo[a,h]pyrene 0.18 N/A 0.05

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New Detection Limits for NitroPAHs

Water Soil Tissue (ng/L) (ng/g) (ng/g) 5-Nitroacenaphthcene 0.18 0.04 0.06 2-Nitrofluorene 0.27 0.01 0.05 4-Nitropyrene 0.22 0.05 0.10 1-Nitropyrene 0.27 0.02 0.07 6-Nitrochrysene 0.39 0.08 0.18

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LOQs for the Additional PAHs

Water(ng/L) Soil(ng/g) Tissue(ng/g) 5-Methylchrysene* 2.00 0.20 0.50 7,12Dimethylbenzo[a]anthracene* 4.00 1.28 2.34 Benzo[b]fluoranthene 2.00 0.20 0.20 Benzo[k]fluoranthene 2.00 0.20 0.20 Benzo[j]fluoranthene 2.00 0.20 0.20 3-Methylcholanthrene 2.00 TBD 0.20 Dibenzo[a,h]acridine 2.00 0.20 0.20 Dibenzo[a,j]acridine 2.00 TBD 0.20 7H-Dibenzo[c,g]carbazole 2.00 0.20 0.20 Dibenzo[a,l]pyrene 2.00 0.20 0.20 Dibenzo[a,e]pyrene 2.00 0.20 0.20 Dibenzo[a,i]pyrene 2.00 0.20 0.20 Dibenzo[a,h]pyrene 2.00 0.20 0.20

* - Background Interference TBD - To Be Determined

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Bias and Precision of Additional PAHs Water

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Methylchrysene 22 97 6 93 3 98 7,12-Dimethylbenzo[a]anthracene 12 855 13 99 4 96 Benzo[b]fluoranthene 17 125 4 86 2 110 Benzo[k]fluoranthene 8 110 4 94 3 100 Benzo[j]fluoranthene 11 109 5 104 3 97 3-Methylcholanthrene 9 152 15 140 5 105 Dibenzo[a,h]acridine 4 96 3 143 36 102 Dibenzo[a,j]acridine 9 98 3 140 45 99 7H-Dibenzo[c,g]carbazole 10 97 14 91 7 100 Dibenzo[a,l]pyrene 10 108 13 119 6 101 Dibenzo[a,e]pyrene 8 95 4 101 4 92 Dibenzo[a,i]pyrene 12 98 5 98 2 97 Dibenzo[a,h]pyrene 7 89 12 90 13 92

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Bias and Precision of Additional PAHs Soil

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Methylchrysene 12 97 7 70 5 109 7,12-Dimethylbenzo[a]anthracene 15 267 4 90 7 75 Benzo[b]fluoranthene 15 189 10 127 4 110 Benzo[k]fluoranthene 11 123 1 98 6 94 Benzo[j]fluoranthene 11 116 3 89 3 94 3-Methylcholanthrene

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88 Dibenzo[a,h]acridine 22 64 12 67 4 62 Dibenzo[a,j]acridine

• 7H-Dibenzo[c,g]carbazole

8 73 9 69 5 72 Dibenzo[a,l]pyrene 22 89 5 99 5 100 Dibenzo[a,e]pyrene 27 102 7 98 6 104 Dibenzo[a,i]pyrene 8 95 2 88 2 88 Dibenzo[a,h]pyrene

• 33

53 47 48

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Bias and Precision of Additional PAHs Tissue

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Methylchrysene 21 111 7 95 6 110 7,12-Dimethylbenzo[a]anthracene 29 732 26 151 10 77 Benzo[b]fluoranthene 13 164 12 103 13 112 Benzo[k]fluoranthene 9 116 9 78 8 103 Benzo[j]fluoranthene 14 110 8 86 8 110 3-Methylcholanthrene 27 79 6 96 4 94 Dibenzo[a,h]acridine 16 75 5 70 30 83 Dibenzo[a,j]acridine 26 66 8 77 47 78 7H-Dibenzo[c,g]carbazole 15 59 16 89 5 81 Dibenzo[a,l]pyrene 15 97 8 83 5 89 Dibenzo[a,e]pyrene 7 92 4 67 4 90 Dibenzo[a,i]pyrene 7 97 12 75 5 87 Dibenzo[a,h]pyrene 9 101 7 72 17 72

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LOQs for the Nitro PAHs

Water(ng/L) Soil(ng/g) Tissue(ng/g) 5-Nitroacenaphthcene 2.00 0.20 0.20 2-Nitrofluorene 2.00 0.20 0.20 4-Nitropyrene 2.00 0.20 0.20 1-Nitropyrene 2.00 0.20 0.20 6-Nitrochrysene 2.00 0.20 0.20

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Bias and Precision of Nitro PAHs Water

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Nitroacenaphthcene 7 98 5 97 2 99 2-Nitrofluorene 9 107 23 139 2 102 4-Nitropyrene 8 101 4 112 3 106 1-Nitropyrene 9 105 3 99 2 101 6-Nitrochrysene 9 153 6 104 1 104

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Bias and Precision of Nitro PAHs Soil

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Nitroacenaphthcene 12 133 4 93 3 90 2-Nitrofluorene 6 84 5 99 2 93 4-Nitropyrene 13 122 3 86 2 95 1-Nitropyrene 7 86 2 94 2 92 6-Nitrochrysene 24 125 3 104 2 91

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Bias and Precision of Nitro PAHs Tissue

LOQ CS3 CS5 Precision Bias Precision Bias Precision Bias %RSD % %RSD % %RSD % 5-Nitroacenaphthcene 13 83 5 82 5 86 2-Nitrofluorene 9 100 12 92 3 89 4-Nitropyrene 14 127 7 94 3 84 1-Nitropyrene 13 101 2 86 3 90 6-Nitrochrysene 22 144 7 90 2 90

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Soil Sample from HWY 401 Toronto

Naphthalene 4.23 Benzo[b]fluoranthene 22.4 2-Methylnaphthalene 3.43 Benzo[k]fluoranthene 8.20 1-Methylnaphthalene 2.25 Benzo[j]fluoranthene 7.51 2-Chloronaphthalene

• Benzo[e]pyrene

10.1 1-Chloronaphthalene

• Benzo[a]pyrene

19.2 2,6-Dimethylnaphthalene 1.86 6-Nitrochysene 0.64 Acenaphthylene 3.49 Perylene 4.45 Acenaphthene 0.92 3-Methylcholanthrene

• Fluorene

1.59 Dibenzo[a,h]acridine 0.09 Dibenzothiophene 0.68 Dibenzo[a,j]acridine 0.25 Phenanthrene 15.6 Indeno[1,2,3-cd]pyrene 12.4 Anthracene 6.59 Dibenzo[a,h]anthracene 3.04 1-Methylphenanthrene 3.60 Benzo[g,h,I]perylene 22.5 Fluoranthene 32.4 7H-Dibenzo[c,g]carbazole 0.21 Pyrene 36.0 Dibenzo[a,l]pyrene 6.23 Benzo[a]anthracene 16.2 Dibenzo[a,e]pyrene 4.28 Chrysene 30.3 Coronene 33.2 5-Methylchrysene 3.50 Dibenzo[a,i]pyrene

• 7,12-Dimethylbenzo[a]anthracene

4.55 Dibenzo[a,h]pyrene

• values in ng/g

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Conclusions

• Detection Limits for all 3 matrices were 4 to 50

times lower than LRMS.

• Recoveries and Linearity of the 18 new compounds

met EPA1625 criteria.

• Background levels for Naphthalene and 7,12-

Dimethylbenzo[a]anthracene were significantly higher than expected.

• Nitro-PAHs recoveries ranged from 60 to 130%

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Conclusions cont’d.

Next Steps

• Further Experimentation including Derivitization for

the Di-Nitro-PAH compounds.

• Deuterium Labelled Isotopes for Dibenzoacridines

and 7H-Dibenzo[c,g]carbazole as they become available.

• Continuous Improvement of sample preparation

techniques to eliminate background levels

Questions? Thank You