Analysis of Semi-Volatile Compounds in

Marine Sediment By GC/MS-MS Greg Perez

Senior Environmental Analyst

City of Tacoma Environmental Services Laboratory

Center For Urban Waters

City of Tacoma Environmental Services Laboratory

Tacoma Washington

Thea Foss Waterway

The Project

• Thea Foss and Wheeler Osgood Waterways Remediation

Project

History

• 1983 - EPA identified Thea Foss and Wheeler-Osgood

waterways as part of the 12-acre Commencement Bay

Superfund site.

• 2002 – 2006 426,000 cubic yards were dredged from the

waterway, at a cost of $105 million.

History

• 2007 - Ongoing monitoring begins

• The City monitors storm drains by testing the water and

sediments regularly for possible contaminants.

• This "nonpoint" source pollution comes mostly from

stormwater runoff, soapy water, oil and fertilizers which

travel from residential areas through the City's 18,000

storm drains and 500 miles of pipes.

Sediment Quality

Objectives

• Sediment Quality Objectives (SQOs) were developed as

part of the Commencement Bay Nearshore / Tideflats

Remedial Investigation / Feasibility Study.

• The SQOs were used to identify problem chemicals,

identify sources of problem chemicals, and define

problem areas during the remedial design.

Sediment Quality

Objectives

The City and the EPA found the following chemicals

polluting the sediment in the waterways:

• Phthalates

• Polyaromatic Hydrocarbons

• Phenolics

• Pesticides

• Arochlors

• Metals

Analytes - Phenolics

• Phenol

• 2-Methylphenol

• 4-Methylphenol

• 2,4-Dimethylphenol

• Pentachlorophenol

Analytes – LPAH’s

• Naphthalene

• 2-Methylnaphthalene

• Acenaphthylene

• Acenaphthene

• Fluorene

• Phenanthrene

• Anthracene

Analytes – HPAHs

• Fluoranthene

• Pyrene

• Benzo(a)Anthracene

• Chrysene

• Benzo(a)Pyrene

• Benzo(b&k)fluoranthenes

• Indeno(1,2,3-cd)pyrene

• Dibenzo(a,h)anthracene

• Benzo(g,h,i)perylene

Analytes – Phthalates

• Dimethyl Phthalate

• Diethyl phthalate

• Di-n-Butyl phthlalate

• Butylbenzylphthalate

• Bis(2-ethylhexyl)phthalate

• Di-n-octylphthalate

Analytes – Chlorinated

Aromatics

• 1,3-Dichlorobenzene

• 1,2-Dichlorobenzene

• 1,4-Dichlorobenzene

• 1,2,4-Trichlorobenzene

• Hexachlorobenzene

Analytes – Miscellaneous

• Hexachlorobutadiene

• Benzyl Alcohol

• Benzoic Acid

• Dibenzofuran

• N-nitrosodiphenylamine

Challenges

• Reporting Limits

Analyte

SQO

ug/Kg

Reporting Limit

ug/Kg

Hexachlorobenzene 22 11

Hexachlorobutadiene 11 5.5

N-Nitrosodiphenylamine 28 14

Challenges

• Matrix

Traditional Process

• 10g sample extracted by Accelerated Solvent Extraction

(ASE)

Traditional Process

• Extensive Cleanup

• Gel Permeation Chromatography

• Copper cleaning

• Alumina

• Dilution

Traditional Process

• Analysis by GC/MS

• Multiple injections

• Most samples analyzed at least twice per analyte group.

Traditional Process

• Time Intensive

• Labor intensive

• QC Issues caused by matrix interference

• Internal Standard Failures

• Surrogate Failures

• Matrix Spike Failures

A New Approach using

GC/MS-MS

• Instrument sensitivity allows

• Smaller sample size

• Less matrix effects

• More specificity

Extraction

• Accelerated Solvent Extraction

• 2g sample

• Dichloromethane

• Concentrated to 1ml

Method

• J&W DB-5 20m X 0.18 µm X 0.18 µm

• 40° for 1 min/ 23°C/min to 260° for 0 min

• Then 10°C/min to 290°C for 4 min

• Flow 1.3ml/min

• Acquisition time 17.6 minutes

Method

• Multi Mode Injector (MMI)

• 10 µl injection (5µl X 2)

Calibrations

Data

Analyte 2g Result 10g data

Hexachlorobutadiene 0.6 0.5

N-Nitrosodiphenylamine 8 11

Hexachlorobenzene 9 0.6

Data

Analyte 2g 10g

µg/Kg dry µg/Kg dry

Fluoranthene 940 770

Pyrene 2600 1700

Butyl benzyl phthalate 490 150

bis(2-Ethylhexyl)phthalate 1000 880

Benzo(a)anthracene 650 410

QC Recoveries – 10g

2-Fluorophenol 24.0 12.4 35.3

Phenol-d5 44.0 37.5 53.5

Nitrobenzene-d5 51.0 59.1 56.9

2-Fluorobiphenyl 63.0 70.2 69.8

2,4,6-Tribromophenol 38.5 14.8 57.8

Terphenyl-d14 98.7 99.5 123

1,4-Dichlorobenzene-d4 108 109 103

Naphthalene-d8 108 109 103

Acenaphthene-d10 114 113 108

Phenanthrene-d10 113 113 106

Chrysene-d12 74.4 75.9 57.5

Perylene-d12 28.7 27.8 17.1

QC Recoveries – 2g

2-Fluorophenol 73.2 68 57.5 46.3

Phenol-d5 51.8 90.3 44.3 55.5

Nitrobenzene-d5 70.1 111 61.9 110

2-Fluorobiphenyl 50.2 64 43.9 54.8

2,4,6-Tribromophenol 131 149 83.4 118

Terphenyl-d14 123 128 111 97.6

1,4-Dichlorobenzene-d4 98.7 80.6 99.5 86.9

Naphthalene-d8 72.3 102 74.5 73.3

Acenaphthene-d10 265 139 274 96.1

Phenanthrene-d10 380 201 408 162

Chrysene-d12 103 102 105 117

Perylene-d12 59.7 76.3 59.6 93.3

Why use MS-MS?

Why use MS-MS?

Why use MS-MS?

Why use MS-MS?

Why use MS-MS?

Why use MS-MS?

Why Use MS-MS?

Why Use MS-MS?

Why Use MS-MS?

Why use MS-MS?

Some remaining issues

• MDL for Bis(2-ethylhexyl)phthalate & Di-n-butyl

phthalate did not meet the acceptance criteria. blank

levels close to spike level.

• Benzoic Acid extraction recoveries were very low and

erratic. MDL did not meet the acceptance criteria. MDL

< mean recovery.

Some remaining issues

• Additional calibration points could be added to the curve

to decrease the gap between MDL and MRL except for

Benzyl Alcohol and Di-n-octyl phthalate.

• MMI injection could use more optimization

Some remaining issues

• Wide range of reporting limits for project makes selection

of calibration points difficult.

• Have to balance sensitivity for non-detects to meet

reporting limits.

• Refine method optimization by selecting less sensitive

transition or collision energy for compounds requiring a

higher upper range.

Transitions Selection

Transitions Selection

Analyte Method RT

Precursor

Ion Product Ion Dwell Time

Collision

Energy

Relative

Intensity

Indeno[1,2,3-cd]pyrene 19.23 138.1 137.1 10 10 100%

Indeno[1,2,3-cd]pyrene 19.23 137.0 136.0 10 15 89%

Indeno[1,2,3-cd]pyrene 19.23 276.0 274.1 10 40 34%

Indeno[1,2,3-cd]pyrene 19.23 138.1 125.1 10 15 20%

Indeno[1,2,3-cd]pyrene 19.23 137.0 124.0 10 15 20%

Indeno[1,2,3-cd]pyrene 17.23 274.1 272.0 10 40 8%

Compounds at a Glance

Conclusions

The sensitivity of the MS-MS, allows us to simplify

sample prep by:

• Reducing sample size

• Minimizing the amount of extract cleanup required

• Improving extraction efficiency by increasing solvent

to sample ratio

Conclusions

• MS-MS Improves analysis by:

• Minimizing the effect of matrix in the

chromatogram

• Providing options to reduce the effect of

interfering peaks.

• Product ions add additional level of confidence in

the identification of target compounds.

Contact Information

• Greg Perez

• gperez@cityoftacoma.org

• Leonora Litzi-Davis

• ldavis@cityoftacoma.org