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Gas Chromatography/Mass

Spectrometry Analysis
(GC/MS)
Fundamentals and Special Topics

Zbigniew Bernie Wilk, Ph.D.


Russell Confer, M.S.
Office of Quality Assurance
New Jersey Department of Environmental Protection

Gas Chromatography/Mass Spectrometry


GC/MS Overview

50 min.

the nuts and bolts of how GC/MS works

Break

GC/MS Analysis Special Topics

10 min.

50 min.

Chromatograms & Peak Integration


TICs & MS Libraries, Interferences

Break

Dioxins and PCB Analyses


GC/High Resolution Mass Spectrometry

10 min.

50 min.

Gas Chromatography/Mass Spectrometry

Introduction

Organic Analysis Overview


History
The wide world of Mass Spectrometry
How it all works
Tuning/Calibration

Break

Gas Chromatography/Mass Spectrometry (GC/MS)

From Chromatograms to final report


Mass Spectrometry Libraries and Compound Identification (TICs)
Proper and Improper Peak Integrations - Manipulating Results
Dealing with Interferences

Break

- Dioxin and PCB Analyses Using GC/High Resolution Mass Spectrometry

Review of EPA Methods


Why High Resolution Mass Spectrometry
High Resolution Mass Spectrometry Fundamentals
Dioxin and PCB Analysis Methods Highlights
Comparing PCB Methods 1668A to 8082 - Aroclors or Congeners.

Gas Chromatography/Mass Spectrometry


(GC/MS)
Gas
Chromatography

Separates mixture of pollutants


so each can be identified individually

Mass
Spectrometry

Gas Chromatography Mass Spectrometry

A Chemical Analysis Technique combining


two instruments to provide for powerful
separation and identification capabilities

Identifies (detects) pollutant molecules


based on their molecular weight or mass

Gas Chromatography/Mass Spectrometry


The mass spectrometry results at a
resolving power of 10,000 indicate that
isobaric interferences exist that make the
chlorine ion intensities inconsistent with
their natural isotopic abundance at the
molecular ion.

WHAT THE MASS SPECTROMETRIST SAYS

The mass spectrometry results blah,


blah, blah, blah, blah, blah, blah, blah,
blah, blah, blah, blah that make the
chlorine blah, blah, blah, blah, blah,
blah, blah, blah, blah, blah, blah, blah,
blah, blah, blah, blah.

WHAT THE AVERAGE PERSON HEARS

Historical Timeline of GC/MS


1952
Martin and Synge
Nobel Prize
Chromatography

1900

1906
Sir J.J. Thompson
Nobel Prize for
discovery of electron

1979
USEPA Publishes
Wastewater Methods
Under Clean Water Act

EPA Born

1942
First Commercial
Mass Spectrometer

1971
USEPA Purchases 6
Finnigan GC/Mass Specs

2000
GC/MS
LC/MS
ICP/MS

Dates of Historical Note

1906 - Sir J.J. Thomson (Cambridge) gets Nobel Prize for the discovery of the
electron.
1930 - Aston uses MS to study isotopes
1942 - first commercial magnetic mass spectometer
1952 - Martin and Synge win Nobel Prize for Chromatography
1959 - Gas Chromatography interfaced to Mass Spectrometer
1968 - Finnigan Corp. delivers first Quadrupole GC/MS
1969 - Finnigan Corp. delivers first Quadrupole GC/MS with computer
1970 - USEPA is born
1971 - USEPA purchases 6 Finnigan GC/MS systems
1972 - Federal Water Pollution Control Act (CWA) is passed
1976 - Hewlett Packard introduces fully computerized GC/MS system
1976 - RCRA Enacted
1979 - USEPA publishes wastewater methods under CWA
1983 - Development of LC/MS interface by Vestal et. al.

Various Forms of Mass Spectrometry

A whole range of possibilities/permutations

Sample Introduction

Ionization

Mass Separator
Quadrupole

Detector

Gas Chromatography

EI (electron impact)

channeltron

Liquid Chromatography
Electrospray

CI (chemical ionization)
Ion Trap
discrete dynode
NCI negative CI
Time-of-Flight(TOF)
photo-optical
FAB(fast atom bombardment) Sector(BE, EB, EBE)
image current
n
API (atmospheric pressure)
FTMS (MS )
LIMS (laser ionization)
Ion Mobility
FI/FD (field desorption)
Triple Stage Quadrupoles (MS/MS)
MALDI (matrix assisted laser Hybrid Combinations (Q-TOF, BEQ)
desorption ionization)
Particle Beam (PB/LC/MS Interface)
Thermospray (TSP/LC/MS Interface)
Atmospheric Pressure Ionization (API/LC/MS)
ETC.

GC/MS
Great For the Analysis of Organics
Gas Chromatography Analysis Requirement
Organics to be analyzed must be VOLATILE or at least
Partially VOLATILE .
First 30 years of EPA have concentrated on relatively volatile organics
Next 30 years?

Polar and Non-Volatiles?

LC/MS?

Broad Range of Organic Compounds


(How many are there?)

Chemical Abstracts Service

16, 000, 000

(based on CAS #s as of 1998)

NIST Organic MS Database

approx. 150,000

Federal Pollutant Database

approx 700

e.g.
Most Organic Analyses:
approx. 10 to 80 compounds in one analysis

Classification of Organic Compounds


Boiling Point

Polarity *

Technique

Ionic

high

high

HPLC, HPLC/MS

NonVolatiles

high

high

HPLC, HPLC/MS

SemiVolatiles

medium

low-medium

GC; GC/MS; HPLC

Volatiles

low

low-medium

GC; GC/MS

Increasing polarity = Increasing solubility in water

Survey of GC/MS Methods


(by Program)
SDWA
EPA 500 series e.g. 524.2, 525

Clean Water Act


EPA 600 and 1600 series
1625, 1666

e.g. 624, 625, 1624,

RCRA (Solid and Hazardous Waste)


EPA 8000 series e.g. 8260, 8270

CERCLA (Superfund)
OLMO contracts

Clean Air Act


TO (Toxic Organics) series
TO-17
(Some ASTM and Standard Methods are also EPA approved)

e.g. TO-14, TO-15,

Principles of Gas Chromatography Mass Spectrometry


Advantages
- high sensitivity
excellent detection limits. Typically low ppb to high ppt

- high selectivity
identification is based on two parameters not one
(retention time and mass spectrum must match standard)
selects analyte of interest with very high confidence

- Speed
typical analysis takes from 1/2 hour to approx. 1 hour
analysis can contain upwards of 80 and more pollutants

Disadvantages
- higher capital cost (approx. $ >85 K vs. $15 K for GC)
- higher maintenance (time, expertise and money)
- for optimum results requires analyst knowledgeable in both
chromatography and mass spectrometry

The Analytical Process - GC/MS is Last Step


Data Received by
DEP

Sample Site
Contaminated Site

5.6 ppb

Monitoring Well

Benzene

Permittee Effluent
Drinking Water Facility

Laboratory Side

Sample Analysis
Sample
Preparation

Sample
Clean-Up
(optional)

Determinative Step
Gas Chromatography (GC)
Gas Chromatography/Mass Spectrometry
(GC/MS)
High Pressure Liquid Chromatography (HPLC)

The Analytical Process


(It all starts with Sample Preparation)
Sample Analysis
Determinitive Step

Sample
Sample
Preparation Clean-Up
(optional)

Gas Chromatography (GC)


Gas Chromatography/Mass Spectrometry
(GC/MS)
High Pressure Liquid Chromatography (HPLC)

Purge and Trap


Liquid-Liquid Extraction
Sonication
Solid Phase Extraction (SPE)
Soxhlet Extraction
(not an exhaustive listing)

Sample Preparation Techniques


Preparation - v.v. important first step
1)

2)

used to separate organic contaminants from


their environmental matrix (e.g. groundwater
or soil)
used to concentrate the contaminants

Typical Preparation Techniques include:


Purge and Trap, LLE, Soxhlet, LSE (Sep Paks,
Cartridges)

Purge and Trap


(Aqueous and Soils / Volatiles Preparation)

Courtesy of Environmental Conservation Laboratories, Inc.

Liquid/Liquid Extraction
(Separatory Funnel)
(Aqueous Samples / Semivolatiles Analysis)

Courtesy of Environmental Conservation Laboratories, Inc.

Sonication
(Soils, Solids / Semivolatiles)

Courtesy of Environmental Conservation Laboratories, Inc.

Solid Phase Extraction


(Aqueous / Semivolatiles)

Sample
Cartridge

Courtesy of Stanford Laboratory

Soxhlet Extraction
(Soils, Solids / Semivolatiles)

Courtesy of Environmental Conservation Laboratories, Inc.

Sample Clean-Up Techniques


Clean-Ups - used if interferences are a problem
stand alone methods are available
also procedures written into some methods
these are often optional and choices often rest with analyst
and is dependent on the sample

Examples of typical clean-up procedures include:


Alumina, Silica, Flourisil, Gel Permeation
Chromatography, Acid Wash etc.

Sample Clean-Up Techniques from SW-846


(stand alone methods strictly for cleanups)

Analytes of Interest

Methods

Aniline & aniline derivatives


Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Haloethers
Chlorinated hydrocarbons
Organophosphorus pesticides
Petroleum waste
All base, neutral, and acid
priority pollutants

3620
3630, 3640, 8041a
3610, 3620, 3640
3610, 3620, 3640
3610, 3620, 3630, 3660, 3665
3620, 3640
3611, 3630, 3640
3620, 3640
3620, 3640
3620
3611, 3650
3640

Gas Chromatography Mass Spectrometry


(Operational Description)

Introduction System - Gas Chromatography


Ionization
Mass Separation
Mass Spectrometer
Mass Detection
Data System

Gas
Chromatography

Ionization
Source

Mass
Analyzer

Particle
Detector

Vacuum System - approx. 10-6 torr

Dedicated
Data System

Gas Chromatography
Powerful Analytical Chemistry technique
used to separate and identify organic
compounds from mixtures.
One requirement:
organics must be volatile or semivolatile
any very polar, non volatile or ionic compounds in sample will
not be detected

Gas Chromatography

Columns
Packed

Capillary

Cross section

THE CHROMATOGRAPHIC PROCESS - PARTITIONING


(gas or liquid)

MOBILE PHASE

Sample
out

Sample
in

STATIONARY PHASE
(solid or heavy liquid coated onto a solid or support system)

Parameters Affecting Separation


Temperature Control
Isothermal
Gradient

240
200
Temp (deg C)

Column Type (Phase)


Polar (DB-1701
NonPolar (DB-1)
Phase Thickness
Column Dimensions

160
120
80
40
0
0

10

20

30
Time (min)

40

50

60

Phases

Chromatograms - 551.1

Same Organic Mixture Different Capillary Columns

Instrumentation - Detectors
Destructive
Mass Spectral (CI/EI) [625]
Flame Ionization (FID) [604]
Nitrogen-Phosphorus (NPD) [8141A]
Flame Photometric (FPD) [8141A]
Electrolytic Conductivity (Hall/ELCD) [502.2]
Non-Destructive
Thermal Conductivity (TCD)
Electron Capture (ECD) [551.1]
Photo Ionization (PID) [502.2]

How Mass Spectrometry Detectors Works


All Organic Molecules are made up of combinations of atoms
containing Carbon and Hydrogen
In addition to Carbon and Hydrogen, other elements are frequently a part of
a molecule to provide a variety of chemical and physical properties (e.g.
Oxygen, Nitrogen, Chlorine, Fluorine, etc.)
Molecular weights can be calculated knowing the elemental composition of a
molecule.

Mass Spectrometry analyzes (identifies) organic


molecules according to their molecular and fragment
weights.

How Mass Spectrometry (Mass Analysis) Works


(Use Table to Calculate Molecular Weights)
Element

Symbol

Nomi
nal
Mass

Exact
Mass

Abundanc
e

Hydrogen

H
D or 2H

1
2

1.00783
2.01410

99.99
0.01

C
C

12
13

12.0000
13.0034

98.91
1.09

N
N

14
15

14.0031
15.0001

99.6
0.37

O
O
18
O

16
17
18

15.9949
16.9991
17.9992

99.76
0.037
0.20

19

18.9984

Si
Si
30
Si

28
29
30

27.9769
28.9765
29.9738

92.28
4.70
3.02

31

30.9738

100

S
S
34
S

32
33
34

31.9721
32.9715
33.9679

95.02
0.74
4.22

Cl
Cl

35
37

34.9689
36.9659

75.77
24.23

Br
Br

79
81

78.9183
80.9163

50.5
49.5

Carbon
Nitrogen

12
13

14
15

16

Oxygen

Fluorine

17

28

Silicon
Phosphorus

29

32

Sulphur

Chlorine
Bromine

33

35
37

79
81

100

Isotopes

Calculating Molecular Weight (Mass)


Element
Carbon(C)
Hydrogen(H)
Chlorine(Cl)
Fluorine (F)
Oxygen(O)
Nitrogen(N)

atomic mass (amu)


12
1
35
19
16
14

H
H

H C C C H

H C

C
N

C
C

H
H

Benzene
(C6H6)
6 x 12 = 72
6x1 = 6
MW = 78 amu
amu - atomic mass units

Pyridine
(C5H5N)
5 x 12 = 60
5x1 = 5
1 x 15 = 15
MW = 79 amu

Gas Chromatography Mass Spectrometry


(Operational Description)

Introduction System - Gas Chromatography


Ionization
Mass Separation
Mass Spectrometer
Mass Detection
Data System

Gas
Chromatography

Ionization
Source

Mass
Analyzer

Particle
Detector

Vacuum System - approx. 10-6 torr

Dedicated
Data System

The Ionization Process


(Electron Impact)
Neutral molecules are converted into Ions (charged particles)

e +

Neutral Molecule

+.
Molecular
Ion

+ 2e

(70 Electron Volts)

Fragment Ion 1

Fragment Ion 2, etc.

H
H

e +
*

H
C

H C C C H

H C C C H

Mass Analysis can only work for charged species - not for neutrals.

+ 2e

GC/MS - Mass Analysis


Wavelength Separation

Continuous Light

Mass Separation
(quadrupole)

m
4V
z = qr22
Ions

Principles of Gas Chromatography/Mass Spectrometry


(NIST Library Mass Spectra for Benzene)

Abundance (Signal)

m/z 78

Benzene
H

H C C C H
H
78 amu

mass/charge (m/z) ------>

Principles of Gas Chromatography/Mass Spectrometry

Abundance (Signal)

(NIST Library Mass Spectra for Pyridine)

H
H

Pyridine
H C

m/z 79

C
C

H
H

79 amu

mass/charge (m/z) ------>

One More Example for o-Xylene


(Fragment Ions contain Useful Information)

Element
Carbon(C)
Hydrogen(H)
Chlorine(Cl)
Fluorine (F)
Oxygen(O)
Nitrogen(N)

mass
12
1
35
19
16
14

C
C

Xylene
(C8H10)

8 x 12 = 96
10 x 1 = 10
MW = 106

H
C
H

Molecular Ions can break down into smaller fragments

H
H

C
C

H
H

C
H

m/z 106

H
H

.
C

C
H

m/z 91

H
H

C
H

C
C

C
C
H

m/z 77

Principles of Gas Chromatography/Mass Spectrometry


(NIST Library Mass Spectra for Xylene)
mass
12
1
35
19
16
14

C
C

H
H
H

C
H

Abundance (Signal)

Element
Carbon(C)
Hydrogen(H)
Chlorine(Cl)
Fluorine (F)
Oxygen(O)
Nitrogen(N)

mass/charge (m/z) ------>

o-Xylene
(C8H10)
8 x 12 = 96
10 x 1 = 10
MW = 106

What Does GC/MS Data Look Like?

Abundance (Signal)

GC/MS Chromatogram of a 4 Component Mixture

Retention Time ------>

What Does GC/MS Data Look Like?

Abundance (Signal)

GC/MS Chromatogram of a 4 Component Mixture

Retention Time ------>

What Does GC/MS Data Look Like?


GC/MS Chromatogram From EPA Method 524.2 Analysis

Abundance (Signal)

Courtesy of the NJDHSS Laboratory

Retention Time ------>

What Does GC/MS Data Look Like?


Reviewing of Mass Spectra

6.99 min.

Abundance (Signal)

Retention Time ------>


m/z 78

mass/charge ------>

What Does GC/MS Data Look Like?


Reviewing of Mass Spectra

6.77 min.

Abundance (Signal)

Retention Time ------>


m/z 78

mass/charge ------>

1,1-dichloropropene/carbon tetrachloride

Difficult Mass Spectra


usually

Mass Spectrometry does not always provide an easily


interpretable compound identification: e.g. MTBE
use of mass spectral libraries for ID determination
use of manual interpretation techniques
use of alternate MS and other techniques

100

73

MTBE MW= 88

50
15
0

41

29
27

39
31

57
45

10
20
30
40
( m a in lib ) P ro p a n e , 2 - m e t h o x y - 2 - m e t h y l-

55
50

79
60

70

80

90

100

Mass Spectral Interpretation Procedures


GC/MS Interpretation Procedures
Identify Molecular Ion if present
Evaluate any Isotopic Observations
Use Isotopes to calculate probable carbon #s for Molecule and/or
fragments
Review all losses observed to determine substructures
Review major fragments
Hypothesize a molecular structure consistent with above observations

Must Confirm Hypothesis with additional data.

Typically chemical ionization MS


High resolution mass spectrometry
Infra Red Spectroscopy
Nuclear Magnetic Resonance Spectrometry
Obtaining a pure standard and confirming mass spectra with unknown

GC/MS Summary
Powerful analytical tool combining the separation capability of Gas
Chromatography and the identification capability of Mass Spectrometry.
Provides for a higher level of confidence in the identification of organics
(Both retention time AND the mass spectrum are used).
Capable of analyzing upwards of 80 pollutants in one analysis.

Typical Detection Limits (Aqueous) are in low ppb and high ppt
range.

Appropriate calibrations and controls must be performed before any


samples can be analyzed.

GC/MS Analysis
(Special Topics)
From Raw Data Chromatograms to final report
Proper and Improper Peak Integrations Data Processing
Dealing with Interferences
Mass Spectrometry Libraries and Tentatively Identified
Compounds (TICs)

GC/MS Data Processing


Important to Review Peak Integration

Chromatogram
(maximum
information content)

GC/MS
Final Report

GC/MS Data Processing


Important to Review Peak Integration

Calibrations and quantitation of organics all rely


on correct chromatographic peak integrations

Standards (Ax/Ais)----->Response Factors----->Sample Quantitation

Ax

Ais

NJDEP
OQA
OCTOBER 2002

Manual Integration
FOR GC/MS

Definition
A Manual Integration is any editing of the
area of integration by the chemist. Manual
integration is a perfectly acceptable,
scientifically valid, analytical technique
used to accurately reflect the area of a peak
when auto-integration fails.

A Manual Integration is not a way to


compensate for an improperly
maintained instrument. Manual
integrations are not to be used in lieu
of establishing appropriate integration
events using the analytical system
software.

Manual integration may be done in the


following cases where the automatic
integrator has:

failed to integrate a peak or part of a peak


integrated one peak as two peaks
integrated the wrong peak out of two similar peaks
not integrated from baseline to baseline
integrated a peak due to an elevated baseline
integrated a negative peak
integrated a peak beyond baseline resolution (too much area)
Any additional situations in which the auto-integrator fails to perform
properly and/or consistently

Manual integrations are NOT to be


performed for the sole purpose of making a
calibration curve, ICV,CCV, &/ or a QC
check sample (LCS, MS, surrogate, etc.)
pass acceptance criteria.

History
Most of the software programs used for chromatography
are capable of quantitating, using either peak area or peak
height and employ mathematical algorithms related to the
slope of the response to detect the beginning and end of
peaks.

History
Due to the complex nature of some sample matrices, the
ability to manually adjust an incorrect integration became
necessary. This flexibility is necessary in the production
of quality data.
Much of this process is based on analyst judgment. Each
peak must be evaluated and adjusted when necessary.
However, this flexibility has led to several instances of
improper laboratory activities.

IMPROPER INTEGRATIONS
According to the EPA Region 5s SOP on manual
integrations, inappropriate integration is any
integration, either automated or manual, which
excludes area associated with the target peak or
includes area not reasonably attributable to the
target peak, such as area due to a second peak or
excessive peak tailing due to a noisy baseline.

CORRECT INTEGRATIONS
This is an example of proper integrations when several peaks
are not completely resolved (i.e., the response does not return
to the baseline between peaks). The lowest point between two
points, the valley, is selected as the appropriate start and stop
points.

CORRECT INTEGRATIONS

Peaks with slight interferences either just prior to or


immediately after the target peak.
In these cases, part of the automatic integration may
include the interfering analyte. The following
integration techniques may be employed:

TYPES OF IMPROPER INTEGRATIONS


Peak shaving is the common term for unjustifiably
excluding area when integrating a
chromatographic
peak.
Almost all of us would agree that cutting a peak in half
horizontally or vertically is unjustified. But what to do
about the in between cases? How can judgment be
applied correctly when integrating peaks?

TYPES OF IMPROPER INTEGRATIONS

Baseline addition or subtraction


Do not add or subtract from the baseline. Another
example of an incorrect manual integration

TYPES OF IMPROPER INTEGRATIONS


Poor sensitivity. Signal is not 3 times the background.

WHY IS THIS HAPPENING?


Cost factors
Level of Expertise factors
Unethical Behavior

Cost Factors

The price paid is often not sufficient to


cover the costs of producing the product.

The client should not accept low bids


without considering the quality factor.

This is a free market economy - Let the


buyer beware or You get what you pay
for.

Level of Expertise Factors

Some laboratories have let their most


experienced staff go.

Lack of understanding regarding the


fundamentals of analytical chemistry at
both the laboratory and data user levels.

Thinking that the computer will always


give you the correct answer.

Why Unethical Behavior Occurs


Real or perceived pressures
Lack of ethics education and awareness
Lack of management oversite and review
Lack of knowledge or confidence in appropriate
ways to solve problems

Prevention
Efforts should be made during method
development to include the best instrument
parameters that allow for automatic integration
by the data system in most cases.
However, regardless of the sophistication of the
software, instances occur when the automated
software does not integrate a peak correctly.

Prevention
The failure of the software to appropriately
integrate a peak is usually obvious from visual
inspection of the chromatogram (at an appropriate
scale). Electronic review of analytical raw data is
essential in detecting improper activities.
The use of proper documentation protocols should
be established to allow manual integrations to be
reviewed during data validation.

DOCUMENTATION

All data must be integrated consistently in


standards, samples and QC samples. Integration
parameters, both automated and manual, must
adhere to valid scientific chromatographic
principles. Manual integration is employed to
correct an improper integration performed by the
data system and must always include
documentation that clearly states the reason
manual integration was performed.

Proper documentation is vital when conducting


manual integrations. The following is an example
documentation requirement:
Print the improperly integrated peak. initial, date
and provide a reason on the original for the manual
integration. Perform the necessary manual
integration. Print the manually integrated peak,
initial and date. Submit the manual integration data
along with the original automatic integration data as
part of the final data package.

GENERAL OBSERVATIONS
The fundamental principle of quantitative integration is
that samples should be integrated in the same style
chosen for integrating calibration standards.
If properly documented and conducted in a scientifically
defensible manner, manual integrations are perfectly
acceptable.

WHAT CAN LABS DO TO PREVENT


IMPROPER ACTIVITIES
Develop a detailed standard operating procedure that
includes examples and documentation requirements.
Enforce a zero tolerance policy for any improper
activities.
Have all analysts sign an ethics statement.
Electronically review random data files.

Questions?

GC/MS Interferences
What are Interferences?
Any compound or mixture of compounds that elutes at
the same time as the compound of interest. Therefore
the compound of interest can not be properly identified
or quantified.

EPA Office of Water Says:


Stating that the sample couldnt be analyzed is
not sufficient and will not be accepted as
justification for a claim of matrix interference.

Interferences in GC/MS Analysis


Problems they cause
quantitation accuracy of targets may be negatively
impacted
can make identification of target among interferences
difficult or impossible
if dilution is required, may raise detection limits
above required regulatory limits.

Interferences - What do they look like


(Example 1)

interferences

Extract could only be concentrated to 5 mls.

Interferences - What Do They Look Like


(Example 2 )

- Can only concentrate to 5 mls.


- diluted extract 1:5
- total dilution factor = 25x

a - Napthalene
b - dimethyl phthalate
c - diethyl phthalate
d - di-n-butyl-phthalate

b c

Interferences - What Are They


(Example 2)

1,3-dichloro-2-propanol
(a chlorinated alcohol)

1-methyl, 2,4-diisocyanato benzene


(a diisocyanate)

Interferences - What Can Be Done


(Example 2)

Analyze Base/Neutrals and Acid Fractions Separately - may isolate


interferences into fraction of less interest

Perform GPC Analysis to remove any potential high molecular weight


interferences
may help for samples that can only be blown down to 5 mls.
no guarrantee that GC or GC/MS analysis is seeing all of the sample

Perform Appropriate CleanUps


methods exist for cleaning up samples so that analytes of interest can be analyzed

GPC and Cleanups can be performed on the same sample.

Identify interferences and clean up waste stream


permittee likely has most intimate knowledge of their own waste stream.
Additional non-EPA method testing may be appropriate to identify interferences.

Clean-Up Techniques from SW-846


(stand alone methods strictly for cleanups)

Analytes of Interest

Methods

Aniline & aniline derivatives


Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Haloethers
Chlorinated hydrocarbons
Organophosphorus pesticides
Petroleum waste
All base, neutral, and acid
priority pollutants

3620
3630, 3640, 8041a
3610, 3620, 3640
3610, 3620, 3640
3610, 3620, 3630, 3660, 3665
3620, 3640
3611, 3630, 3640
3620, 3640
3620, 3640
3620
3611, 3650
3640

Interferences in GC/MS Analysis

From the EPA OCPSF (Organic Chemicals, Plastics and Synthetic Fibers) rules Guidance
on Evaluation, Resolution, and Documentation of Analytical Problems Associated with
Compliance Monitoring

Stating that the sample couldnt be analyzed is not sufficient and will not be
accepted as justification for a claim of matrix interference.
EPA provides for flexibility in wastewater methods and allows use of cleanups etc
provided method QA/QC are met.
As per Fed Reg. 49 FR 43234

Department can require additional work to be performed to get at an


accurate number. Not just take the easy way out and say interferences are
present.
Alternate methods
use of clean-up procedures
identify source of interference

Mass Spectral Libraries


What are mass spectral libraries?
A compendium of electron impact mass spectra collected
from a variety of sources

Why are they important?


Identifying non-target or tentatively identified
compounds (TICs), relies exclusively on these libraries

Mass Spectral Libraries


Why are they important - cont.?
Site Remediation for example typically requests:
VOAs + 10 TICs
BNs + 15 TICs
frequently drinking water methods

If TICs are found, proper identification is very important


may need correct ID for remediation
may need to provide data to County Health Dept and Owners
of Potable Well (as in BUST)

Mass Spectral Libraries


Why are they important - cont?
Waste Water Permitting:
some industries indicate that interferences are present which
preclude them analyzing the sample to permit detection limits
Identification of interferences can be used to determine what
options for cleanup may exist. Interferences may also be
environmentally unfriendly compounds that may need to
reviewed.

Bureau of Safe Drinking Water


BSDW reporting form has ability to enter TIC observations
from a laboratory.

Mass Spectral Libraries


How many libraries are there?
NIST/NIH/EPA Mass Spectral Library
NBS 75K
NIST 98
NIST 02

Wiley Mass Spectral Library


Combination Wiley/NIST
Custom Libraries
industry specific
proprietary

Mass Spectral Libraries


For NIST75K Library
Approx 50,000 Mass Spectra
Approx 25,000 Replicates
This library is very old
Not very well reviewed
Variety of Sources not well filtered.

Labs should NOT be using this!

Mass Spectral Libraries


For NIST98 Library - (a 75% increase over NBS75K
library)

107,886 Compounds
107,829 Chemical Structures
129,136 Spectra
21,250 Replicate Spectra
13,205 Compounds with Replicate Spectra
93 Average Peaks per Spectrum
78 Median peaks per Spectrum
75% Increase in coverage from high quality sources

Labs should be using at least this revision!

Mass Spectral Libraries


For NIST98 Library
(where does this 75% increase come from?)

Mass Spectra from other sources were added in


Chemical Concepts - including Prof Henneberg's industrial
chemicals collection
Georgia and Virginia Crime Laboratories
TNO Flavors and Fragrances
AAFS Toxicology Section, Drug Library
Association of Official Racing Chemists
St. Louis University Urinary Acids
VERIFIN & CBDCOM Chemical Weapons

Mass Spectral Libraries


For NIST 02 Library - 35% increase in coverage over NIST 98
Library

27,750 Replicate Spectra


from high quality sources
147,198 Compounds with Spectra
18,598 Compounds with Replicate Spectra
147,194 Chemical Structures
111 Average Peaks/Spectrum
174,948 spectra
98 Median Peaks/Spectrum

Mass Spectral Libraries


Comparison of NIST/NIH/EPA Libraries - different
revisions
NBS75K

NIST98

NIST 02

Total Spectra

75, 000

129,136

174,948

Total Replicates

20,000

21,250

27,750

Mass Spectral Libraries


Wiley Registry of Mass Spectral Data - 7th
Edition

the world's largest reference database of over


250,000 Electron-Impact mass spectra
Wiley Library may or may not include NIST library
Wiley contains mass spectra that are not as well reviewed.
Still very useful, if NIST library comes up short.

Why MS Library Version is Important


(example)

Air Analysis Example from 1996 (TO-14)


Samples consistently showed large peak in the analysis but
compound could not be identified by library.
Library search result was so poor, even a good quality TIC could not
be obtained.
At the time the NBS75K library was the only one available.
Pre 1998

Requested Chromatogram and Mass Spectrum to evaluate

Mass Spectral Libraries


(example of why version of library is important)

Mass Spectral Libraries


(example of why version of library is important)

Mass Spectral Libraries


(example of why version of library is important)

Mass Spectral Libraries


(example of why version of library is important)
Synonyms
1,1-Dichloro-1-fluoroethane
Ethane, 1,1-dichloro-1-fluoro Freon 141

Mass Spectral Libraries


Library Search Against NIST 98 Library
produced an excellent hit.

Best Hit
NBS75K

81

100

Cl
50

61
26
31
0

35
37

10
20
30
40
50
( m a in lib ) 1 , 1 - D ic h lo ro - 1 - fl u o ro e t h a n e

Freon 141

45
Cl

63
60

83
70

80

101
90

100

110

120

130

Best Hit
NIST98

Summary
Mass Spectral Libraries
Identities of non-target compounds (TICs)
may be dependent on the version of library
being used.
Most laboratories still use NBS75K library.
Be aware that other libraries exist.

Dioxins and PCB Analysis


Using
GC/High Resolution Mass Spectrometry

(actually high resolution gas chromatography/high resolution mass spectrometryHRGC/HRMS)

Overview
Review of EPA Dioxins and PCB structures & methods
Typical Mass Spectrometry Instrumentation
Why High Resolution Mass Spectrometry?
High Resolution Mass Spectrometry (MS) Overview
Use of Isotopically Labeled Targets
Comparison of PCB congener and Aroclor methods
Toxicity Equivalents (TEQs) and TEFs

Dioxin/Furans/PCBs
(Chemical Structures)

Dioxin Analysis Target Compounds


Both 1613 and
8290 analyze for
these 17
Dioxins and
Furans
Drinking water
regulates only
the 2,3,7,8TCDD

PCB Terminology

PCBs (can mean anything)


Aroclors (mixture of PCBs)
PCB Congeners (209 individual)
Dioxin-Like PCBs
Coplanar PCBs
WHO PCBs - a list of 12 specific PCBs
Homologs (all congeners having same # of chlorines
attached)

More PCB Terminology

BZ/IUPAC
Congener
Number

Prefix to Chlorobiphenyl

PCB-77

3,3',4,4'-Tetra-Chlorobiphenyl

PCB-81

3,4,4',5-Tetra-

PCB-105

2,3,3',4,4'-Penta-

PCB-114

2,3,4,4',5-Penta-

PCB-118

2,3',4,4',5-Penta-

PCB-123

2,3',4,4',5'-Penta-

PCB-126

3,3',4,4',5-Penta-

PCB-156

2,3,3',4,4',5-Hexa-

PCB-157

2,3,3',4,4',5'-Hexa-

PCB-167

2,3',4,4',5,5'-Hexa-

PCB-169

3,3',4,4',5,5'-Hexa-

PCB-189

2,3,3',4,4',5,5'-Hepta-

a total of 209 PCB congeners e.g. PCB 1 ---> PCB 209

Still More PCB Terminology


PCBs as Arochlors
no longer referring to individual PCBs
Arochlors are complex mixtures

Often designated Aroclor XXXX


e.g Aroclor 1242
on average, this molecule contains 42 % by weight of Chlorine

Method Overview
Dioxin Analyses
EPA Method 1613B1 - For drinking water and waste water use
EPA Method 8290 - for SHW samples

PCB Congener Analysis Methods


EPA Method 1668 - Revision A
can be used for all matrices

dated December of 1999


contains all 209 possible PCB congeners

EPA Method 8082 - usually used for Aroclors - SHW Samples


has the option to perform limited set of 19 congeners
can be modified to do other congeners
1

as old NPDES permits requiring dioxin analyses by 613, they will be reissued with
requirement for 1613B

Method Overview

PCB as Aroclors Analysis Methods


EPA Method 508 and 608 - for Drinking and Wastewater
EPA Method 8082 - solid and hazardous waste samples use
all of these are GC/ECD techniques

Dioxin and PCB Analysis


(Why analyze for them?)

Dioxins and PCBs have been shown to be


toxic at varying levels.
e.g. Drinking Water MCLs (NJ State Standards)
2,3,7,8-T etra C hloro D ibenzo D ioxin (TCDD)
3 x 10-5 ppb

PCBs
0.5 ppb

or

0.00003 ppb

Why did EPA choose GC/High Resolution


Mass Spectrometry to analyze for Dioxins
and PCBs?

MCLs for these compounds are very low


Need sensitive method(s) capable of low detection limits
Provide a high level of confidence in compound identification
Need to minimize effect of interferences

How Does GC/High Resolution Mass


Spectrometry Accomplish These Criteria?
1) Need for Very High Identification Certainty/Minimize
Interferences
High Resolution Mass Analysis
Use of Chlorine Isotope Masses
two masses for each target
Isotope Ratios must meet theoretical value

2) Need for very low detection limits


Combination of High Voltage Operation and Selected Ion
Monitoring Scan (SIM)
Concentrate sample to ul range instead of ml.

Nominal and Exact Masses for Common Elements


Element

Symbol

Nomi
nal
Mass

Exact
Mass

Abundanc
e

Hydrogen

H
D or 2H

1
2

1.00783
2.01410

99.99
0.01

C
C

12
13

12.0000
13.0034

98.91
1.09

N
N

14
15

14.0031
15.0001

99.6
0.37

O
O
18
O

16
17
18

15.9949
16.9991
17.9992

99.76
0.037
0.20

19

18.9984

Si
Si
30
Si

28
29
30

27.9769
28.9765
29.9738

92.28
4.70
3.02

31

30.9738

100

S
S
34
S

32
33
34

31.9721
32.9715
33.9679

95.02
0.74
4.22

Cl
Cl

35
37

34.9689
36.9659

75.77
24.23

Br
Br

79
81

78.9183
80.9163

50.5
49.5

Carbon
Nitrogen

12
13

14
15

16

Oxygen

Fluorine

17

28

Silicon
Phosphorus

29

32

Sulphur

Chlorine
Bromine

33

35
37

79
81

100

What is High Resolution Mass Spectrometry

High Resolution Mass Spectrometry is capable of obtaining mass


spectra and measuring masses to approximately the fourth decimal
place.
322

100

320
35

C12H4 Cl4O2
MW = 319.896542

Cl

Cl

Cl

Cl

50

C12H437Cl135Cl3O2

257
194
74

MW = 321.8936

50 62
0

160

97
85

113
122

144

50
80
110
140
170
( m a in lib ) 2 , 3 , 7 , 8 - T e t ra c h lo ro d ib e n z o - p - d io x in

187

287

229
200

230

260

290

320

Specialized MS Instrumentation
VG70-250SE High Res. MS

HP5973 Low Res. MS

What is Mass Resolution?


Very Simply - The ability to distinguish between
different masses.
e.g. Can we distinguish mass 78 from 79?
Can we distinguish between mass 78.003 and 78.004?
A quantitative approach to determining how well we can distinguish
different masses is called Resolving Power. Different than
chromatographic resolution.

Resolving Power
by definition:

Resolving Power(R.P.) = m/ m
ppm = R.P. / 1 x 106
a resolving power of 10,000 = 100 ppm
***All High Resolution EPA Methods use an R.P. of 10,000***

Calculation of Mass Resolution

Resolution Example
were asked to separate a three component gas mixture
containing
carbon monoxide
nitrogen
ethylene

Calculating Molecular Weights


nominal mass
carbon
monoxide - CO

nitrogen - N2
ethylene - C2H4

accurate mass

1 x 12 = 12
+ 1 x 16 = 16
28

1 x 12.0000 = 12.0000
+ 1 x 15.9949 = 15.9949
27.9949

2 x 14 = 28
28

2 x 14.0031 = 28.0062
28.0062

2 x 12 = 24
+ 4x 1= 4
28

2 x 12.0000 = 24.0000
+ 4 x 1.0078 = 4.0312
28.0312

What Resolution Do We Need to See


All 3 Components?
carbon
monoxide - CO

1 x 12.0000 = 12.0000
+ 1 x 15.9949 = 15.9949
27.9949

nitrogen - N2

2 x 14.0031 = 28.0062
28.0062

ethylene - C2H4

2 x 12.0000 = 24.0000
+ 4 x 1.0078 = 4.0312
28.0312

0.0113

0.025

What Resolution Do We Need to See


All 3 Components? (contd)
nominal
mass
CO
N2
C2H4

28
28
28

exact
mass

mass

Resolving Power
Needed (m / m)

27.9949
0.0113

2,478

0.0250

1,120

28.0062
28.0312

- Need at least 2,500 to see all three components.

Low and Medium Resolution Mass Spectra


of Ternary Mixture

Applications to Dioxins/PCB Congener Analyses


(2,3,7,8-TetrachloroDibenzoDioxin (TCDD))

Calculation of Mass for 2,3,7,8-TCDD Analysis

2,3,7,8-TCDD
C
H
Cl
O

37

Nominal Mass
12 x 12 = 144
4x 1 =
4
4 x 35 = 140
2 x 16 = 32
320

Cl = 36.9659

C12H4Cl4O2
Exact Mass
12 x 12.000000 = 144.000000
4 x 1.007825 =
4.031300
4 x 34.968853 = 139.875412
2 x 15.994915 = 31.989830
C12H435Cl4O2
319.896542
C12H437Cl4O2

321.8936

Table From EPA Method 1613B

m/z 320 & 322

Same Calculation for PCB Congeners


360

100

HexaChloroBiphenyl

C12H4Cl6

50

290
145
109

37

49

218

127

74

98

61

180

163

0
30
50
70
1,1'-Biphenyl, 3,3',4,4',5,5'-hexachloro-

C
H
Cl

37

90

110

Nominal Mass
12 x 12 = 144
4x 1 =
4
6 x 35 = 210
358

Cl = 36.9659

130

150

254

204
170

190

324

240
210

230

250

270

290

310

330

350

Exact Mass
12 x 12.000000 = 144.000000
4 x 1.007825 =
4.031300
6 x 34.968853 = 209.813118
C12H435Cl6
357.844418
C12H437Cl137Cl3O2 359.8415
C12H437Cl237Cl2O2 361.8385

From Table 7 of EPA Method 1668A

m/z 360
362
364

Isotope Ratio QA/QC Requirements


(from EPA 8290)
(same as 1613B & 1668A)

15 %

Common Chemical Interferences in the GC/MS determination


of 2,3,7,8-TCDD

Selected Ion Monitoring - Better DLs


(Sector Instruments Use Voltage Scanning for Accuracy)
322

100

Full Scan
Detect all masses
over a given scan
range.
e.g. m/z 100-500

Cl

Cl

Cl

Cl

50

50 62

74

85

97

113

160

194
187

143

50
80
110
140
170
( m a in lib ) 2 , 3 , 7 , 8 - T e t ra c h lo ro d ib e n z o - p - d io x in

257
287

229
200

230

260

290

322

100

SIM
Look only for
masses relevent
to targets

320

Cl

Cl

Cl

Cl

50

50 62
0

74

85

97

113

160
143

50
80
110
140
170
( m a in lib ) 2 , 3 , 7 , 8 - T e t ra c h lo ro d ib e n z o - p - d io x in

194
187

257
287

229
200

230

260

290

320

High Resolution MS Advantages


Enhanced Identification Capabilities
Ability to analyze exact masses provides for better identification
capability over LRMS
Detecting multiple isotopes (chlorine) adds yet another level of
confidence in compound identification
Eliminates or minimizes interferences in dirty samples
Cleanups are the rule not the exception

Enhanced Sensitivity
High Resolution Mass Spectrometers operate at High Voltage (8
KV)
Voltage Scanning Selected Ion Monitoring (SIM)
Concentration of Sample down to ul as opposed to mls.

Approximate Method Detection Limits


Depends on Matrix
Method

Aqueous

Other

Method 1668

5-300 ppq

1-25 ppt

Method 1613B
Method 8290

3 ppq

1 ppt

10 ppq

1 ppt

Disadvantages of HRMS
high capital cost ( approx. $400,000)
higher maintenance
maint. contract 8% of purchase price annually.
skilled staff required
analysis costs high
$1,000 /analysis
special facility requirements
Vibration
Footprint is large
Temp/Humidity Control
Special Power Requirements

Use of Isotopic Labeling


Methods 1613B, 8290 and 1668A all make
use of Isotopic Labeling

C and 37Cl labeled target compounds are


used for quantitation (internal standards are
also used)
13

Use of Isotopic Labeling


Methods 8290 - Dioxins/Furans
9 out of the 17 targets are labeled

Methods 1613B - Dioxins/Furans


15 out of 17 targets are labeled

Methods 1668A - PCB Congeners


27 out of 209 are labeled.

Benefits of Isotopic Labeling


Isotopically labeled target compounds will behave
identically to targets of interest.
If targets are lost during processing, labeled standards
will also be lost. Corrects for recovery 100%
Provides for more accurate quantitation of targets.

Isotopically labeled target compounds elute


seconds prior to target of interest
Enable analyst to readily identify the target
If interferences are present, this is extremely helpful
This too increases ID accuracy

Sample Chromatogram
(showing Isotopically Labeled Standards)

Sample Chromatogram
(Typical Raw Data Page Dioxins - HxCDD)

Target
HxCDD

Labeled
HxCDD
Interfering
Compounds
Lock Mass
Check Channel

PCB Congener Analysis vs. Aroclor Analysis


(pros)

The toxicity of PCBs is very congener specific


measurement on an Aroclor basis may not accurately reflect toxicity.

Identification of a PCB is more definitive. Interferences are more easily


detected.

Quantitation of individual congeners is more accurate than estimating


Aroclors

Composition of weathered, degraded and metabolized PCB mixtures can


be measured and interpreted easier using congener vs. Aroclor analysis

Aroclor concentrations can be estimated using congener concentrations


(depending on the list of congeners being analyzed for)

PCB Congener Analysis vs. Aroclor Analysis


(cons)

Very high cost (typically greater than $1,000

TEFs are not available for all congeners


World Health Organization (WHO) has a list of 12 TEFs

Comparability among laboratories


labs vary in how they perform PCB congener analysis
different labs may use different columns (different coelutions)
PCB congener ID comparability

no good PE samples are available (some SRMs)


there is a NIST Intercomparison Exercise for Organic Contaminants in the
Marine Environment
cost $2500 for two matrices

Comparison of EPA Method 8082 and


1668A
8082

DLs
Cost $75 - $300
Aroclor Using GC/ECD
May not meet DQOs.
Aroclor analysis may over or underestimated PCB concentrations.
Does not measure individual congeners but rather relies not a pattern
recognition
Aroclor analysis may severely underestimate toxicity.

1668A
PCB Congeners using GC/HRMS
Detection Limits
Cost > $1,000

EPA Method 1668A Misnomers


All 209 congeners are analyzed for, BUT
Does not provide quantitative values for each of the 209
individually
Not all 209 are quantitated in the same manner.
Multipoint vs. single point calibration

Not all 209 congeners are chromatographically resolved


about 130 congeners are fully resolved
everything else is reported as coelutions

Analyzed under low voltage conditions


not at 70 eV (Typically 30 - 40 eV)

Proficiency Evaluation (PE) Samples for Dioxin


and PCB Analysis
PE samples for 2,3,7,8-TCDD - Available
PE Samples for Aroclors - Available
PE samples for PCB congeners - NOT AVAILABLE
For congeners
SRMs are available from NIST
Some standards available from CIL, Wellington, others?
Still a problem
none of the above contain all of the WHO PCBs - presumably the most important
ones.
Need to go with a reliable lab

Dioxins and PCB Analysis


Hold Times

From 1613B Dioxins


8.4.1 There are no demonstrated maximum holding times associated with
CDDs/CDFs in aqueous, solid, semi-solid, tissues, or other sample matrices. If
stored in the dark at 0-4C and preserved as given above (if required), aqueous
samples may be stored for up to one year. Similarly, if stored in the dark at <10C, solid, semi-solid, multi-phase, and tissue samples may be stored for up to
one year.
8.4.2 Store sample extracts in the dark at <-10C until analyzed. If stored in the
dark at <-10C, sample extracts may be stored for up to one year.

From 1668A PCB Congeners


8.5.1 There are no demonstrated maximum holding times associated with the
CBs in aqueous, solid, semi-solid, tissues, or other sample matrices. If stored in
the dark at 0-4 EC and preserved as given above (if required), aqueous samples
may be stored for up to one year. Similarly, if stored in the dark at <-10 EC,
solid, semisolid, multi-phase, and tissue samples may be stored for up to one
year.

Reporting Dioxin and PCB Data Results


Two Approaches
1) Provide a quantitative value for each target compound
2) Report a single number a Toxicity Equivalent

This approach used frequently for Risk Assessment purposes,


Dioxins/Furans/PCBs are often combined together as a Toxic
Equivalent Quantity (TEQ)

To calculate TEQ, need to use Toxic Equivalency Factors

(TEFs)

TEFs and TEQs


Toxic Equivalent Quantity (TEQ)
Over the years, researchers have
determined the relative toxicities for
a variety of different compounds with
the most toxic 2,3,7,8-Tetrachlorodibenzodioxin
- being assigned a toxic equivalency
factor (TEF) of One (1)

TEFs and TEQs


TEF for 2,3,7,8-TCDD = 1
TEF = Toxic Equivalency Factors.
A method of weighting the toxicity
of individual dioxin/furan/coplanar
PCB compounds, as compared to
2,3,7,8-TCDD.

TEFs and TEQs


1994 WHO TEFs(1)

1997 WHO TEFs(2)


Humans/Mammals

Fish

Birds

PCB-77

0.0005

0.0001

0.0001

0.05

PCB-81

--

0.0001

0.0005

0.1

PCB-105

0.0001

0.0001

<0.000005

0.0001

PCB-114

0.0005

0.0005

<0.000005

0.0001

PCB-118

0.0001

0.0001

<0.000005

0.00001

PCB-123

0.0001

0.0001

<0.000005

0.00001

PCB-126

0.1

0.1

0.005

0.1

PCB-156

0.0005

0.0005

<0.000005

0.0001

PCB-157

0.0005

0.0005

<0.000005

0.0001

PCB-167

0.00001

0.00001

<0.000005

0.00001

PCB-169

0.01

0.01

0.00005

0.001

PCB-170

0.0001

--

--

--

PCB-180

0.00001

--

--

--

PCB-189

0.0001

0.0001

<0.000005

0.00001

Calculating TEFs and TEQs


Conc. MDL

DIOXINS
OCDD
1234678-HpCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
12378-PeCDD
2378-TCDD
FURANS
OCDF
1234678-HpCDF
1234789-HpCDF
123478-HxCDF
123678-HxCDF
234678-HxCDF
123789-HxCDF
12378-PeCDF
23478-PeCDF
2378-TCDF

TEF

TEQ

ng/kg

ng/kg

ng/kg

5500
410
nd
10
8.8
nd
nd

10
5.0
2.5
5.0
5.0
4.8
0.75

1E-04
0.01
0.1
0.1
0.1
1
1

0.550
4.100
0.125
1.000
0.880
2.400
0.375

130
39
nd
nd
nd
nd
nd
nd
nd
nd

10
5.0
3.1
4.1
1.8
1.0
0.94
0.61
2.7
2.90

1E-04
0.01
0.01
0.1
0.1
0.1
0.1
0.05
0.5
0.1

0.013
0.390
0.016
0.205
0.090
0.050
0.047
0.015
0.675
0.145

Calculating TEFs and TEQs


Conc. MDL
ng/kg

1
2
3
4
5
6
7
8
9
10
11
12

COPLANAR PCB'S
3,4,4',5-TCB (#81)
170
3,3',4,4'-TCB (#77)
12
3,3',4,4',5-PeCB (#126)
19
3,3',4,4',5,5'-HxCB (#169)
nd
2,3,3',4,4'-PeCB (#105)
1000
2,3,4,4',5-PeCB (#114)
71
2,3',4,4',5-PeCB (#118)
2300
2',3,4,4',5-PeCB (#123)
93
2,3,3',4,4',5-HxCB (#156) 280
2,3,3',4,4',5'-HxCB (#157) 71
2,3',4,4',5,5'-HxCB (#167) 500
2,3,3',4,4',5,5'-HpCB (#189) 47

TEF

ng/kg

4.0
0.0001
4.0
0.0001
4.0
0.1
4.0
0.01
4.0
0.0001
4.0
0.0005
4.0
0.0001
4.0
0.0001
4.0
0.0005
4.0
0.0005
4.0
1E-05
4.0
0.0001
TOTAL TEQ

TEQ
ng/kg

0.017
0.001
1.900
0.020
0.100
0.036
0.230
0.009
0.140
0.036
0.005
0.005
13.574

Summary
PCB Congener Data can be obtained by two
methods: EPA Method 8082 and 1668A.
GC/High Resolution Mass Spectrometry provides
for the analysis of compounds with excellent
identification capability and sensitivity.
PPQ detection levels can only be achieved using
GC/High Res Mass Spectrometry