Food Icpms
Food Icpms
10/22/04
5:23 PM
Page 1
A Primer
Food Safety
Applications in Mass Spectrometry
Trap
TOF
Quad
to food analysis.
Agilent Technologies, Inc. 2004. All rights reserved.
Reproduction, adaption, or translation without prior written
permission is prohibited, except as allowed under the copyright
laws. This information is subject to change without notice.
Printed in the U.S.A. June 3, 2005.
5989-1270EN
A Primer
Table of Contents
Primer Introduction ............................................................................................................. 01
Introduction to MS ............................................................................................................. 03
GC/MS Basics .................................................................................................................... 05
GC/MS Instrumentation ....................................................................................................
Ionization Sources ...............................................................................................................
Mass Analyzers ...................................................................................................................
Detector & Data System .....................................................................................................
08
10
12
13
Primer Introduction
Public safety concerns. International
trade regulations. The food industry is
under unprecedented pressures to meet
ever more stringent food safety standards,
regulations, and expectations regarding
the chemical residues present in
foodstuffs. On the journey from the farm
or factory to our plates, many food
products will have come into contact
with various chemical substances from
fertilizers, pesticides, herbicides, growth
hormones, and antibiotics, to food
additives and migratory compounds
from packaging materials.
01
Analytical Solutions
Food analysts require analytical methods
to detect and identify the nature and
concentration of chemicals in all
components of foodstuffs from the raw
materials to the end product. These
sample analyses are challenging due to
the complexity of the matrix compounds
in food extracts, which often interfere
with detection of target compounds
and elements.
Traditionally, methods based on
high-performance liquid chromatography
(HPLC), gas chromatography (GC),
graphite furnace atomic absorption
spectroscopy (GFAAS), and inductively
coupled plasma optical emission
spectroscopy (ICP-OES) were commonplace in food-monitoring laboratories.
But as regulatory levels are driven down
and new analytical challenges arise,
analysts require instrumentation that
offers low limits of detection with high
degrees of accuracy and precision. As
a result, more and more laboratories
are relying upon detection by mass
spectrometry.
Agilent's Mass
Spectrometry Capabilities
To address these requirements,
Agilent offers a wide range of innovative
MS solutions for the analysis of food to
complement their chromatography
products take a closer look at the
fundamental concepts and instrumental
considerations of GC/MS, LC/MS, and
ICP-MS in the Instrumental part of
the Primer.
Each of these mass spectrometry systems
is designed to ensure that all food analyses
are conducted accurately, reliably, and
efficiently, detecting the lowest level of
chemicals and elements in complex
matrices. Food analysts can draw on
Agilents applications know-how,
sophisticated software solutions, highquality accessories and consumables,
and service support to improve sample
throughput, solve problems, and deliver
reliable results.
02
03
Introduction to MS
Mass spectrometry (MS) is an analytical technique which can be applied to the
identification and quantification of organic or inorganic constituents in a sample.
Although many aspects of the instrumentation used for the analysis of organic
molecules is different to that used to measure the elements from the periodic table,
the basic principles are the same.
The sample introduction system of a mass spectrometer includes an ionization source that
places a small electrical charge on samples converting them to ions. When characterizing
organic compounds, it is often important to keep the structure of the molecule intact, so
low energy or soft ionization processes are used. When measuring elements or metals
using mass spectrometry, it is necessary to break down the samples to their fundamental,
atomic elements, so a much more powerful ion source is utilized.
Ions produced by the ionization source are separated according to their mass-to-charge
ratios using a mass filter and detected with a sensitive detector. The number of ions at
each mass-to-charge ratio is collected, and a plot of ion abundance versus mass-to-charge
ratio is created. This is called a mass spectrum. Like fingerprints, mass spectra can be
used to identify chemical compounds or isotopic composition of a sample.
Mass spectrometry is often combined with a separation technology such as gas
chromatography (GC) or liquid chromatography (LC) to form a powerful system for
analyzing complex mixtures. The chromatograph separates sample mixtures into their
constituent parts. The mass spectrometer then analyzes the sample components to
provide data for identification and quantification.
An inductively coupled plasma (ICP) is used as a high-energy source for mass
spectrometry for the analysis of trace and ultra-trace elements in a range of solutions.
ICP-MS can be combined with a laser ablation (LA) sample introduction device for the
direct analysis of solid samples. ICP-MS can also be combined with LC or GC for use
as an element-specific detector for many applications.
Agilents MS portfolio features various kinds of MS instruments built around three
main types of mass filter technologies quadrupole, ion trap, and time-of-flight (TOF)
to meet a variety of needs and applications. Agilents mass spectrometers are often
coupled with the companys industry-leading gas and liquid chromatographs to form
powerful GC/MS and LC/MS systems, as well as GC-ICP-MS and LC-ICP-MS systems.
04
GC/MS Basics
05
GC/MS Basics
Mass spectrometry (MS) represents the most definitive general detector for gas
chromatography (GC) work used in environmental, foods, clinical, pharmacological,
and forensic applications. Its wide acceptance is due to its effectiveness in separating,
identifying, and quantifying compounds in complex sample-types.
Capabilities of GC/MS
GC/MS can provide general or specific information
GC/MS can provide data to identify unknown peaks
GC/MS can provide data to recognize co-eluting peaks
GC/MS can provide quantitative information in complex matrices
A Chemical Ionization (CI) mass spectrum can provide molecular weight information
06
GC/MS Basics
Ionization modes
Electron impact ionization results in classical spectra for library matching; see Figure 1.
Positive chemical ionization produces protonated molecules and adduct ions to
confirm molecular weights; see Figure 2.
Negative chemical ionization for trace-level detection
Example spectra:
FIGURE 1. MASS SPECTRUM OF DI-N-BUTYL
PHTHALATE USING ELECTRON IMPACT IONIZATION
(EI). THE MOLECULAR ION IS PRESENT IN VERY
LOW ABUNDANCE AT 278 M/Z.
07
GC/MS Instrumentation
GC/MS instrumentation can be
considered under the following
five headings:
Separation
- Gas chromatography
Ionization Source
- Electron ionization (EI)
- Chemical ionization (CI)
Mass Analyzer
- Quadrupole
- Ion Trap
Detector
- Electron multiplier
- Photomultiplier
Data System
Separation
Most samples are introduced into a
mass spectrometer through a gas
chromatograph. Although direct insertion
probes are needed for certain specialized
applications, GC/MS is the predominant
mode of operation. The separation
capabilities of the GC far exceed what
could be done even with temperature
programming of a probe.
Sample Introduction
The first step to producing a mass
spectrum is directing molecules into the
mass spectrometer through the sample
inlet. Gas, liquid, and solid compounds
can be introduced into the ion source
through specially designed inlets. The
most common inlet used in the gas
chromatograph is the split/splitless
injection port.
08
GC/MS Instrumentation
Other devices commonly associated with
the GC/MS include the purge and trap
and the headspace samplers. Purge and
trap samplers work by concentrating
volatile components on a packed trap,
which is then thermally desorbed onto
the analytical column for separation.
Headspace samplers, on the other hand,
work by injecting a fixed or variable
gaseous sample volume onto the analytical
column. In both cases the GC oven
temperature is set at a low temperature
to refocus the analytes, then the oven is
ramped to separate them. These sampling
devices minimize or eliminate the sample
preparation stage.
Column
Modern GC/MS instruments are
optimized to work with capillary
columns. In older instruments, various
devices, such as the jet separator, were
used to reduce the column flow to a level
suitable for the pumping system. These
devices were troublesome to maintain
and compromised performance. Fused
silica capillary columns were a vast
improvement in matching flow rates and
providing an inert sample path directly
into the mass spectrometer source. The
most common column size used in
GC/MS is 0.25 mm id, although larger
and smaller columns are used. The
sensitivity of mass spectrometry is so
high that it is highly recommended that
the lowest bleed columns be used.
Column manufacturers typically have
an MS line of some of the most
common columns.
09
Transfer Line
Mass spectrometers are much larger than
conventional GC detectors. The connection
to the mass spectrometer must be done
centimeters away from the GC oven
itself. Between the oven wall and the ion
source, the column must be maintained
at a sufficiently high and uniform
temperature that compounds do not
condense. Similarly, the temperature
cannot be so high that thermally labile
compounds degrade. To join the GC
oven and the ion source, a heated
transfer line is used. The most important
characteristics of this transfer line are
that it is as short as possible and that it
is independently and uniformly heated.
Vacuum System
For proper operation, the interior of the
mass spectrometer must be evacuated.
The ion source, mass filter, and detector
all are under vacuum. The vacuum
system makes it possible for ions to
move from the ion source to the detector
without colliding with other ions and
molecules. Typical operating pressures
-5
-6
for GC/MS are around 10 and 10 torr.
This vacuum is achieved by using a high
vacuum pump backed by a mechanical
rough pump.
Ionization Sources
Ionization Sources
Sample molecules are introduced into
the ion source through the sample inlet.
Before the mass spectrometer can
analyze a sample, the sample molecule
must be ionized. In the ion source, the
molecules go through an ionization and
fragmentation process. The ions are then
directed into the mass filter.
Electron Impact Ionization (EI)
Electron impact ionization (EI) is the
most common mode of operation for
GC/MS, accounting for over 90% of all
work and a high number of commercially
available spectral reference libraries. In
EI, a molecule emerging from the GC
column is ionized by interaction with a
stream of relatively high-energy electrons
(70 eV). These collisions produce
(primarily) positive ions. Upon ionization,
the molecules of a given substance
fragment in very reproducible patterns.
EI is a direct process: energy is
transferred collisionally from electrons
FIGURE 3. MASS SPECTRUM OF THE COMMON PESTICIDE ENDOSULFAN USING EI IONIZATION. NOTICE THE MOLECULAR
ION IS OF VERY LOW ABUNDANCE AT 407/408 M/Z AND THERE IS A GREAT DEAL OF FRAGMENTATION.
10
Ionization Sources
Chemical Ionization (CI)
Chemical ionization (CI) is another
technique that is available to complement
EI and extend the use of mass
spectrometry. In chemical ionization,
sample molecules are introduced into
an abundance of reagent gas, typically
methane or ammonia. Because there is so
much more reagent gas than sample,
most of the emitted electrons collide with
reagent gas molecules, forming reagent
ions. In the case of ammonia, you can get
[M+H] + and [M+NH4] + as the products.
These reagent gas ions react with each
other, in primary and secondary reaction
processes that establish an equilibrium.
They also react in various ways with
sample molecules to form sample ions.
CI ion formation involves much lower
energy and is, therefore, much more
gentle than EI. Because CI results in
much less fragmentation, CI spectra
usually show high abundance of the
molecular ion; see Figure 4. For this
FIGURE 4. MASS SPECTRUM OF ENDOSULFAN USING CHEMICAL IONIZATION WITH METHANE BUFFER GAS.
11
Mass Analyzers
Mass Analyzers
The ions that are formed either by EI
or CI technique must be separated by
their mass-to-charge ratio. There are
four classes of mass filters (analyzers)
that are used to select and filter ions:
Radio frequency (both quadrupole
filter and ion trap)
Time-of-flight (TOF)
Fourier Transform: Ion Cyclotron
Resonance (ICR or FTMS)
Magnetic sector
In this section, the principles for
quadrupole and ion trap mass filters
are discussed. Refer to the LC/MS
section for further information on TOF.
Quadrupole (Q)
The quadrupole is the most widely used
MS analyzer due to its ease of use, mass
range, linear working analytical range
for quantitative work, resolution, and
quality of mass spectra. Analyses at low
picogram levels are routine and data are
reproducible, with RSDs of less than
5 percent. A quadrupole mass analyzer
consists of four parallel rods arranged in
a square (see Figure 5). The analyte ions
are directed down the center of the
square. Applying precisely controlled DC
voltages and a radio frequency to
opposing sets of poles generates
electrostatic fields that act as a mass
filter. These fields determine which
mass-to-charge ratio of ions can pass
through the filter at a given DC voltage.
12
Data System
The data system is an integral part of
the GC/MS system. Modern instruments
cannot be operated apart from the
computer that collects the data, displays
the results, and generates the reports.
Former laborious processes like
instrument calibration (tuning) are now
automated with software. The computer
system also provides diagnostic tools for
troubleshooting.
13
Qualitative Applications
The lines in the mass spectrum represent
the mass-to-charge ratio (m/z) of the
molecular ion and the fragment ions.
An expert mass spectrometrist may be
able to interpret this information and
identify a molecule by deducing
information from its mass spectrum.
Using well-documented interpretation
methods, mass spectrometrists can
identify molecules that are not in a
library or database. However, the majority
of GC/MS users search the unique spectral
pattern with reference library spectra.
In a library search, a computer is used to
match an acquired spectrum to a database
of spectra by peak matching. This method
uses the only two variables available, the
mass-to-charge ratios in the spectrum
and their relative abundances. Using a
computer to do a library search is one
way to eliminate a lot of possibilities
from a large database of compounds.
However, while a spectrum is
characteristic of a compound, it may
not be unique. Compounds with similar
fragmentation patterns (for example,
isomers) are difficult to identify based
on spectra alone and co-eluting
compounds can compromise identification.
Retention time locking (RTL) can be used
to distinguish between multiple isomers
that exhibit very similar mass spectra
and therefore require retention time
information for confirmation, and
spectral deconvolution helps to identify
compounds even when they are buried
under co-eluting matrix compounds. See
RTL and Deconvolution sections on the
next two pages for more information.
Quantitative Applications
Target Compound Analysis
A target ion is an ion characteristic of
the target compound, preferably one that
distinguishes this compound from any
others with similar retention times. The
extracted ion chromatogram for this ion
will be used for quantitation. Qualifier
ions are selected from the mass spectrum
of the target compound. The presence
of these ions in the correct amounts
relative to the target ion gives evidence of
correct target compound identification.
Typically, quantitation is based on peak
areas (or heights) from chromatographic
data generated from the analysis of a
calibration standard containing a known
concentration of the compound(s) to be
quantitated (target compounds). An
internal standard (ISTD) is often added
to the calibration sample and actual
samples. The sample is then analyzed
under the same operating conditions.
The results are compared to calculate
the amount of each target compound in
the unknown.
14
15
AMDIS
- Identification of 567 targets based
on deconvoluted spectra (instead
of four ions)
- Qualify targets based on retention
times (using RTL)
NIST02 Search>147,000 different spectra
- The component spectra of unknown
compounds not in the target library
can be searched against the NIST02
main library for identification.
- Confirm targets using full
deconvoluted spectra from AMDIS
DRS contains a 567-pesticide compound
library in appropriate formats and is
applicable to a range of industries, for
example, environmental, food safety,
flavors, toxicology, homeland security,
PCB analysis, drug testing, forensic,
volatiles. Users can tailor the library to
their own requirements by adding their
own spectra.
References
[1] H. Prest and Dave Peterson, New Approaches to the
Development of GC/MS Selected-Ion-Monitoring
Acquisition and Quantitation Methods Agilent Technologies,
publication 5988-4188EN, www.agilent.com/chem.
[2] V. Giarocco, B. Quimby and M. Klee, Retention Time
Locking: Concepts and Applications, Agilent Technologies,
publication 5966-2469E, www.agilent.com/chem.
[3] http://www.chem.agilent.com/cag/servsup/usersoft/
main.html#RTL.
[4] M. Szelewski and C.K. Meng, Building and Editing RTL
Screener Databases and Libraries, Agilent Technologies,
publication 5989-0916EN, www.agilent.com/chem.
[5] National Institute of Standards and Technology, AMDIS
Literature and Downloads website: http://www.amdis.net/
What_is_AMDIS/AMDIS_Literature_and_Downloads/
amdis_literature_and_downloads.html.
16
LC/MS Basics
17
LC/MS Basics
Invented more than a century ago, liquid chromatography (LC) is an established
analytical method of separating compounds within a sample so they can be identified
and quantified. Strengths of the technique are attributable to its sensitivity, quantitative
capabilities, and its suitability for separating nonvolatile and thermally fragile
molecules typical of 80% of all natural and man-made compounds. With applications
in many fields of science and chemical analysis across diverse industries and public
services, LC is used to analyze a very wide range of organic compounds, from small
molecules, metabolites, peptides, to large, fragile biomolecules such as proteins.
Most applications using mass spectrometry detection will require a separation step
so that complex samples are separated into single chemical species to allow:
Accurate interpretation of mass spectral information
the spectrum must relate to a single chemical species.
Accurate quantification of an analyte the mass-specific response
must relate to a single chemical species and must be reproducible.
Interference reduction through effective separation for trace analysis.
High level of selectivity through use of retention time identification
matching target analyte retention time and related mass spectrum
with a target reference
fference standard.
By combining MS with LC, sample components are separated in both time (LC) and
mass (MS) to isolate, identify,
y, and quantify an
y
ny
n
y ionizable component in any mixture.
The identification of complex samples presents a problem for LC analysis using
traditional detection techniques. Coeluting compounds generally can be identified
using UV absorbance detection with diode array technology, but this method may not
be specific
ffic enough where spectral differences are low. Detection techniques such as
fluorescence may
ay offer higher selectivity than UV detection, but if many different
a
compounds are to be analyzed, these techniques also may not yield desired results.
With mass spectrometry (MS), several different analyte classes in a wide variety of sample
types can be identified with greater certainty. Although GC/MS is a well-established
technique for food analysis, LC/MS is emerging as a useful tool in this area. A GC-based
analysis is appropriate only for those food compounds that are volatile and thermally
stable. However, many compounds are nonvolatile, extremely polar, or thermally labile.
Such compounds often can be separated successfully with LC, and the development of
improved interfaces has made LC/MS more popular.
18
LC/MS Instrumentation
LC/MS instrumentation can be
considered under four major stages.
The options in each category are not
exhaustive but represent the most
widely used technologies and
demonstrate the number of potential
alternatives in LC/MS:
Separation
Reversed-phase LC
Normal-phase LC
Size-exclusion LC
Ion-exchange LC
Capillary electrophoresis
Ionization Interface
Electrospray ionization (ESI)
Atmospheric pressure chemical
ionization (APCI)
Atmospheric pressure
photoionization (APPI)
Mass Analyzer
Quadrupole
Ion trap
Time-of-flight (TOF)
MS/MS*
Detector
Electron multiplier
Microchannel plate
19
Ionization Sources
Much of the advancement in LC/MS over
recent years has been in the development
of ion sources and techniques that ionize
the analyte molecules and separate the
resulting ions from the mobile phase.
The introduction of atmospheric pressure
ionization (API) techniques greatly
expanded the number of compounds that
can be successfully analyzed by LC/MS.
As the term suggests, ionization takes
place at atmospheric pressure and is
considered to be a soft ionization
method. Following ionization of the analyte
molecules, the resultant analyte ions are
then mechanically and electrostatically
separated from neutral molecules.
Common API techniques are:
20
Ionization Sources
Eventually, the repulsive force between
ions with like charges exceeds the
cohesive forces, and ions are ejected
(desorbed) into the gas phase. The heated
drying gas causes solvent clusters in the
droplets to evaporate. As the droplets
shrink, the charge concentration in the
droplets increases, and the above
process is repeated. The ions are
transported to the mass analyzer through
a series of vacuum stages and ion-focusing
elements. Some gas-phase reactions, mostly
proton transfer and charge exchange,
can also occur between the time ions are
ejected from the droplets and the time
they reach the mass analyzer.
21
Atmospheric Pressure
Photoionization (APPI)
Suitable for: Molecular weight
determination, structure with CID
or MS/MS
Applicable to: Compounds less polar
than those ionizable by APCI
Ionization modes: APPI positive/negative
Atmospheric pressure photoionization
(APPI) for LC/MS is a relatively new
technique. As in APCI, a vaporizer
converts the LC eluent to the gas phase.
A discharge lamp generates photons in a
narrow range of ionization energies. The
range of energies is carefully chosen to
ionize as many analyte molecules as
possible while minimizing the ionization
of solvent molecules. The resulting ions
pass through a glass capillary into the
mass analyzer.
APPI is applicable to many of the same
compounds that are typically analyzed
by APCI. It shows particular promise in
applications of compounds not ionized by
APCI, such as polyaromatic hydrocarbons.
22
Mass Analyzers
Although any type of mass analyzer
could be used for LC/MS, these types
are used most often:
Strengths
Robust operation
Least expensive analyzer
Ease of use
High sensitivity in SIM mode
Excellent quantitation
Quadrupole (Q)
Ion trap (IT)
Time-of-flight (TOF)
Each has advantages and disadvantages
depending on the requirements of a
particular analysis.
The mass analyzer separates ions
according to their mass-to-charge ratio.
The filtration process differs depending
on whether the MS is a quadrupole, ion
trap, or time-of-flight (TOF).
Quadrupole (Q)
Ionized molecules are guided by a series
of lenses into the quadrupole filter. The
quadrupole consists of two pairs of rods
(or their equivalent) where a direct
current (DC) and a radiofrequency (RF)
are applied. By controlling the DC and
RF, the quadrupole can be set to select
the mass-to-charge ratios that can
transverse the distance to the detector
without colliding into the rods.
A quadrupole mass filter can be operated
in a scan mode or select ion monitoring
(SIM) mode. In SIM, the mass filter is set
to pass one selected m/z. This provides
the greatest sensitivity for quantitative
applications. It is used when the analyst
has prior knowledge of what ions to
expect. In scan mode, the mass filter is
set to sequentially pass a range of masses.
It has lower sensitivity because most of
the ions strike the rods during the scan.
This mode is used to collect spectra for
interpretation or a library search.
23
Limitations
Structural information only by
up-front CID
Lack of accurate mass information
Slower scan speed than ion trap
and time-of-flight (TOF)
Ion Trap (IT)
An ion trap is another type of mass filter
where the ions are stored in a single
cavity. The ions are selectively ejected
out of the trap and into the detector.
While a single linear quadrupole can only
perform a single stage MS determination,
the ion trap can be used to perform more
complex experiments. An ion trap can
select an ion and subject it to another
cycle of fragmentation. This technique is
useful when you need to understand the
fragmentation of a particular ion.
Following release from the trap, ions are
detected by an electron multiplier. The
ability to collect multiple levels of MS
data in a single run is one of many
advantages of the ion trap. All MS/MS
n
and MS data acquired from a run are
stored in a single file.
Strengths
n
Multiple-stage MS
Fast-scanning capability
Good resolution
Full-scan MS/MS sensitivity
Auto generation of MS/MS with
higher sensitivity than triple
quadrupole systems (QQQ)
Well-defined fragmentation pathways
from precursor to product ions,
allowing more detailed interpretation
Limitations
No accurate mass information
Less sensitive than QQQ for low
level quantitative studies
Less fragmentation than QQQ in
MS/MS mode because product ions
are not further fragmented (however,
this makes QQQ spectra more
difficult to interpret)
Time-of-Flight (TOF)
Time-of-flight (TOF) mass analyzers
have a wide mass range and can be very
accurate in their mass measurements
with the accuracy and resolution to
distinguish empirical formulas (to identify
unknown compounds) and separate
interfering compounds with the same
nominal mass. They are used to provide
both molecular weight and detailed
structural information for total sample
characterization. TOF is particularly suited
to the analysis of high mass compounds
6
(500 - >10 Daltons), e.g., biomolecules.
FIGURE 2. TIME-OF-FLIGHT MASS ANALYZER.
24
Mass Analyzers
Detection Modes
Narrow dynamic range has traditionally
been a severe limitation on the usability
of TOF MS. New instrumentation, e.g.,
the Agilent LC/MSD TOF, uses an
analog-to-digital conversion that
eliminates the dead-time correction
needed in many traditional TOF
instruments. The result is up to three
decades of dynamic range, which
eliminates the need to match internal
reference mass and sample concentrations.
A reference mass can be introduced at a
lower concentration for less risk of
suppression or interference.
Strengths
Accurate mass information
High resolution
Fast scanning rates
Good scan sensitivity
Limitations
No MS/MS capability except
with up-front CID
Not as sensitive relative to
quadrupole SIM, MS/MS SRM
on QQQ, and ion trap
25
26
ICP-MS Basics
27
ICP-MS Basics
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a powerful technique
for the measurement of elements in a wide range of sample types. Strengths of the
technique include:
Wide elemental coverage virtually all elements can be measured
by ICP-MS, including alkali and alkaline earth elements, transition
and other metals, metalloids, rare earth elements, most of the halogens,
and some of the non-metals.
Performance high sensitivity and low background signals combine
to give very low detection limits (sub-ng/L parts-per-trillion (ppt)
in most cases).
Fast analysis times with a high-speed scanning quadrupole analyzer
measurement of a full suite of elements takes only about 4 minutes
per sample.
Wide analytical working range up to 9 orders in a single acquisition.
Isotopic information.
As the technology behind the technique continues to evolve, ICP-MS is now considered
as a viable alternative to ICP-Optical Emission Spectrometry (OES) for fast measurement
of higher concentration elements (ug/L to mg/L or ppb to ppm concentrations), while
also rivaling or, in many cases, exceeding the detection capability of Graphite Furnace
Atomic Absorption Spectrometry (GFAAS) for the determination of trace and ultra-trace
elements (ng/L or ppt concentrations).
In summary: ICP-MS can measure a full suite of elements in a single multi-element
acquisition, offers a solution to reduce interference effects, accepts almost any sample
type, and also provides isotopic information. These capabilities help to explain the
widespread acceptance of ICP-MS across all industry types including foods and flavors.
28
29
30
The final stage: Analyte ions are separated by the mass spectrometer (MS), which
scans rapidly across the mass range and passes each mass of interest sequentially to
the electron multiplier (EM) detector. After processing, the output of the detector is
a mass spectrum containing the mass and abundance of each ion (Figure 3). Each ion
corresponds to an individual element or isotope in the original sample, and the
abundance is directly proportional to the original concentration.
31
Ar+ + H2 Ar + H2+
In this example the ionized argon is
neutralized by H2 which then allows for
the measurement of Ca at mass 40.
FIGURE 4. SCHEMATIC OF AGILENT 7500CE AND 7500CS ICP-MS
SHOWING THE OCTOPOLE REACTION SYSTEM (ORS) CELL.
32
33
34
T
Techniques
Agilents portfolio of food analysis solutions encompasses
state-of-the-art instrumentation based primarily on mass
spectrometry techniques plus sophisticated software packages.
Each system is designed to deliver the highest level of
performance, while retaining ease of use, flexibility, and
reliability demanded by food analysts all over the world.
Innovations include the powerful Retention Time Locking
software tool and improved acquisition methods for GC/MS.
System innovations include the LC/MSD TOF for identification
of uncharacterized compounds and ICP-MS with Octopole
Reaction System (ORS) technology for trace level quantification
of elements in the most challenging sample matrices.
35
Techniques
Building and Editing RTL Screener/Quant Databases and Libraries
The powerful software techniques of
Retention Time Locking (RTL) [1],
Target Compound Screening [2], and
Deconvolution Reporting [3] all use
retention times (RTs) for an additional
level of compound confirmation. It is
important for maximum productivity and
quality that RTs are constant/reproducible
and embedded in mass spectral libraries
[4]. However, not all compounds are in a
commercially available mass spectral
library, and most mass spectral libraries
do not have RTs.
References
[1] V. Giarocco, B. Quimby, and M. Klee, Retention Time Locking: Concepts and Applications, Agilent Technologies,
publication 5966-2469E www.agilent.com/chem
[2] H. Prest, P. Wylie, K. Weiner, and D. Agnew, Efficient Screening for Pesticides and Endocrine Disrupters Using the
6890/5973 GC/MSD System, Agilent Technologies, publication 5968-4884E www.agilent.com/chem
[3] P. Wylie, M. Szelewski, and C.K. Meng, Comprehensive Pesticide Screening by GC/MSD using Deconvolution
Reporting Software, Agilent Technologies, publication 5989-1157EN www.agilent.com/chem
[4] K. Weiner and H. Prest, Retention Time Locking: Creating Custom Retention Time Locked Screener Libraries,"
Agilent Technologies, publication 5968-8657E www.agilent.com/chem
36
Techniques
Comprehensive Pesticide Screening by GC/MSD
using Deconvolution Reporting Software
Typical target compound analysis
requires finding target ions and meeting
qualifier ion ratios. It is always very
difficult to identify target compounds
from a high matrix background because
the matrix affects the ion ratios of the
target compounds. Background subtraction
and manual integration are often
required to be certain of the results.
This is a time-consuming process; it can
take an experienced analyst an hour to
review/confirm one data file.
Two powerful GC/MS techniques
Retention Time Locking (RTL) and peak
deconvolution have been combined to
create a quantitation and screening tool
that can identify 567 pesticides and
endocrine disrupters from a single run
in a minute or two.
37
Increase Confidence
f
fidence
with Combined Report
The Deconvolution Reporting Software
(DRS) for target compound analysis
combines the results from Agilent
ChemStation, AMDIS, and the NIST 2002
Mass Spectral Search Program (NIST02,
>143,000 compounds) into one easy-toread report, shown in Figure 2.
Pesticides in an Herbal Mix
Figure 1 shows a total ion chromatogram
(TIC) from the extract of an herbal mix.
This sample was chosen because herbs
are among the most difficult vegetable
products to analyze. Their extracts contain
a large number of natural products that
interfere with pesticide analysis.
38
Techniques
New Approaches to the Development of GC/MS
Selected Ion Monitoring Acquisition and Quantitation Methods
Operating a GC/MS in selected ion
monitoring (SIM) mode leads to a
sensitivity increase for target analytes
through the selective detection of ions
most indicative of the compounds of
interest. GC/MS-SIM methods are useful
and widely applied, although they can
be complicated to develop and maintain,
especially when the compound list is
long. The AutoSIM feature of the Agilent
Mass Selective Detector Productivity
ChemStation software and retention time
locking (RTL) reduces the difficulty in
managing SIM acquisition and quantitation
databases. RTL makes retention times
permanent despite column maintenance
or even replacement.
Example
Figure 1 shows a GC/MS total ion
chromatogram for 83 compounds that
are part of the EPA 8270 method. Notice
the separation is very poor in the 6-to-13minute region. Applying the defaults of
the SIM setup produces 13 SIM groups
and a warning that there are too many
FIGURE 1. MERGED QUANTITATION ION CHROMATOGRAM OF THE HIGHEST STANDARD IN A SIM METHOD GENERATED BY THE SIM
SETUP SETTINGS WITH A SHORTER TIME FOR THE MINIMUM TIME BETWEEN PEAK AND GROUP START PARAMETER. THERE ARE
19 SIM GROUPS TO ACCOMMODATE ALL THE COMPOUNDS.
39
40
Techniques
Identification of Unknowns using the Agilent LC/MSD TOF
Atmospheric pressure ionization
time-of-flight (API-TOF) MS can be
used for identifying true unknowns.
Identification is based on the generation
of an accurate mass for the protonated
molecular ion that is sufficient to
determine the correct empirical formula.
This high-precision technique does not
depend on fragmentation, although
fragmentation data derived using the
ion trap or by up-front collision-induced
dissociation in the single quad is
complementary and helpful.
Processed Waste Water Sample
A 20-L portion of a process in-feed water
sample for drug analysis was injected
into the ESI-TOF-MS, under optimized
conditions. Appropriate extracted ion
chromatograms (EICs) were generated and
FIGURE 1. STACKED EICS FOR WATER SAMPLE 119, FOR DIPHENHYDRAMINE, SULFAMETHOXAZOLE, AND CARBAMAZAPINE.
THERE ARE THREE POSSIBLE HITS SINCE MASSES AND RTS MATCH EXPECTATIONS.
41
FIGURE 1. RESULTS OF 13 SEPARATE ANALYSES OF THE CCV SAMPLE OVER THE 15.5 HOUR SAMPLE SEQUENCE. ALL ANALYTE
A METHOD 6020 ARE +/- 10%.
PA
P
ELEMENTS ARE REPORTED. ACCEPTABLE
TTABLE CONTROL LIMITS ACCORDING TO US EP
42
Foods
Agilents instruments, systems, and supplies are used
throughout the food production chain, including incoming
inspection, new product development, quality control and
assurance, and packaging. Innovative instrumental and
software data-handling developments, such as the LC/MSD
Trap XCT and TOF, ICP-MS with Octopole Reaction System
technology, and Retention Time Locking, help analysts solve
problems more reliably, more efficiently, and with higher
quality results than ever before.
43
Foods
GC/MS Approaches to the Analysis of Acrylamide in Foods
The discovery of acrylamide (2-propenamide) in fried and baked foods at
levels many times that allowed in water
suggested a much higher exposure than
previously estimated. Acrylamide, a known
neurotoxin, is considered a probable
human carcinogen. The World Health
Organization considers 0.5 g/L the
maximum level for acrylamide in water.
However, foods such as french fries,
baked potato chips, crisp breads, and
other common cooked foods were found
to contain acrylamide between 100 and
1000 g/kg. Recent work has suggested
that acrylamide forms via the Maillard
reaction, which occurs when amino acids
and sugars (for example, asparagine and
sucrose) are heated together. The concern
over these relatively high concentrations
has led to studies of the occurrence of
acrylamide in a wide variety of foods.
Rapid Screening via GC/MS-SIM with
Positive Chemical Ionization
A wide variety of instrumental approaches
has been applied to acrylamide analysis,
including a simple GC/MS-SIM approach
with positive chemical ionization (PCI)
which provides good selectivity and
picogram-sensitivity for acrylamide.
FIGURE 1. EXTRACTED ION CHROMATOGRAMS FOR ACRYLAMIDE (84 ng/g) IN SAMPLE OF WHITE BREAD.
44
Foods
Improving the Analysis of Fatty Acid Methyl Esters Using Retention Time Locked
Methods and Retention Time Databases
The analysis of fatty acid methyl esters
(FAMEs) is used for the characterization
of the lipid fraction in foods and is one
of the most important applications in
food analysis. Lipids mainly consist of
triglycerides, which are esters of one
glycerol molecule and three fatty acids.
Most edible fats and oils are composed
largely of 12 to 20 carbon fatty acids
[lauric acid (dodecanoic acid) to
arachidic acid (eicosanoic acid)]. Besides
linear saturated fatty acids, branched,
mono-unsaturated, di-unsaturated, and
higher unsaturated fatty acids can occur.
45
46
Pesticides
Most of the fruit and vegetables we put in our shopping bags
are grown using pesticides chemicals used to protect crops
from insects and weeds. While it is important to ensure the
food we eat is safe from disease and damage caused by insects,
it is also vital for the protection of human health that pesticide
residues are routinely monitored in food and water samples.
Agilents comprehensive range of chemical analysis
instrumentation is used daily in food labs around the world
to screen for pesticides to ensure that regulated Maximum
Residue Levels (MRLs) are not exceeded. Analytical techniques
are overwhelmingly based on chromatography (GC, LC),
with detection by mass selective detectors.
47
Pesticides
Identification and Quantitation of Pesticides in the Parts-per-Trillion Range
Using Retention Time Locking and GC/MS
Traditionally, pesticides are analyzed
on a gas chromatograph (GC) with
element-selective detectors (ESDs).
Although these ESDs provide low ppb
detection limits and are easy to operate,
the data does not provide sufficient
information to confirm a compounds
presence with confidence. In contrast,
a mass spectrometer (MS) provides
additional information and increased
confidence
ffidence in the assignment of
compound identity. In addition GC/MS
detection limits can be optimized in
various ways:
Run the MS in single ion monitoring
(SIM) mode
Make large volume injections (LVIs)
Combine both the above methods
FIGURE 1. ION CHROMATOGRAMS OF 100-L CHLORTHALDIMETHYL INJECTED AT 0.05 pg/L. THE TOP PORTION WAS
FROM A FULL-SCAN RUN, AND THE BOTTOM PORTION WAS
FROM A SIM RUN.
Experimental
A mixture from the California Department
of Food and Agriculture (CDFA) of
80 pesticides at 5000 pg/L each was
used as the stock solution for this study.
The mixture containing carbamate,
organochlorine, organophosphorus,
and organonitrogen pesticides was used
to compare the lowest detection limits
of splitless injection and L
LVI under Scan
and SIM modes.
48
Pesticides
Trace Level Pesticide Analysis by GC/MS Using Large-Volume Injection
Concern has increased that certain
pesticides and other synthetic chemicals
may be acting as pseudo hormones which
disrupt the normal function of the
endocrine system in wildlife and humans.
Because the endocrine system can be
sensitive to extremely low hormone
concentrations, there is a need to measure
concentrations of suspected endocrine
disrupters (many of which are pesticides)
at very low legislated levels in food and
water supplies. To achieve the required
sensitivity, GC system detection limits
can be improved by one to two orders
of magnitude over standard methods
that call for 1- or 2-L injections using
large-volume injection (LVI) with a
programmable temperature vaporizer
(PTV) inlet operating in solvent-vent mode.
Experimental
An Agilent 6890 Series gas chromatograph
(GC), configured with a programmable
temperature vaporizer (PTV) inlet, a 6890
Series automatic liquid sampler (ALS),
and an Agilent 5973 mass selective
detector (MSD), was used for the analysis
of pesticides in standards and several
food extracts. By making 100-L injections,
several pesticides could be identified by
scanning gas chromatography/mass
spectrometry (GC/MS) at the 100-ppt
(100 ng/L) level (Figure 1).
Analysis of a bell pepper extract revealed
several pesticide residues. As seen in
Figure 2, chlorpyrifos and the endosulfans
were easily detected. The Florida
Department of Agriculture determined
the concentration of chlorpyrifos,
alpha-endosulfan, beta-endosulfan, and
endosulfansulfate to be 0.210, 0.011,
49
50
Pesticides
Rapid Screening Method for the Analysis of Paraquat and Diquat by LC/MSD
Using Selective Ion Monitoring and Large-Volume Injection
Paraquat and diquat, bipyridilium salts,
are used in agriculture as nonselectivecontact herbicides. They are also
commonly used in commercial weed
killer formulations for domestic weed
control. Screening of these herbicides is
possible using LC/MS and a direct
aqueous injection of the sample.
The World Health Organization (WHO)
has set an advisory value of 10 g/L
for paraquat in drinking water. In this
application, a limit of detection (LOD)
of well below 1 g/L is achieved for
paraquat and diquat, as well as for
amitrole and chlormequat.
51
Use of Optional Gas and Collision Cell for Enhanced Sensitivity of the
Organophosphorus Pesticides by GC-ICP-MS
Organophosphorus pesticides (OPs) are
used widely as insecticides, herbicides,
and fungicides. Concern over the levels
of these compounds in our environment
exists because they pose a threat to human
health. As cholinesterase inhibitors, the
OP pesticides are potent neurotoxins.
A novel method has been developed
using ICP-MS to detect phosphorous
following separation of the OPs by GC.
Instrument Detection Limits
Table 1 depicts detection limits according
to two EPA methods (columns 1,2) and by
GC-ICP-MS (columns 3,4). A comparison
of columns 1 and 3 demonstrates the
superior sensitivity of GC-ICP-MS
compared to conventional EPA methods.
Analyte
Diazinon
26 ppb
30 ppb
0.2 ppb
0.012 ppb
Disulfoton
5.8 ppb
50 ppb
0.2 ppb
0.004 ppb
Terbufos
11 ppb
50 ppb
0.2 ppb
0.004 ppb
Fonofos
60 ppb
0.2 ppb
0.007 ppb
52
Veterinary Drugs
Animal diseases caused by viruses, bacteria, protozoa, and/or
fungi are prevented or treated with drugs. It is also common
practice to administer growth-enhancing drugs to livestock
and poultry during their lifetime. Because drug residues may
be found in foods of animal origin such as milk, eggs, and meat,
government agencies around the world implement strict
surveillance and monitoring programs to ensure food safety.
Agilents advanced technologies and methodologies based on
mass spectrometry are highly suitable for the rapid and
reliable analysis of drug residues in foods at regulated levels.
53
Veterinary Drugs
High-Resolution Quantitative Analysis of Nitrofuran Derivatives
in Poultry and Shrimp Using a New oa-ESI-TOF
The drugs furazolidone, furaltadone, nitrofurazone, and nitrofurantoin belong to a
group of nitrofuran antibacterial drugs which are widely used as feed additives to
prevent bacterial enteritis, Escherichia coli, and Salmonella infections in cattle, fish,
swine, and poultry.
Time-of-Flight (TOF) mass spectrometry is well known for its high resolution and
accurate mass-measurement capabilities. The high-resolving power enables good
mass-measurement accuracy and the differentiation of isobaric species, i.e., two
compounds with the same nominal mass but different elemental composition and,
therefore, different exact masses.
Operating the time-of-flight (TOF) mass spectrometer with a dual orthogonal electrospray
source in positive ion mode provides fully automated, accurate mass assignments in the
low ppm range with wide dynamic range for nitrofuran metabolites. The method allows
quantitation of nitrofuran antibiotics down to 0.5 ppb in shrimp (Figure 1) and poultry
with very good relative standard deviations. Mass accuracy is maintained throughout
the concentration range with standard deviations less than 1 ppm. Internal referencing
through a dual orthogonal ESI sprayer design ensures routine operation.
FIGURE 1. MH REGION FOR NPAMOZ AT THE 0.5 PPB LEVEL IN SHRIMP WITH EMPIRICAL FORMULA CALCULATION RESULTS.
54
Veterinary Drugs
Quantitation of Nitrofuran Metabolites in Shrimp and Poultry by
LC/MS/MS Using the LC/MSD Trap XCT
Nitrofuran antibiotics are widely used for
the treatment of infectious diseases in
cattle, pigs, shrimp, and poultry. Due to
their rapid metabolism, nitrofuran parent
substances are not suitable for monitoring,
and typically their metabolites are
analyzed. An LC/MS/MS method exists
for the qualitative and quantitative
measurement of nitrofuran metabolites
in chicken and shrimp, using an ion trap
with an orthogonal electrospray source in
positive ion mode and multiple reaction
monitoring (MRM).
Very low limits of detection (LOD) are
required for nitrofuran metabolites, and
the metabolite derivatization method
increased the ionization efficiency, as
well as improved the chromatographic
separation. Operating the ion trap mass
spectrometer in MRM mode, only
precursor ions are chosen and full-scan
MS/MS-spectra of the corresponding
analytes are acquired. These full-scan
MS/MS spectra are then used for
identification by comparing them with
MS/MS spectra stored in a library. No
further qualifier ion has to be monitored.
The European Union has set a Minimum
Required Performance Level (MRPL) of
1 g/kg for Nitrofuran metabolites. These
detection limits are easily reached using
55
Compound Identification
and Confirmation
The Agilent 1100 MSD has the capability
of acquiring up to four separate MS
signals during the same run, where each
signal can be made up of a number of
selected ions (SIM) or a full-scan
spectrum. For example, Signal 1, with a
low fragmentor voltage to maximize
parent-ion response, can include each of
+
the [M+H] ions in the target list, while
Signal 2, at higher fragmentor voltages,
can acquire the confirmatory fragment
ions. For analytes expected at higher
concentrations, Signal 1 could acquire
in SIM mode for quantitation, while
Signal 2 could be set for scan mode for
identification. Figure 1 demonstrates the
former example, with the Fragmentor set
to 70 V for Signal 1 (MSD1), and 200 V
for Signal 2 (MSD2).
56
Veterinary Drugs
Detection, Confirmation and Quantification of Chloramphenicol in Honey and
Shrimp at Regulatory Levels Using Quadrupole and Ion Trap LC/MS
Chloramphenicol (CAP) is a broad-range
antibiotic that has found its way into
foodstuffs, such as honey and shrimp.
Because it has displayed significant
toxicological effects on humans, it has
been banned from foods in the European
community and the United States at
levels greater than 0.1 ppb. Methodology
capable of meeting these regulatory
requirements has been developed based
on quadrupole (with negative mode
electrospray ionization) and ion trap
LC/MS. The quadrupole instrument
provides excellent results for quantitative
analysis and can give some confirmation
information. The ion trap system gives
excellent full-spectrum confirmation at
the regulated concentration.
57
58
Packaging
The packaging used to present and protect foodstuffs is
essential to keeping food fresh. However, additives for the
manufacturing process can unintentionally migrate into foods
from packaging materials. These are permitted only if the
amounts present are so low as to be considered insignificant.
Direct additives are intentionally added to foods to perform
a specific function. Examples include preservatives, colorings,
and flavorings. Used principally to improve and maintain food
quality, all additives must be proven to be safe, effective, and
measurable before being allowed in the foods we consume.
Most countries food-additive legislation is based on a positive
list, with only authorized substances permitted for use and
in limited quantities. Agilents portfolio of instrumentation
and applications expertise provides food scientists with the
tools they need to meet their analytical challenges.
59
Packaging
GC/MS Approaches to the Analysis of Monochloropropanediol
Hydrolyzed vegetable protein (HVP) is a
widely used flavoring found in soups,
sauces, and some meat products. During
the acid hydrolysis process of vegetable
proteins, the hydrochloric acid agent
reacts with triglycerides to produce the
suspected carcinogen 3-chloro-1,2propanediol (3-MCPD) [1]. The Association
of Official Analytical Chemists (AOAC)
has published a method for the extraction,
separation and identification of 3-MCPD
in foods and ingredients, using electron
impact (EI) ionization GC/MS [2].
The 3-MCPD is eluted with diethyl
ether and a portion is derivatized
with heptafluorobutyrylimidazole.
The resulting EI mass spectrum lacks a
molecular ion and has a base peak at m/z
169 from [C3F7]+ fragments; see Figure 1.
However, selected ion monitoring (SIM) of
m/z fragments at 453, 289, 275, and 253
in a standard solution suggests detection
at subpicogram levels is possible.
The methodology can be improved further
using electron capture negative ionization
(ECNI) GC/MS. Figure 2 shows the ECNI
mass spectrum of the 3-MCPD derivative
under standard conditions with methane
buffer gas. Unlike the EI results, the
molecular ion (502 m/z) is detected,
although at low relative intensity. Analysis
of standards suggests that it would be
possible to detect a few picograms in the
scanning mode and less than one picogram
in the selected ion mode (SIM).
Further optimization of ECNI is possible,
such as a lower source temperature to
take advantage of the low boiling point
of the derivative, which may improve the
spectrum and detection limits. The real
advantage, though, is expected to be in
typical food samples where its greater
selectivity will demonstrate a strong
suppression of chemical noise and
enhance method detection limits.
60
Packaging
A New Approach to the Analysis of Phthalate Esters by GC/MS
Some phthalate esters are characterized
as endocrine disruptors capable of liver
and kidney damage, and possible
testicular or reproductive-tract birth
defect problems. GC/MS methodology
using positive chemical ionization (PCI)
and retention time locking exists for the
determination of 29 phthalate esters,
including six recently banned from baby
toys by the European Union [1], in a wide
variety of matrices. Using ammonia as
the PCI reagent gas provides a high
degree of selective ionization for the
phthalates, primarily producing spectra
in which the protonated molecule (M+1)
is the base peak. PCI is also an advantage
in complex matrices, where the nonselective ionization of Electron Impact
(EI) ionization produces a high chemical
background. The chromatograms presented
in Figure 1 illustrate this point. The EI
spectra of the phthalates produce m/z
149 as the base peak for all the phthalates
present; distinguishing ions are minor
constituents (<10% relative intensity),
making identification complicated.
However, by examining the appropriate
PCI-ammonia ions, the various phthalates
are easily distinguished.
Locking the retention time enhances
confidence in the characterization of the
various phthalate isomers on the basis
of their definitive retention time. This is
especially helpful for determinations
using selected ion monitoring (SIM),
since SIM groups need not be edited after
column maintenance [2].
61
62
Metals
Analysis of metals in foods is critical. While metals such as Zn,
Cu, Ca, Mg, Fe, Se, Li, Co, Mn, and P are important nutrients
required for human and animal health, other metals including
Pb, Cd, As, Be, Ni, and Hg have no known nutritional function
and may be highly toxic, even at very low concentrations.
Many metals have nutritional functions at low concentrations
and are toxic at higher concentrations. The nutritional value
or toxicity of metals is also dependent on the form or species
of the metal. Agilents highly sensitive ICP-MS series of
instruments and leadership in coupling chromatographic
techniques to ICP-MS provide food labs with the analytical
tools they can rely on.
63
Metals
A Comparison of the Relative Cost and Productivity of Traditional Metals
Analysis Techniques Versus ICP-MS in the Analysis of Foods
As our understanding of the effects of
metals on human and animal health
increases, we find it necessary to monitor
more elements in more types of samples
at lower levels than ever before. The
challenge is to implement suitable
techniques capable of cost-effective and
high-quality analytical measurement of
a full range of elements in a variety of
sample types.
Traditionally, elemental analysis in foods
has been performed by atomic absorption
and atomic emission spectroscopy.
The trace elements have generally been
measured by graphite furnace atomic
absorption (GFAA), a highly sensitive
single-element technique. The more
common elements have been measured
by inductively coupled plasma optical
emission spectroscopy (ICP-OES), which
is less sensitive but capable of
simultaneous multi-element analysis.
However, as the need for more analyses
at lower detection limits increases, the
combination of GFAA plus ICP-OES is
not up to the task, and many labs are
investing in ICP-MS for the analysis of
all metals in foods and drugs.
64
Metals
Determination of Mercury in Microwave Digests of Foodstuffs by ICP-MS
The determination of sub ng/g
concentrations of mercury is of special
importance in the field of trace metal
analysis. Even at trace levels, mercury
is toxic and causes neurological damage,
particularly in fetuses and young children.
Anthropogenic sources of mercury in the
environment include coal-fired power
stations and chlor-alkali works. In the
aquatic environment, bacteria convert
elemental mercury Hg(0) to methylmercury,
which is accumulated and passed up the
food chain. Fish and shellfish are significant
contributors of mercury to the human diet.
Mercury is recognized as a problem element
analytically. It is known to adsorb onto
the walls of storage containers and
volatilize as mercury vapor. Additionally,
its high first ionization potential and
numerous isotopes have limited its
sensitivity in ICP-MS analysis. However,
a quantitative method for the determination
of mercury in foodstuffs is available
using a 7500 ICP-MS. Microwave digests
were prepared and then analyzed by
ICP-MS equipped with the integrated
sample introduction system (ISIS) in
the high sample throughput mode, and a
microflow concentric nebulizer. To avoid
memory effects, gold was added offline to
all standards/samples and wash solutions
to act as a cleansing agent. Five calibration
plots over a 36-hour period are shown in
Figure 1 to demonstrate the systems
stability. As can be seen, good linearity
was achieved over an extended calibration
range, indicating that memory effects had
been effectively eliminated. Between the
calibrations, more than 120 various
microwave foodstuff digests were analyzed.
Two certified reference materials (CRMs)
were analyzed throughout a survey of
500 samples. These acted as quality control
materials for the microwave digestion as
well as the quantification. The CRMs
used were a crab paste Metals LGC 7160,
0.096 mg/kg and peach leaves NIST 1547,
65
Element
Found (mg/kg)
Certified (mg/kg)
%RSD
Mn
0.26
0.26
1.3%
Cu
0.69
0.70
1.1%
Zn
48
46
0.2%
Se
0.19
0.11
9.1%
Pb
0.020
0.019
3.0%
66
Metals
NIST 1573 Tomato Leaves using an Agilent 7500 ORS ICP-MS
In extracts of complex matrices such as
foods, traditional (non-cell) ICP-MS can
suffer from interferences. Though they
are less severe than with traditional
techniques, e.g., ICP-atomic emission
spectroscopy (AES), they can compromise
detection limits for certain key elements;
see Table 1. The 7500 Octopole Reaction
System (ORS) ICP-MS can eliminate these
interferences, allowing for trace
measurement even in difficult matrices.
The data in Table 2 was obtained from
the analysis of a perchloric/nitric acid
digestion of NIST 1573 Tomato Leaves
using an Agilent 7500c ORS instrument.
The excellent agreement between the
reference and obtained values for Cr, Fe,
and As for multiple isotopes illustrates
how the ORS eliminates interferences
from ArC, ArO, and ArCl. The data was
obtained in a single acquisition highlighting
the wide dynamic range of the 7500 Series.
For more information on this topic,
go to www.agilent.com/chem,
click the library link and search for
pub. # 5988-6795EN.
67
Element
Molecular
Interference
Cr
40
35
Fe
40
12
38
16
Ar C, Ar O
16
Cl O
16
Ar O
Element
Molecular Interference
Cu
40
As
40
Se
40
23
Ar Na
35
Ar Cl
37
40
38
40
40
Ar Cl, Ar Ar, Ar Ar
Element
Certified
(mg/kg)
Found
(mg/kg)
Element
Element
Element
43Ca
5.05%
5.08%
63Cu
4.7
4.4
39K
2.70%
2.62%
65Cu
4.7
4.4
52Cr
1.99
1.79
75As
0.112
0.115
53Cr
1.99
1.79
78Se
0.054
0.06
54Fe
368
368
111Cd
1.52
Se
56Fe
368
368
1.42
TABLE 2. ANALYSIS OF NIST 1573 TOMATO LEAVES USING THE 7500 ORS.
Appendix
Agilent Pesticide Library
Pesticide identification is efficient and certain with Agilents GC/MS instrumentation, retention
time locking (RTL) software tool, and RTL pesticide library of 567 compounds, as listed below.
Each entry in the RTL library has a full spectrum and a target retention time. When the sample is
run on an Agilent GC/MS system for confirmation, RTL will ensure that the analytes appear at the
same retention times consistently. The match or mismatch of the retention times with the library
entries can be used as a qualifier, adding another level of confidence in the results.
Note: The pesticide library can be updated by the user at any time.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Compound name
1,2,4-Trichlorobenzene
1,2-Dibromo-3-chloropropane
17a-Ethynylestradiol
2-(1-naphthyl)acetamide
2-(2-Butoxyethoxy)ethyl thiocy
2-(Octylthio)ethanol
2,3,4,5-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
2,3,5-Trichlorophenol
2,3,5-Trimethacarb
2,3,5-Trimethylphenyl methyl c
2,3,7,8-Tetrachlorodibenzofura
2,3,7,8-Tetrachlorodibenzo-p-d
2,4,5-T methyl ester
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2,4-D methyl ester
2,4-D sec-butyl ester
2,4-DB methyl ester
2,4-Dichlorophenol
2,4-Dichlorophenyl benzenesulf
2,4-Dimethylaniline
2,6-Dichlorobenzonitrile
2,6-Dimethylaniline
2-[3-Chlorophenoxy]propionamid
2-Ethyl-1,3-hexanediol
2-Hydroxyestradiol
2-Methylphenol
2-Phenoxypropionic acid
3,4,5-Trimethacarb
3,4-Dichloroaniline
3,5-Dichloroaniline
3-Chloroaniline
3-Hydroxycarbofuran
4,4-Dichlorobenzophenone
4,6-Dinitro-o-cresol (DNOC)
4-Chloroaniline
4-Methylphenol
No.
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
CAS #
120-82-1
96-12-8
57-63-6
86-86-2
112-56-1
3547-33-9
4901-51-3
58-90-2
935-95-5
933-78-8
2655-15-4
2655-15-4
51207-31-9
1746-01-6
1928-37-6
95-95-4
88-06-2
1928-38-7
N/A
18625-12-2
120-83-2
97-16-5
95-68-1
1194-65-6
87-62-7
5825-87-6
94-96-2
362-05-0
95-48-7
940-31-8
2686-99-9
95-76-1
626-43-7
108-42-9
16655-82-6
90-98-2
534-52-1
106-47-8
106-44-5
69
Compound name
5,7-Dihydroxy-4-methoxyisofla
9,10-Anthraquinone
Acephate
Acetochlor
Acifluorfen methyl ester
Alachlor
Aldrin
Allidochlor
Ametryn
Amidithion
Aminocarb
Amitraz
Ancymidol
Anilazine
Aniline
Atraton
Atrazine
Azaconazole
Azamethiphos
Azinphos-ethyl
Azinphos-methyl
Aziprotryne
Azobenzene
Barban
Benalaxyl
Benazolin-ethyl
Bendiocarb
Benfluralin
Benfuresate
Benodanil
Bentazone
Bentazone methyl derivative
Benthiocarb
Benzo(a)pyrene
Benzophenone
Benzoylprop ethyl
b-Estradiol
BHC alpha isomer
BHC beta isomer
CAS #
491-80-5
84-65-1
30560-19-1
34256-82-1
N/A
15972-60-8
309-00-2
93-71-0
834-12-8
919-76-6
2032-59-9
33089-61-1
12771-68-5
101-05-3
62-53-3
1610-17-9
1912-24-9
60207-31-0
35575-96-3
2642-71-9
86-50-0
4658-28-0
103-33-3
101-27-9
71626-11-4
25059-80-7
22781-23-3
1861-40-1
68505-69-1
15310-01-7
25057-89-0
N/A
28249-77-6
50-32-8
119-61-9
22212-55-1
50-28-2
319-84-6
319-85-7
No.
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
Compound name
BHC delta isomer
Bifenox
Bifenthrin
Binapacryl
Bioallethrin
Bioallethrin S-cyclopentenyl i
Bioresmethrin
Biphenyl
Bis(2-ethylhexyl)phthalate
Bisphenol A
Bitertanol I
Bitertanol II
Bromacil
Bromobutide
Bromocyclen
Bromophos
Bromophos-ethyl
Bromopropylate
Bromoxynil
Bromoxynil octanoic acid ester
Buprofezin
Butachlor
Butamifos
Butoxycarboxim
Butralin
Butyl benzyl phthalate
Butylate
Butylated hydroxyanisole
Captafol
Captan
Carbaryl
Carbetamide
Carbofuran
Carbofuran-3-keto
Carbophenothion
Carbosulfan
Carboxin
Chinomethionat
Chloramben methyl ester
Chloranocryl
Chlorbenside
Chlorbromuron
Chlorbufam
Chlordecone
Chlordimeform
Chlorfenethol
Chlorfenprop-methyl
Chlorfenson
Chlorfenvinphos
CAS #
319-86-8
42576-02-3
82657-04-3
485-31-4
584-79-2
28434-00-6
28434-01-7
92-52-4
17-81-7
80-05-7
55179-31-2
55179-31-2
314-40-9
74712-19-9
1715-40-8
2104-96-3
4824-78-6
18181-80-1
1689-84-5
1689-99-2
69327-76-0
23184-66-9
36335-67-8
34681-23-7
33629-47-9
85-68-7
2008-41-5
25013-16-5
2425-06-1
133-06-2
63-25-2
16118-49-3
1563-66-2
N/A
786-19-6
55285-14-8
5234-68-4
02439-01-2
7286-84-2
2164-09-2
103-17-3
13360-45-7
1967-16-4
143-50-0
6164-98-3
80-06-8
14437-17-3
80-33-1
470-90-6
No.
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
70
Compound name
Chlorflurecol-methyl ester
Chlormefos
Chlornitrofen
Chlorobenzilate
Chloroneb
Chloropropylate
Chlorothalonil
Chlorotoluron
Chlorpropham
Chlorpyrifos
Chlorpyrifos Methyl
Chlorthal-dimethyl
Chlorthiamid
Chlorthion
Chlorthiophos
Chlorthiophos sulfone
Chlorthiophos sulfoxide
Chlozolinate
cis-Chlordane
Clomazone
Coumaphos
Crimidine
Crotoxyphos
Crufomate
Cyanazine
Cyanofenphos
Cyanophos
Cycloate
Cycluron
Cyfluthrin I
Cyfluthrin II
Cyfluthrin III
Cyfluthrin IV
Cyhalothrin I (lambda)
Cymoxanil
Cypermethrin I
Cypermethrin II
Cypermethrin III
Cypermethrin IV
Cyprazine
Cyprofuram
Cyromazine
d-(cis-trans)-Phenothrin-I
d-(cis-trans)-Phenothrin-II
Dazomet
Decachlorobiphenyl
Deltamethrin
Demephion
Demeton-S
CAS #
2536-31-4
24934-91-6
1836-77-7
510-15-6
2675-77-6
5836-10-2
1897-45-6
15545-48-9
101-21-3
2921-88-2
5598-13-0
1861-32-1
1918-13-4
500-28-7
60238-56-4
N/A
N/A
84332-86-5
5103-71-9
81777-89-1
56-72-4
535-89-7
7700-17-6
299-86-5
21725-46-2
13067-93-1
2636-26-2
1134-23-2
2163-69-1
68359-37-5
68359-37-5
68359-37-5
68359-37-5
68085-85-8
57966-95-7
52315-07-8
52315-07-8
52315-07-8
52315-07-8
22936-86-3
69581-33-5
6215-27-8
26002-80-2
26002-80-2
533-74-4
2051-24-3
52918-63-5
8065-62-1
126-75-0
Appendix
No.
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
Compound name
Demeton-S-methylsulfon
Desbromo-bromobutide
Desmedipham
Desmetryn
Dialifos
Di-allate I
Di-allate II
Diamyl phthalate
Diazinon
Dibrom (naled)
Dicamba
Dicamba methyl ester
Dicapthon
Dichlofenthion
Dichlofluanid
Dichlone
Dichlormid
Dichlorophen
Dichlorprop
Dichlorprop methyl ester
Dichlorvos
Diclobutrazol
Diclofop methyl
Dicloran
Dicrotophos
Dicyclohexyl phthalate
Dicyclopentadiene
Dieldrin
Diethatyl ethyl
Diethofencarb
Diethyl dithiobis(thionoformat)
Diethyl phthalate
Diethylene glycol
Diethylstilbestrol
Difenoconazol I
Difenoconazol II
Diflufenican
Dimefox
Dimethachlor
Dimethametryn
Dimethipin
Dimethoate
Dimethylphthalate
Dimethylvinphos(z)
Dimetilan
Di-n-butylphthalate
Diniconazole
Dinitramine
Dinobuton
CAS #
17040-19-6
N/A
13684-56-5
1014-69-3
10311-84-9
2303-16-4
2303-16-4
131-18-0
333-41-5
300-76-5
1918-00-9
6597-78-0
2463-84-5
97-17-6
1085-98-9
117-80-6
37764-25-3
97-23-4
120-36-5
57153-17-0
62-73-7
75736-33-3
51338-27-3
99-30-9
141-66-2
84-61-7
77-73-6
60-57-1
38727-55-8
87130-20-9
502-55-6
84-66-2
111-46-6
56-53-1
119446-68-3
119446-68-3
83164-33-4
115-26-4
50563-36-5
22936-75-0
55290-64-7
60-51-5
131-11-3
2274-67-1
644-64-4
84-74-2
83657-24-3
29091-05-2
973-21-7
No.
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
71
Compound name
Dinocap I
Dinocap II
Dinocap III
Dinocap IV
Dinoseb
Dinoseb acetate
Dinoseb methyl ether
Dinoterb
Dinoterb acetate
Di-n-propyl phthalate
Dioxacarb
Dioxathion
Dioxydemeton-S-methyl
Diphacinone
Diphenamid
Diphenylamine
Dipropetryn
Disulfoton
Ditalimfos
Dithiopyr
Diuron
Dodemorph I
Dodemorph II
Drazoxolon
Edifenphos
Endosulfan (alpha isomer)
Endosulfan (beta isomer)
Endosulfan ether
Endosulfan lactone
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Epoxiconazole
EPTC
Erbon
Esfenvalerate
Esprocarb
Etaconazole
Ethalfluralin
Ethiofencarb
Ethiolate
Ethion
Ethofumesate
Ethoprophos
Ethoxyquin
Ethylenethiourea
Etridiazole
CAS #
39300-45-3
39300-45-3
39300-45-3
39300-45-3
88-85-7
2813-95-8
6099-79-2
1420-07-1
3204-27-1
131-16-8
6988-21-2
78-34-2
17040-19-6
82-66-6
957-51-7
122-39-4
4147-51-7
298-04-4
5131-24-8
97886-45-8
330-54-1
1593-77-7
1593-77-7
5707-69-7
17109-49-8
959-98-8
33213-65-9
3369-52-6
3868-61-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
2104-64-5
106325-08-0
759-94-4
136-25-4
66230-04-4
85785-20-2
71245-23-3
55283-68-6
29973-13-5
2941-55-1
563-12-2
26225-79-6
13194-48-4
91-53-2
96-45-7
2593-15-9
No.
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
Compound name
Etrimfos
Famphur
Fenarimol
Fenazaflor
Fenbuconazole
Fenchlorphos
Fenfuram
Fenitrothion
Fenobucarb
Fenoprop
Fenoprop methyl ester
Fenoxycarb
Fenpropathrin
Fenson
Fensulfothion
Fenthion
Fenthion sulfoxide
Fenuron
Fenvalerate I
Fenvalerate II
Fepropimorph
Flamprop-isopropyl
Flamprop-methyl
Fluazifop-p-butyl
Flubenzimine
Fluchloralin
Flucythrinate I
Flucythrinate II
Flumetralin
Fluometuron
Fluorodifen
Fluotrimazole
Flurenol-butyl ester
Flurenol-methylester
Fluridone
Flurochloridone I
Flurochloridone II
Fluroxypyr-1-methylheptyl este
Flusilazole
Flutolanil
Flutriafol
Fluvalinate-tau-I
Fluvalinate-tau-II
Folpet
Fonofos
Formothion
Fuberidazole
Furalaxyl
Furathiocarb
CAS #
38260-54-7
52-85-7
60168-88-9
14255-88-0
119611-00-6
299-84-3
24691-80-3
122-14-5
3766-81-2
93-72-1
4841-20-7
79127-80-3
64257-84-7
80-38-7
115-90-2
55-38-9
N/A
101-42-8
51630-58-1
51630-58-1
67564-91-4
52756-22-6
52756-25-9
79241-46-6
37893-02-0
33245-39-5
70124-77-5
70124-77-5
62924-70-3
2164-17-2
15457-05-3
31251-03-3
2314-09-2
1216-44-0
59756-60-4
61213-25-0
61213-25-0
81406-37-3
85509-19-9
66332-96-5
76674-21-0
102851-06-9
102851-06-9
133-07-3
944-22-9
2540-82-1
3878-19-1
57646-30-7
65907-30-4
No.
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
72
Compound name
Furmecyclox
Heptachlor
Heptachlor epoxide
Heptachlor exo-epoxide isomer
Heptenophos
Hexabromobenzene
Hexachlorobenzene
Hexachlorophene
Hexaconazole
Hexazinone
Hexestrol
Imazalil
Ioxynil
Iprobenfos
Iprodione
Isazophos
Isobenzan
Isobornyl thiocyanoacetate
Isocarbamide
Isodrin
Isofenphos
Isomethiozin
Isoprocarb
Isopropalin
Isoprothiolane
Isoproturon
Isoxaben
Isoxathion
Jodfenphos
Kinoprene
Lenacil
Leptophos
Leptophos oxon
Lindane
Linuron
Malathion
Malathion-o-analog
MCPA methyl ester
MCPB methyl ester
m-Cresol
Mecarbam
Mecoprop methyl ester
Mefenacet
Mefluidide
Menazon
Mephosfolan
Mepronil
Metalaxyl
Metamitron
CAS #
60568-05-0
76-44-8
1024-57-3
28044-83-9
23560-59-0
87-82-1
118-74-1
70-30-4
79983-71-4
51235-04-2
84-16-2
35554-44-0
1689-83-4
26087-47-8
36734-19-7
42509-80-8
297-78-9
115-31-1
30979-48-7
465-73-6
25311-71-1
57052-04-7
2631-40-5
33820-53-0
50512-35-1
34123-59-6
82558-50-7
18854-01-8
18181-70-9
43588-37-4
2164-08-1
21609-90-5
25006-32-0
58-89-9
330-55-2
121-75-5
1634-78-2
2436-73-9
57153-18-1
108-39-4
2595-54-2
23844-56-6
73250-68-7
53780-34-0
78-57-9
950-10-7
55814-41-0
57837-19-1
41394-05-2
Appendix
No.
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
Compound name
Metasystox thiol
Metazachlor
Methacrifos
Methamidophos
Methfuroxam
Methidathion
Methiocarb
Methiocarb sulfone
Methiocarb sulfoxide
Methomyl
Methoprene I
Methoprene II
Methoprotryne
Methoxychlor
Methyl paraoxon
Methyl parathion
Methyl-1-naphthalene acetate
Methyldymron
Metobromuron
Metolachlor
Metolcarb
Metribuzin
Mevinphos
Mirex
Molinate
Monalide
Monocrotophos
Monolinuron
Myclobutanil
N,N-Diethyl-m-toluamide
N-1-Naphthylacetamide
Naphthalic anhydride
Napropamide
Nicotine
Nitralin
Nitrapyrin
Nitrofen
Nitrothal-isopropyl
N-Methyl-N-1-naphthyl acetamid
Norflurazon
Nuarimol
o,p-DDD
o,p-DDE
o,p-DDT
Octachlorostyrene
o-Dichlorobenzene
Omethoate
o-Phenylphenol
Oryzalin
CAS #
919-86-8
67129-08-2
62610-77-9
10265-92-6
2873-17-8
950-37-8
2032-65-7
2179-25-1
2635-10-1
16752-77-5
40596-69-8
40596-69-8
841-06-5
72-43-5
950-35-6
298-00-0
2876-78-0
42609-73-4
3060-89-7
51218-45-2
1129-41-5
21087-64-9
7786-34-7
2385-85-5
2212-67-1
7287-36-7
6923-22-4
1746-81-2
88671-89-0
134-62-3
N/A
81-84-5
15299-99-7
54-11-5
4726-14-1
1929-82-4
1836-75-5
10552-74-6
N/A
27314-13-2
63284-71-9
53-19-0
3424-82-6
789-02-6
29082-74-4
95-50-1
1113-02-6
90-43-7
19044-88-3
No.
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
73
Compound name
Oxabetrinil
Oxadiazon
Oxadixyl
Oxamyl
Oxycarboxin
Oxychlordane
Oxydemeton-methyl
Oxyfluorfen
p,p-DDD
p,p-DDE
p,p-DDT
Paclobutrazol
Paraoxon
Parathion
p-Dichlorobenzene
Pebulate
Penconazole
Pendimethalin
Pentachloroaniline
Pentachloroanisole
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Pentanochlor
Permethrin I
Permethrin II
Perthane
Phenamiphos
Phenkapton
Phenoxyacetic acid
Phenthoate
Phorate
Phosalone
Phosfolan
Phosmet
Phosphamidon I
Phosphamidon II
Phthalide
Picloram methyl ester
Pindone
Piperalin
Piperonyl butoxide
Piperophos
Pirimicarb
Pirimiphos-ethyl
Pirimiphos-methyl
Plifenat
p-Nitrotoluene
Pretilachlor
CAS #
74782-23-3
19666-30-9
77732-09-3
23135-22-0
5259-88-1
27304-13-8
301-12-2
42874-03-3
72-54-8
72-55-9
50-29-3
76738-62-0
311-45-5
56-38-2
106-46-7
1114-71-2
66246-88-6
40487-42-1
527-20-8
1825-21-4
608-93-5
82-68-8
87-86-5
2307-68-8
52645-53-1
52645-53-1
72-56-0
22224-92-6
2275-14-1
122-59-8
2597-03-7
298-02-2
2310-17-0
947-02-4
732-11-6
13171-21-6
13171-21-6
27355-22-2
14143-55-6
83-26-1
3478-94-2
51-03-6
24151-93-7
23103-98-2
23505-41-1
29232-93-7
21757-82-4
99-99-0
51218-49-6
No.
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
491
492
493
494
495
496
497
498
499
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
518
519
Compound name
Probenazole
Prochloraz
Procymidone
Profenofos
Profluralin
Promecarb
Prometon
Prometryn
Propachlor
Propamocarb
Propanil
Propargite
Propazine
Propetamphos
Propham
Propiconazole-I
Propiconazole-II
Propoxur
Propyzamide
Prothiofos
Prothoate
Pyracarbolid
Pyrazon
Pyrazophos
Pyrazoxyfen
Pyributicarb
Pyridaben
Pyridaphenthion
Pyridate
Pyridinitril
Pyrifenox I
Pyrifenox II
Pyrimethanil
Pyroquilon
Quinalphos
Quinoclamine
Quizalofop-ethyl
Resmethrin
S,S,S-Tributylphosphorotrithio
Sebuthylazine
Secbumeton
Simazine
Simetryn
Sulfotep
Sulfur (S8)
Sulprofos
Swep
Tamoxifen
TCMTB
CAS #
27605-76-1
67747-09-5
32809-16-8
41198-08-7
26399-36-0
2631-37-0
1610-18-0
7287-19-6
1918-16-7
24579-73-5
709-98-8
2312-35-8
139-40-2
31218-83-4
122-42-9
60207-90-1
60207-90-1
114-26-1
23950-58-5
34643-46-4
2275-18-5
24691-76-7
1698-60-8
13457-18-6
71561-11-0
88678-67-5
96489-71-3
119-12-0
55512-33-9
1086-02-8
88283-41-4
88283-41-4
53112-28-0
57369-32-1
13593-03-8
2797-51-5
76578-14-8
10453-86-8
78-48-8
7286-69-3
26259-45-0
122-34-9
1014-70-6
3689-24-5
10544-50-0
35400-43-2
1918-18-9
10540-29-1
21564-17-0
No.
520
521
522
523
524
525
526
527
528
529
530
531
532
533
534
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
556
557
558
559
560
561
562
563
564
565
566
567
74
Compound name
Tebuconazole
Tebutam
Tecnazene
Temephos
Terbacil
Terbucarb
Terbufos
Terbumeton
Terbuthylazine
Terbutryne
Tetrachlorvinphos
Tetradifon
Tetraethylpyrophosphate (TEPP)
Tetramethrin I
Tetramethrin II
Tetrapropyl thiodiphosphate
Tetrasul
Thenylchlor
Thiabendazole
Thiofanox
Thiometon
Thionazin
Tiocarbazil I
Tiocarbazil II
Tolclofos-methyl
Tolylfluanid
trans-Chlordane
Triadimefon
Triadimenol
Tri-allate
Triamiphos
Triazophos
Tributyl phosphate
Tributyl phosphorotrithioite
Trichlorfon
Trichloronate
Triclopyr methyl ester
Tricyclazole
Tridiphane
Trietazine
Triflumizole
Trifluralin
Tryclopyrbutoxyethyl
Tycor (SMY 1500)
Uniconizole-P
Vamidothion
Vernolate
Vinclozolin
CAS #
107534-96-3
35256-85-0
117-18-0
3383-96-8
5902-51-2
001918-11-2
13071-79-9
33693-04-8
5915-41-3
886-50-0
961-11-5
116-29-0
107-49-3
7696-12-0
7696-12-0
3244-90-4
2227-13-6
96491-05-3
148-79-8
39196-18-4
640-15-3
297-97-2
36756-79-3
36756-79-3
57018-04-9
731-27-1
5103-74-2
43121-43-3
55219-65-3
2303-17-5
1031-47-6
24017-47-8
126-73-8
150-50-5
52-68-6
327-98-0
N/A
41814-78-2
58138-08-2
1912-26-1
68694-11-1
1582-09-8
64470-88-8
64529-56-2
83657-17-4
2265-23-2
1929-77-7
50471-44-8
Index
A
D
Deconvolution reporting software
(DRS) 16, 37
O
Octopole reaction system (ORS),
ICP/MS 32, 42
P
Packaging, applications 5962
Pesticide Library 69
Electrospray ionization
(ESI) 20, 40, 54, 57, 58
R
Retention time locking (RTL)
and databases 15, 36, 45, 61
G
GC/MS, introduction 69
S
Selected ion monitoring
(SIM) 12, 39, 44, 48, 50, 62
T
H
Herbicides 40, 51
Vacuum system 9
Insecticides 40, 50
76
AGI_74445_FS_Primer_NewCover
10/22/04
5:23 PM
Page 1
A Primer
Food Safety
Applications in Mass Spectrometry
Trap
TOF
Quad
to food analysis.
Agilent Technologies, Inc. 2004. All rights reserved.
Reproduction, adaption, or translation without prior written
permission is prohibited, except as allowed under the copyright
laws. This information is subject to change without notice.
Printed in the U.S.A. June 3, 2005.
5989-1270EN
A Primer