NOVEMBER 2017

Atomic Absorption
Spectroscopy

Sponsored by Presented in partnership with

 LEADING THE WAY IN
ATOMIC SPECTROSCOPY INNOVATION
Our comprehensive and trusted portfolio offers you the most diverse application coverage for AA, ICP-OES
and ICP-MS, while our unique MP-AES and ICP-QQQ technologies deliver new possibilities for your lab.
Now we introduce the next-generation atomic spectroscopy equipment that will redefine the way you
work. Choose Agilent: Together well take the path to success. www.agilent.com/chem/atomic

Agilent ICP-MS Agilent ICP-QQQ

Agilent AA Agilent MP-AES Agilent ICP-OES

Learn more about the Agilent Atomic Spectroscopy Portfolio:

www.agilent.com/chem/atomic

Agilent Technologies, Inc. 2017

 INTRODUCTION
A
tomic absorption (AA) spectroscopy may not be a new analytical
technique, but that doesnt mean it is any less important than other newer
tools. Many analytical methods and regulations have grown up with AA
spectrometry, and it remains a center point of sample analysis at many labs
to this day.

Indeed, such instruments continue to be appealing for several reasons such as a lower
price point and operational costs. At the same time, instrument makers are continuing
to develop AA technology in ways that both keep these tools relevant and may ease
the transition to other options when labs are ready to invest in other techniques.

In Atomic Absorption Spectrometry, an ebook presented by Spectroscopy with

materials from our sponsor Agilent Technologies, Jean-Pierre Lener of Agilent,
explains some important ways that this technique meets the increasingly stringent
demands of modern food analysis. Here, he discusses:
Historical and modern uses of AA spectrometry,
Regulatory issues,
Usage of flame versus graphite AA spectrometry,
Quality control for milk products,
Automation,
Heavy metals analyses, and
Challenging matrices such as wine.

Throughout this ebook, readers will also find links to several other important resources
from the sponsor that provide detailed information on available instrumentation and
other technical notes.

One important resource is a method development e-Primer on Flame Atomic

Absorption Spectroscopy, created by Agilent. Intended to help analysts develop flame
atomic absorption analytical methods, this reference e-Primer offers information about
setting up instrumentation and operating conditions for more than 60 elements.
Sample types include environmental, food, agriculture, chemicals, minerals, and more.

In summary, this ebook demonstrates how some analytical techniques can be better
with age.

3 | November 2017 | Spectroscopy

 NOVEL ATOMIC ABSORPTION
SPECTROMETRY TECHNIQUES
FOR FOOD ANALYSIS
An interview with Jean-Pierre Lener

SPONSORED
Though atomic absorption (AA) spectrometry
Flame AA Method has been routinely used by analytical
Development
Click to Primer laboratories for decades, it is certainly no less
view PDF
This easy-reference important and relevant for modern analyses.
e-Primer helps you
set up instrumenta- Even as regulations become more stringent
tion and operating (thus making analytical work more complex),
conditions for more
than 60 elements, with tips for opti- AA instruments have kept pace and maintain
mal performance. It also includes ap-
plication guidance for sample types
their place as a go-to analytical technique for
in areas such as food and agriculture, food analysis. In this interview, Spectrometry
environmental, chemicals, minerals,
and more. checks in with Jean-Pierre Lener, AAS/MP-AES
Marketing Manager for Agilent Technologies,
about innovations in flame and graphite furnace
SPONSORED AA spectrometry for analyzing complex matrices
like wine and milk.
200 Series
AA video
Click to
launch Agilents AA Spectroscopy: How widely used is AA
instruments
spectrometry in food testing labs?
video

are produc-
tive, user-
friendly and exceptionally reliatble.
Watch this video and discover how
Agilent AA Systems can help you
handle your analytical challenges.
Lener: For decades, AA spectrometry has
LABORANT/SHUTTERSTOCK.COM; KUBAIS/SHUTTERSTOCK.COM
been a very well-established technique for food
analysis and for other applications. With this
technique, samples are atomized in a flame or a
graphite furnace.
AA spectrometry techniques can analyze more
than 60 elements and covers a wide analytical
range, from % levels down to subparts per
billion. This technique is typically best suited
to applications with up to eight elements, and
sample quantities ranging from a handful to

4 | November 2017 | Spectroscopy

 100 per day. Flame AA spectrometry
can quantify several nutritional
elements such as sodium, potassium,
calcium, magnesium and iron in food
samples which is, very important for
product labeling and quality control.
Quantification of heavy metals like lead,
cadmium and arsenic is mainly done by
graphite furnace AA spectrometry.
The past decade has seen a significant
increase in the use of AA spectrometry
in the food and beverage industry
for many good reasons. This mature
technique is robust, yet very simple to
use. Companion software is also very
straightforward to use. The sensitivity
and accuracy of the method is sufficient
for most food products. Importantly,
AA spectrometry is relatively low
cost to run. In fact, the price of this
instrument is the lowest of all comparable
technologies suitable for food analysis
such as inductively coupled plasmamass
spectrometry (ICPMS), or optical ICP
(ICP-OES) instruments. In addition, there
are typically few interferences in AA
spectrometry compared with ICP-OES or
ICP-MS techniques.
Theres also the convenience factor.
Customers not only can purchase the
instrument itself, but can also access
well established methods to run food
samples. Instead of spending time for
method development and optimization,
customers can install an AA spectrometer,
use template methods available, validate
the method and start running samples for
routine analysis shortly thereafter.
5 | November 2017 | Spectroscopy
Spectroscopy: You mentioned
that AA spectrometry is a mature
technique. How has the technique
kept up with the increasingly
stringent regulations?
Lener: Flame and graphite furnace AA
have been well established since the
1980s. Comparatively, optical ICP and ICP-
MS techniques have been in routine use
for around 20 years. So, the regulations
were developed with flame AA and
graphite furnace AA spectrometry in mind.
Over the years, food safety has become an
increasingly important topic in the world of
consumer safety. More and more stringent
legislation is placed on foodstuffs,
particularly relating to trace elemental
analysis of toxic metals. If new regulations
and standards are based on ICP-OES and
ICP-MS techniques, older AA regulations
continue to be revised and used.
Of note, international or national
standards involving flame AA mainly
cover one or two elements at a time.
Theres one standard for the analysis of
zinc in milk. Youll find other standards for
iron and copper in wine for example. A
separate one covers calcium, magnesium,
and potassium in wine, and so forth.
So, to analyze the full range of sodium,
potassium, calcium, magnesium, iron,
copper, and zinc, you will find different
methods available for flame AA. And for
graphite furnace AA, there are separate
standards for cadmium, for lead, and for
arsenic quantification.
In contrast, just one standard is used
to analyze all elements in wine with
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 optical ICP and one for ICP-MS. We have
approximately 15 standards for milk and
wine analysis for AA, but only two for ICP-
OES and two for ICP-MS.
Spectroscopy: Quality control of
milk products is a hot topic. How
can atomic absorption be used here?
Lener: The elemental analysis of milk is
important or both quality control and
product labeling requirements. Many
such elements can be analyzed in food
products by flame AA spectrometry,
which as I mentioned, is a very simple
technique to run.
As more and more food products are
imported and exported around the
globe, greater quality control methods
are needed, and some laboratories are
looking for optimized AA systems that
can efficiently and accurately analyze
as many as 100 milk samples per day.
Such optimization is essential because
it is inefficient to dedicate one analyst
to manually running large numbers of
samples every day.
With new techniques, you can
automate several processes in AA such
as instrument calibration and sample
dilution.
For instance, because ionization buffer
is needed for sodium and potassium
analysis with Flame AA spectrometry, you
can automatically add the buffer to your
100 samples with new techniques rather
than having to manipulate 100 samples,
do calibration, and potentially introduce
contamination during sample dilution.
6 | November 2017 | Spectroscopy
Such autosampling will dramatically
reduce potential sources of error in this
type of analysis, improve productivity and
reduce costs.
To do so, an Agilent Sample
Introduction Pump System (SIPS 20) for
flame AA uses a dual peristaltic pump
combined with a mixing cell system
for the on-line addition of ionization
buffer during analysis. This accessory
also prepares automatically up to 10
standards from a single bulk standard and
eliminates the task of preparing multiple
calibration standards and provides fast,
accurate online dilution of over-range
samples to bring the concentration into
the working range.
SPONSORED
Learn more about
the Agilent Sample
Introduction Pump System
Click to (SIPS 20) accessory in this
view PDF technical overview.
Spectroscopy: What are the
benefits of using an automated
AA spectrometry technique over
another newer method?
Lener: AA spectrometry is the simplest
technique, especially when using an
autosampler and an accessory like the
SIPS 20 to do fully automated methods.
One could use optical ICP or even ICP-
MS instruments, but they cost significantly
more than an AA instrument. The
purchase price of an AA system is around
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 2.5 times less expensive than an optical
ICP instrument and at least four or five
times less expensive than an ICP-MS
instrument.
The other big difference between
optical ICP and ICP-MS compared to
AA spectrometry is the way samples are
vaporized. Optical ICP and ICP-MS use
argon plasma to atomize/ionize samples,
which is significantly more expensive
than the air and acetylene used with the
automated flame AA technique.
I feel that optical ICP, ICP-MS, and AA
spectrometry all do a good job, but not
at the same analytical price.
One thing to keep in mind with flame
AA is that while you can have automation
with the right tools, it is dangerous
to leave the instrument running and
unattended in the laboratoryespecially
overnight. By contrast, it is not a
problem to have optical ICP and ICP-MS
instruments running unattended.
Six years ago, Agilent introduced
a unique microwave plasma atomic
emission spectrometer (MP-AES). We
were the first to offer microwave plasma
technology using nitrogen plasma coming
from air. Since no flame is needed, this
instrument can be run unattended.
The price of a microwave plasma atomic
emission spectrometer is between that
of a flame AA instrument and an optical
ICP, making it an excellent option for
food analytical laboratories due to
superior detection limit and improved
dynamic range compare to flame AA.
In the future, we believe that a large
7 | November 2017 | Spectroscopy
SPONSORED
Imagine running
your AA on air
Click to Introducing the Agilent
view PDF 4210 MP-AES, the ideal
alternative to AA that per-
forms elemental analysis
using air instead of flam-
mable gases. This innovation:
Saves time and reduces operating costs
Enhances laboratory safety
Improves analytical performance com-
pared to flame AA
Enables reliable unattended multi-ele-
ment overnight operation
Download the Agilent MP-AES
e-Handbook to take a closer look
number of flame AA users will transition
to microwave plasma instruments rather
than argon plasma systems due to cost
considerations.
Spectroscopy: How about beverage
samples like wine? How would you
analyze this type of sample?
Lener: Wine is a complex matrix,
including ethanol, sugar, tannin, and other
organic substances. One of the biggest
factors in the quality control of wine is
measuring concentrations of metals like
iron and copper. These metals must be
very controlled to ensure they do not
exceed certain concentrations that could
affect the quality of the wine. For similar
reasons, calcium and potassium levels is
important information for the winemaker
to have before bottling.
For wine analysis, we can use methods
developed by International Organization
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 of Vine and Wine (OIV), which typically
cover the analysis of certain elements
(e.g., sodium, potassium, calcium,
magnesium, iron, copper, zinc, and
manganese) by flame AA spectroscopy,
optical ICP, or ICP-MS. Again, the flame
AA is the simplest to use while offering
good sensitivity and accuracy without
the interferences that surface in ICP
techniques.
As I mentioned earlier, one needs an
ionization buffer for sodium and potassium,
per the OIV OENO 18/2003 standards.
Again, it is possible to do fully automated
analysis with the Fast Sequential (FS) mode
and the Agilent SIPS 20 accessory.
SPONSORED
Learn more about the
Fast Sequential (FS)
mode in this technical
overview.
Click to
view PDF
For the first time, the FS mode allows
for sequential analysis with flame AA;
all required elements can be analyzed
from a single solution introduced to
an instrument like a MP-AES, ICP-
OES or ICP-MS. Normally, AA is a
mono-elemental technique, requiring
separate analysis of each element and
recalibration. With the FS mode, all
the instruments hollow cathode lamps
are turning on simultaneously and all
eight elements in wine are determined
in a single aspiration of a sample.
8 | November 2017 | Spectroscopy
Again, optimization with the SIPS 20
automatically calibrates the instrument,
dilutes the sample if necessary, and
introduces the ionization buffer, while
the FS mode directly analyzes all eight
elements by providing one sample in
front of the system.
FS mode offers several benefits such
as dramatically reduced analysis time
and smaller sample volume. This feature
also reduces the amount of gas used on
the instrument. Using multi-elements
lamps, even a four-lamps position
instrument can analyze 14 elements from
a single solution. Another feature in the
software, PROMT (Precision Optimized
Measurement Time) allows the operator
to set the acceptance criteria for this
feature to optimize testing requirements.
These features togetherFS mode, SIPS
20, and PROMToffer considerable time-
savings without compromising precision.
SPONSORED
In this brochure, learn
how the PRecision
Optimized Measurement
Click to Time (PROMT) mode
view PDF allows operators to set
the level of precision
they want for sample
results.
The Agilent SIPS 20 features can be used
to avoid matrix matching. Normally for
wine samples, you must have the same
concentration of ethanol in your calibration
standard to reproduce the matrix of the
wine so as to minimize the matrix effect.
In the case of the Agilent SIPS 20 features,
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 analysts can use the standard additions
capability to automatically perform a
calibration from a single standard. Another
unique feature is the internal standard
capability in the software to control the
matrix effect and directly analyze samples.
You dont have to spike your standards
with the normal concentration of ethanol
in wine of approximately 12% ethanol,
offering additional cost savings. Instead,
by using FS mode and SIPS 20 we can
run samples with a single standard and by
using the internal standard to control the
matrix effect, similar to the capability of a
MP-AES, ICP-OES or an ICPMS system.
In addition, you can use a specific
template developed for 240FS, SIPS 20,
PROMT with 14 elements, 18 wavelengths
pre-calibrated to run a semi-quantitative
analysis of your sample in less than 1.5
minutes in flame AA.
Spectroscopy: Has your team done
any studies of how much time is
saved with the sequential technique
with AA spectrometry?
Lener: The gains of the FS mode
compared to the classical way is around
3550%, depending on the analysis time
and the number of replicates.
Spectroscopy: For food analysis,
its also necessary to analyze
heavy metals like arsenic or
mercury that can be present very
low concentrations. Can these
elements be analyzed on flame AA
instruments?
9 | November 2017 | Spectroscopy
Lener: Regulations obligate food
producers to strictly control heavy metals,
like arsenic, mercury, and cadmium.
Flame AA instruments can be used to
analyze hydride elements like arsenic
and mercury. You can attach a vapor
generator accessory to the flame AA to
detect arsenic and mercury at ppb or
even sub-ppb levels.
SPONSORED
Learn how Agilents VGA
77 Vapor Generation
Accessory offers the
convenience of flame AA
Click to
view PDF operation while delivering
flexibility and automation.
For vapor generation, the sample goes
through a pre-reduction process, and then
is reacted with sodium borohydride to
form a volatile hydride forming element or
a cold vapor, in the case of mercury. This is
then passed through to the spectrometer
for determination of the element of
interest. The main advantage of the
hydride generation is the separation of
the analyte from the matrix. This enables
the reduction or even elimination of
interferences and increases sensitivity.
But, this technique of hydride generation
can only be used for a few elements such
as arsenic, selenium or mercury.
Spectroscopy: What about the
other heavy metals like cadmium
and lead? How can they be analyzed
by AA spectrometry?
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 Lener: Flame AA will not be able to reach
the required quantification limits for lead
and cadmium. The hydride generation
technique also wont help. So, we must
use a different technique: graphite
furnace AA spectrometry. Graphite
furnace AA spectrometry is an extremely
sensitive technique and can be used to
reach the same ppb or sub-ppb levels as
those achieved for arsenic and mercury
with hydride generation.
SPONSORED
Learn more about graphite
furnace sensitivity in this
techical note.
Click to
view PDF
Graphite furnace AA spectrometry is
much slower than flame AA spectrometry,
taking around two minutes per replicate.
It would take six minutes to complete
three replicates, whereas flame AA
spectrometry would take six to nine
seconds for three replicates.
10 | November 2017 | Spectroscopy
With graphite furnace instruments,
customers are almost always interested
in using an autosampler, which like flame
AA, can do automatic calibration and
sample dilution if they are over range.
Clients also usually choose to use a
Zeeman background correction to get the
correct quantification for the analysis of
challenging matrices.
We have several software and
hardware tools to help customers to
define the three critical temperatures in
graphite furnace, of drying, ashing and
atomization temperatures, to ensure we
have developed the perfect method for
a specific matrix. For instance, we have
a camera inside the system to look at
the interior of the graphite tube so the
analyst can see the droplet on screen and
whether its boiling or drying well. And,
we give analysts the best methodology to
define the ash and atomize temperatures
by using chemometric techniques.
Graphite furnace analysis has never been
easier.
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