DMA-80 Tips and Techniques

Tips and Techniques for
DMA-80 Optimization
By Stefano Paggio
DMA-80 Product Manager
Tips and Techniques for DMA-80 with T640/1640 and PC software rev. 02 A or higher
Milestone Srl Helping Chemists
www.milestonesrl.com
application@milestonesrl.com
Rev.09/09
Tips and Techniques for DMA-80 Optimization
CONTENTS
1. General Rules
2. Calibration
How to make a liquid standard solution
How to store a liquid standard solution
How to store standard reference materials
How to optimize the blank
How to increase the quality of the calibration curve
3. Quality Control
How to set up a QC program
4. Sample Processing
Recommendations for preservation of samples
How to increase the reproducibility
How to reduce the memory effect
How to work with unknown samples
How to work with non-homogeneous samples
How to increase the recovery of difficult samples
How to work with difficult matrices
How to work with liquid samples in auto-sampler mode
How to work at low concentration
5. Conditioning procedure for new catalyst/amalgamator or if the unit is not used

for a long time
Rev.09/09
Page 2 of 15
1. GENERAL RULES
Before starting to work with the unit, it is necessary to eliminate any contamination
coming from environmental dust or from the samples.
Before each use, a cleaning procedure is always recommended for the metal boats - in
the DMA-80 or in a muffle at 600C for a few minutes - and for laboratory tools such as
spatula, balance plate, tweezers, etc.
It is particularly important to follow this recommendation when working at low
concentrations of Hg.
For contaminations coming from the environmental or the sample, it is important to
evaluate how much waiting time is tolerated by the auto-sampler mode.
Also, it is a good idea to establish a weekly cleaning.
2. CALIBRATION
How to make a standard liquid solution.
Stock solution of 1000 ppm (1mg/ml) of HgCl2 stabilized in diluted HCl.
Standard for atomic absorption.
Low value used for 1st cell calibration:
Standard solution
From 5 ppm in ml
HCl 36% in ml
Deionised water in
ml
Blank
up to 100
0.025 ppm
0.5
up to 100
0.05 ppm
up to 100
0.1 ppm
up to 100
0.15 ppm
up to 100
HCl 36% in ml
Deionised water in
ml
High value used for 2nd cell of calibration curve:

Standard solution
From 5 ppm in ml
0.2 ppm
up to 100
0.3 ppm
up to 100
Rev.09/09
Page 3 of 15
Standard solution
Stock 1000 ppm

in ml
HCl 36% in ml
Deionised water in
ml
1 ppm
0.1
up to 100
2 ppm
0.2
up to 100
5 ppm
0.5
up to 100
7 ppm
0.7
up to 100
10 ppm
up to 100
The working standards solution must be freshly prepared before every calibration.
How to store a liquid standard solution
Stock solution of 1000 ppm can be stored for one year if maintained in its original tightly
sealed bottle away from sunlight and intense sources of radiation, in a refrigerator at
10C.
Diluted liquid standard solution can be stored for one month if maintained in its original
tightly sealed bottle away from sunlight and intense sources of radiation, in a refrigerator
at 10C.
If the determined value of the QC solution differs from the known value by > 5%, the
standard is discarded. The value may differ if the catalyst is exhausted.
How to store standard reference materials
Standard reference material must be stored in its original tightly sealed bottle away from
sunlight, humidity, and intense sources of radiation. Before each use, the standard
should be thoroughly mixed by rotating the bottle before sampling.
If the determined value of the QC solution differs from the specs of known value, the
standard is discarded. The value may differ if the catalyst is exhausted.
How to optimize the blanks
The blanks are optimized by removing the possible causes of contamination:
Causes
Resolution
Sample with high

concentration or in over
range.
Cleaning procedure up to blank absorbance <

0.0010
Program: Max START Temp. 200C,
Drying/Ashing 1 min at 200C, 2 min up to
650C, 1 min at 650C
Rev.09/09
Page 4 of 15
Metal sample boat corroded,

covered with layer of oxides
or with combustion residue
that can retain mercury and
then release it in the next run.
New metal boat or quartz boat*
Traces of Hg originating from

new metal boat
Cleaning procedure up to blank absorbance <

0.0010
Program: Max START Temp. 200C,
Drying/Ashing 2 min up to 650C, 1 min at
650C
The catalyst and or/and

amalgamator exhaust
Change catalyst and amalgamator and repeat

calibration
Oxygen contaminated
Use O2, 99.50% pure for research

or replace supplier
Low temperature of catalyst

and cuvette
Contact your Milestone service representative to

check the temperatures
Contamination from
environment
Cleaning procedure up to blank absorbance<

0.0010, if after this the contamination persist
transfer the unit to another laboratory.
* Quartz boat P/N 8347 (10 pieces) completely inert material.
How to increase the quality of calibration curves

The primary calibration is performed prior to the first use of the instrument and when
spare parts are replaced, such as the catalyst tube, amalgamator, or oxygen cylinder.
Calibration of the DMA-80 can be performed with standard solid reference material or
standard liquid solution. According to our experience, the best results are achieved with
standard liquid solution, because the distribution of Hg is completely homogeneous.
Use freshly prepared standard liquid solutions containing different concentrations of Hg
that have been stabilized with acid (see how to make standard liquid solution).
The curve comprises the entire range of interest, working range 0.25800 ng.
An example:
Sample amount for each standard : 100 l
Blank, 0.25 ng 5 ng,10 ng, 15 ng, 30ng, 100 ng, 200 ng, 500ng, 700ng and 1000 ng
Program: Max START Temp. 200C, Drying/Ashing 1 min at 200C, 2 min up to 650C,
1 min at 650C
Rev.09/09
Page 5 of 15
The DMA-80 with the new Model 640/1640 terminal offers the opportunity to select
different calibration algorithms at the end of calibration: for 1st cell (0-20 ng) and for 2nd
cell (20-1000ng) linear, s-curve or square calibration curve.
For low content of mercury it is possible to force the curve to 0 value.
The quality of the calibration curve can be also improved by using quartz boats, because
quartz is completely inert, and will not interact with aggressive reagents (acid) present in
the liquid standard solution.
If metal boats are used to perform the calibration, we recommend always using new
boats after the cleaning procedure.
In order to reduce error due to operator we suggest using the same volume of standard
for each run (100l) with different concentration, minimum point for calibration 10
(including blank).
Acceptance criteria are used for DMA-80 standardization.
Samples analyzed shall be within the standard calibration range.
Curve linearity shall have r-value >0.995.
Standards should be in the appropriate range for each matrix.
An initial calibration verification standard is checked once per run after calibration.
An initial calibration verification blank is checked once per run after calibration.
Verification standard for instrument calibration and standardization: checked every 10
samples and at end of run.
A method blank is analyzed with each sample batch, or one per 20 samples (5%), for
each matrix.
An external reference sample (laboratory control standard) is analyzed with each batch,
or one of 20 samples (5%) for each matrix.
A matrix spike is analyzed with each sample batch, or one per 20 samples (5%) for each
matrix.
A sample in replicates (spike in replicates) is analyzed with each sample batch, or one
per 20 samples (5%), for each matrix.
All values shall be documented and maintained and available for easy reference and
inspection.
3. QUALITY CONTROL
How to set up a QC program
The QC program is prepared and overseen by the Laboratory Manager, the QC Chemist,
and the Scientific Advisor.
Rev.09/09
Page 6 of 15
QC protocol
Procedure
The stability of the instrument

calibration is checked during the
Control Standards
run by analysis of the control
standards.
Blanks
Method blanks are analyzed to

confirm the absence of
contamination.
Frequency
Checked every 10 samples
With each sample batch or one

per 20 samples(5%) for each
matrix
Duplicates
Duplicates are analyzed to check With each sample batch or one

method and stability and
performance
matrix
Matrix Spikes
Sample matrix effects are

checked by spiking samples with
With each sample batch or one
a known amount of standard and
subsequently measuring the
matrix
recovery of the analyte in the
sample.
Standard
Reference
Materials
Certified standards are used as

control samples to check the
method performance in the
matrix.
For each matrix
All values shall be documented, maintained, and available for easy reference and
inspection.
Acceptance Criteria for QC Samples

For more details refer to EPA method 7473.
ACCEPTANCE LIMITS. Control limits shall be listed on charts for different matrices.
Acceptable criteria should be set through the use of historical analyses. In the absence of
historical data this limit should be set for:
Control standards for checking the stability of the instrument calibration at 10% of their
true value. To do this use two reference standards with range of interest ( see point 3.5 of
EPA Method 7473).
For each batch of samples processed, a method blank must be carried out. A method
blank is prepared by using a volume or weight of reagent water at the volume or weight
specified in the preparation method. In absence of project specifics, if the blank is less
Rev.09/09
Page 7 of 15
than 10% of the lowest sample concentration for each analyte, then the method blank
would be considered acceptable (see point 9.4 of EPA Method 7473).
For each batch of samples processed, a duplicate is carried out to check stability and
performance. The acceptable criteria in absence of historical analysis is set at 10%.
Matrix Spike/Matrix Spike duplicated at 20% of the spiked for precision and 20
relative percent difference. After determination of historical data, 20% must still be the
limit of maximum deviation for both percent recovery and relative percent difference to
express acceptability (see point 9.3 of EPA Method 7473).
5. SAMPLE PROCESSING
Recommendations for preservation of samples
Full preservation of samplesdomestic sewage, industrial wastes, natural waters, etc.
is a practical impossibility. Regardless of the nature of the sample, complete stability for
every constituent can never be achieved. At best, preservation techniques can only
retard the chemical and biological changes that inevitably continue after the sample is
removed from the parent source.
The changes that take place in a sample are either chemical or biological. In the former
case, certain changes occur in the chemical structure of the constituents that are a
function of physical conditions. Metal cations may precipitate as hydroxides or form
complexes with other constituents; cations or anions may change valence states under
certain reducing or oxidizing conditions; other constituents may dissolve or volatilize (Hg)
with the passage of time. Metal cations may also adsorb onto surfaces (glass, plastic,
quartz, etc.), such as, iron and lead.
Biological changes taking place in a sample may change the valence of an element or a
radical. Soluble constituents may be converted to organically bound materials in cell
structures, or cell lysis may result in release of cellular material into solution. The wellknown nitrogen and phosphorus cycles are examples of biological influence on sample
composition.
Therefore, as a general rule, it is best to analyze the samples as soon as possible after
collection. This is especially true when the analyte concentration is expected to be in the
low range.
Rev.09/09
Page 8 of 15
How to increase the reproducibility

After calibration, the reproducibility of the unit should be lower than
<1.5% for 5 measurements with 0.1 ml of a solution of 100 ppb
ug/Kg (10ng).
If this goal is not achieved with your samples, the cause may be
one or more of the following :
Causes
Resolution
Solid/liquid sample contaminated
Repeat the test with new sample.
Solid sample with non-homogeneous

distribution of Hg
Mix well and increase the sample amount.
Solid/liquid sample with low amount of

Hg
Mix well solid and use pre-concentration step up to

satisfactory results.
Old standard liquid solution/liquid

solution with precipitated due to not
enough acid.
Prepare fresh standard liquid solution.
Weight/volume not accurate
Check balance calibration / Pipette calibration.
DMA-80 unit is not cleaned after high

concentration or over range
Cleaning procedure up to blank absorbance < 0.0030
Process parameter too short
Increase: waiting(purge) time/ drying time/

decomposition time.
Leakage of oxygen through the silicone

joint between cuvette/amalgamator,
amalgamator/catalyst or catalyst/flange
Repair as shown in the Maintenance of

the DMA-80 manual.
Oxygen contaminated
Use only O2, 99.50% pure for research, or replace

supplier.
The catalyst and or/and amalgamator

exhaust
Change catalyst and amalgamator and repeat

calibration.
Environment contaminated
Cleaning procedure up to blank absorbance < 0.0010, if

after this the contamination persists, transfer unit to
another laboratory.
How to reduce the memory effect

The memory effect is due to high concentration of sample analyzed. In order to reduce it,
it is possible operate on different parameters.
1. Reduce the sample amount.
2. Perform a cleaning procedure between each run.
3. Increase the decomposition time.
Rev.09/09
Page 9 of 15
4. For liquid sample, always use quartz boats (see key advantages).
Memory effect of catalyst/amalgamator after 1 ppm
Memory effect of quartz boat after 0.1ppm
Memory effect of quartz boat after 1 ppm
How to work with unknown samples

Unknown samples can contain high concentrations of Hg, so in order to avoid
contamination of the catalyst we suggest developing the application with a minimum
quantity of sample (<5 mg) and then increasing according the result.
Note: 1000 ng is our highest absolute value of mercury detectable.
For solid samples with concentrations of Hg higher than our range, it is possible to do a
premix from 1:1 to 1:200 with inert material, such as previously decontaminated
alumina.
For liquid samples with high Hg concentration, it is possible to do a dilution using the
same matrix.
Rev.09/09
Page 10 of 15
How to work with non-homogeneous samples

Non-homogeneous samples can explain poor reproducibility of the results. It is possible
to increase the performance with a sample preparation procedure.
The problem is due to non-homogeneous distribution of Hg in the matrix, or to different
sizes of the same sampleespecially for inorganic samples such as soil, sediment, ore,
rocks, plastic, etc.
To solve the first problem, mixing well should suffice. For the second problem, we need
to reduce the samples particle size to a powder form, normally below 100 um.
Pre-concentration steps may work as an alternative solution.
How to increase the recovery of difficult samples
It is possible with the DMA-80 unit to increase the recovery from difficult inorganic sample
matrices, such as metal oxide, by increasing its decomposition temperature and time.
Matrix
ZnO
MnO
Sample
Program
Recovery
100 mg
(size 100
um)
1.Max START Temp. 200C,

Drying/Ashing 2 min up to 650C, 2 min
at 650C
60%
2. Max START Temp. 200C,

Drying/Ashing 200C, 3 min up to 750C,
2 min at 750C
100.5%
1.Max START Temp. 200C,

Drying/Ashing 2 min up to 650C, 2 min
at 650C
50 %
2. Max START Temp. 200C,

Drying/Ashing 200C, 3 min up to 750C,
2 min at 750C
99.9 %
100 mg
(size 100
um)
How to work with difficult matrices

Difficult matrices such as petrochemical products, samples containing solvent, or large
amounts (> 100 mg) of organic sample (blood , food, feed, agricultural sample, etc.) can
explode without warning, and consequently reduce the sensitivity of the system.
For serious problems, and when it is difficult to determine whether the catalyst or
amalgamator is the source of reduced sensitivity, we recommend replacing both of them.
Dedicated programs must be used for difficult matrices.
Rev.09/09
Page 11 of 15
Matrix
Sample
Petrochemical
products and
samples containing
solvent
Program
Low reactivity
20-50 mg
High reactivity
10-20 mg
High reactivity
100 mg
Food, feed,
Agriculture
Max START Temp. 200C,

Drying/Ashing 1min at 200C,
2 min up to 650C, 1 min at
650C
Low reactivity
200 mg (i.e.
fresh vegetable)
Food
containing oil
Tips and tricks
Reduce the drying

temperature and
extend
the time if strong
exothermic reaction
persists
Use pre-concentration
step to increase
signal of low Hg amount
100 mg
Longer drying step allows a pre-combustion of sample before rapid decomposition at high temperature,
reducing the exothermic reaction.
How to work with liquid samples in auto-sampler mode, in order to avoid

evaporation.
With liquid samples, metal boats can be used only in single mode, to minimize the loss of
mercury due to chemical interaction between the acid matrix and the metal boat.
Milestone offers boats made of quartza completely inert material to solve this
problem and ensure good results.
The following two experiments illustrate the problem, and the effectiveness of this
solution.
Experiment 1:
Metal boat effect with lost of mercury
10 samples of 120 g/Kg (12ng) have been prepared and run by auto-sampler mode.
Rev.09/09
Page 12 of 15
After starting the autosampler, the waiting metal sample boats react chemically with the
liquid standard, and consequently there is a loss of mercury.
The last boat, run after 50 minutes of waiting, has only 22 g/Kg or ppb(2.2 ng). More
than 80% has evaporated.
Experiment 2:
Quartz boats (without lost of mercury).
10 samples of 120 g/Kg (12ng) have been prepared and run in auto-sampler mode.
All the runs have been successfully done without evaporation, good stability and
reproducibility, RSD: 1.24
We recommend using the quartz boats for all liquid samples.
Stabilizing Hg samples if used with the autosampler
Up to 15 quartz boats 1% of HCL
Reproducibility obtained < 1.5 % with 5 ng or higher
How to work at low concentrations of Hg
With the quartz boats, is possible to optimize the recovery (<1 ng absolute) of Hg without
a pre-concentration step.
Rev.09/09
Page 13 of 15
Matrix
Sample
Program
Solid
100 mg (particle
size 100 um and
homogeneous)
liquid
100 mg /ul
Rsd

Drying/Ashing 1min at 200C, 2 < 3 %
min up to 650C, 1 min at 650C
Drying/Ashing 1min at 200C, 2 < 1.5%
min up to 650C, 1 min at 650C
6. Conditioning procedure for new catalyst/amalgamator

Introduction
The following procedure is to be performed after replacing a new
catalyst/amalgamator.
Note: before starting the procedure be sure that the catalyst/amalgamator
is correctly installed, alignment of actuators and Oxygen flow checked (for more details
see operator manual).
DMA 80 procedure for catalyst/amalgamator activation
Run Reagent/ Sample Max START Drying/Ashing Drying/Ashing
Sample amount Temperature
Time
Temperature
type
n.1
Flour
100 mg
n.2 HNO3 5%
*
200C
1 minute
200C
2 minutes
650C
1 minute
650C
Purge Time
60sec
*: quartz boat (suggested)
Rev.09/09
Page 14 of 15
Repeat at least 5 times the above procedure, up to absorbance < 0.0030

After conditioning a stability test is required.
Repeat 5 times: a fresh aqueous standard of 100ppb, the RSD must be <1.5%.
For this evaluation is not important the recovery but only the DMA stability so the previous
calibration curve can be used.
If the stability test is according to the specs, please proceed making new calibration (see user
manual), otherwise repeat the conditioning procedure again.
Rev.09/09
Page 15 of 15

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Tips and Techniques for

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

How to make a liquid standard solution

How to store a liquid standard solution

How to store standard reference materials

How to optimize the blank

How to increase the quality of the calibration curve

How to set up a QC program

Recommendations for preservation of samples

How to increase the reproducibility

How to reduce the memory effect

How to work with unknown samples

How to work with non-homogeneous samples

How to increase the recovery of difficult samples

How to work with difficult matrices

How to work with liquid samples in auto-sampler mode

How to work at low concentration

5. Conditioning procedure for new catalyst/amalgamator or if the unit is not used

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

High value used for 2nd cell of calibration curve:

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

Stock 1000 ppm

Sample with high

Cleaning procedure up to blank absorbance <

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

Metal sample boat corroded,

New metal boat or quartz boat*

Traces of Hg originating from

Cleaning procedure up to blank absorbance <

The catalyst and or/and

Change catalyst and amalgamator and repeat

Use O2, 99.50% pure for research

Low temperature of catalyst

Contact your Milestone service representative to

Cleaning procedure up to blank absorbance<

* Quartz boat P/N 8347 (10 pieces) completely inert material.

How to increase the quality of calibration curves

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

The stability of the instrument

Method blanks are analyzed to

Checked every 10 samples

With each sample batch or one

Duplicates are analyzed to check With each sample batch or one

Sample matrix effects are

Certified standards are used as

For each matrix

Acceptance Criteria for QC Samples

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

Milestone Srl Helping Chemists

Tips and Techniques for DMA-80 Optimization

How to increase the reproducibility

Solid/liquid sample contaminated

Repeat the test with new sample.

Solid sample with non-homogeneous

Mix well and increase the sample amount.

Solid/liquid sample with low amount of