Experiment # 5:

DETERMINATION OF HEAVY METALS IN SOIL SAMPLES USING

INDUCTIVELY COUPLE PLASMA – MASS SPECTROMETRY (ICP-MS)
In this experiment, you will learn the principle of ICP/MS and apply this instrument to determine the
total contents of heavy metals in soil samples followed by the microwave digestion method for breaking
out the soil samples.
Required Readings
(S indicates Skoog, et al. Principles of instrumental analysis, 6th edition, Thomson, 2007.
K indicates Kellner et al. Analytical Chemistry: A Modern Approach to Analytical Science, 2nd
Edition
1S. Chapter 11, “Atomic Mass Spectrometry” Skoog, et al.
or
1K. Section 6.4, “ Mass Spectrometry”,
2K. Section 5.1, “ Sample Preparation ”,
or
A Beginner’s Guide to ICP-MS. Spectroscopy tutorial. spectroscopy 16(10), 2001

Soil is composed of mineral constituents, organic matter (humus), living organisms, air, and water, and it
regulates the natural cycles of these components. Soil, the carrier of agricultural production and an important
part of the ecological environment, is heavily contaminated with hazardous heavy metals. Therefore, it is
obliged to research analytical techniques that could efficiently determine the total content of heavy metals in
soil.
Analytical protocols for the elemental analysis of soil and sediments normally require the partial or total
breakdown of the sample matrix. Various digestion methods are used to determine the mass concentration of
trace elements in solid matrices. Open beakers heated on hot plates, digestion tubes in a block digester, and
digestion bombs placed in microwave ovens are the most commonly used equipment to digest solid sample
matrices. Recoveries and precision of pseudo-total and total digestion methods vary with many factors,
including the mineral composition and origin of the soil, the digestion method, as well as the elements of
interest. Moreover, the determination of some elements in the soil is challenging and may require the
development of various specific methods for a complete multi-element analysis.
Inductively coupled plasma mass spectrometry, ICP-MS has come to be one of the most attractive detection
systems and is routinely used in many diverse research fields such as earth, environmental, life, and forensic
sciences and food, material, chemical, and nuclear industries. ICP-MS is a powerful technique for trace
analysis of elements and the latter is preferred for ultra-trace levels due to its higher sensitivity so. Although
older techniques such as atomic absorption and atomic emission are still in use by some laboratories, there
has been a slow shift toward ICP-MS, particularly in the last decade. 1
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THEORETICAL BACKGROUND
ICP-MS uses a high-temperature plasma discharge to generate positively charged ions. The sample, typically
in liquid form, is pumped into the sample introduction system, which is made up of a spray chamber and
nebulizer. It emerges as an aerosol and eventually finds its way — by way of a sample injector — into the
base of the plasma. As it travels through the different heating zones of the plasma torch it is dried, vaporized,
atomized, and ionized. During this time, the sample is transformed from a liquid aerosol to solid particles,
then into a gas. When it finally arrives at the analytical zone of the plasma, at approximately 6000–7000 K,
it exists as excited atoms and ions, representing the elemental composition of the sample. The excitation of
the outer electron of a ground-state atom, to produce wavelength-specific photons of light, is the fundamental
basis of atomic emission. However, there is also enough energy in the plasma to remove an electron from its
orbital to generate an ion. It is the generation, transportation, and detection of significant numbers of these
positively charged ions that give ICP-MS its characteristic ultra-trace detection capabilities.
The plasma sources developed for atomic emission spectrometry have also been shown to be very
suitable ion sources for mass spectrometry. This is particularly true for electrical discharges at pressures
in the 1±5 mbar range and sources at atmospheric pressure since the powerful vacuum systems became
available, with which the pressure difference between the mass spectrometer (of the order of 10-5 mbar)
and the source can be bridged.
Elemental mass spectrometry, however, goes back to the use of high-vacuum arcs and sparks, with which
ultra-trace and survey analyses of metal samples could be performed. Spark source mass spectrography
with high-resolution sector field mass spectrometers is still very useful for a survey characterization of
electrically-conducting solids down to the ng/g level. The spectra can be recorded on photographic
plates, which are a permanent document and at least enable semi-quantitative analyses to be made. At
the ng/g level, this approach is suitable for the quality control of materials required in micro- electronics.
The technique has become very useful since computer-controlled densitometers have been available,
which automatically record the blackenings of the elemental lines on the photoplates and convert them
into logarithmic intensities, these being proportional to the logarithmic concentrations.
Spark source mass spectrometry requires expensive sector-field mass spectrometers and despite the
possibility of automated read-out of the spectra, highly skilled laboratory personnel for data evaluation
are also required. This situation arises from the fact that high-vacuum sparks are very powerful sources
producing vast amounts of multiply charged ions making the spectra line rich. The analytical precision
achievable in spark mass spectrometry is low, however, special precautions such as the use of rotating
electrodes are helpful. Spark source mass spectrometry has been used for the analysis of compact metals,
from which electrodes could be made by turning-o€ or by fixing drillings in electrode holders. In the
case of metals of low melting point, such as gallium, liquid nitrogen cooled electrodes of the gallium
were used. For electrically conducting as well as non-conducting powders electrodes were pressed from
mixtures with gold powder, which is ductile and leads to electrodes that are electrically and heat
conductive. The method is very powerful for dry solution residues as a result of its sensitivity and has
been used for impurity detection in liquid aliquots obtained from trace ± matrix separations in1 the
analysis of high-purity materials. 7
 In ICP-MS (Fig. 1) the ions formed in the ICP are extracted with the aid of a conical water-cooled
sampler into the first vacuum stage where a pressure of a few mbar is maintained. A supersonic beam is
formed and several collision processes take place as well as an adiabatic expansion. A fraction is sampled
from this beam through the conical skimmer placed a few cm away from the sampler. Behind the
skimmer, ion lenses focus the ion beam now entering a vacuum of 10-5. This was originally done with
the aid of oil diffusion pumps or cryopumps, respectively, but very quickly all manufacturers switched
to turbomolecular pumps backed by roughing pumps.
The sampler and the skimmer are usually made of stainless steel and are both conically shaped with
different cone angles. The sampler can also be made of copper, which has better heat conductivity. In
the case of HF-containing solutions, platinum samplers can also be used. This is particularly worthwhile
for the analysis of geological samples after wet chemical dissolution and removal of the silicates. The
distance between the sampler and skimmer is critical for the maximum power of detection and minimal
ionization interferences. This also applies to the power transmission to the Rf coil, where considerable
differences were found for coils powered centrally and coils powered at one of the ends. The processes
in the intermediate stage together with their influence on the ion trajectories in the interface and also
behind the second aperture (skimmer) are very important for the transmission of ions and related matrix
interferences, this being the topic of fundamental diagnostic studies.
Today's commercially available instrumentation falls into three groups, namely quadrupole-based
instruments, high-resolution instruments, and time-of-light systems. For each system, different ion
extraction conditions must be selected. In a quadrupole, as a result of the high transmission, no high
extraction voltage is required, which is different for a sector field instrument. Here either the
spectrometer or the plasma must be at a high potential. With quadrupoles, a mass resolution of 1 dalton
over the whole spectral range means the method suffers from isobaric interferences, especially at masses
below 80 daltons. In the case of sector field instruments, the resolution may be up to 5000 while in
commercial instruments sufficient transmission can still be maintained. As the spectral background
intensities are low, detection limits are lower, not only as a result of the absence of several interferences
but also because of better signal-to-background ratios. For time-of-light ICP-MS, both orthogonal, as
well as linear end-on arrangements, are used. The instruments available use a reflection.

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Fig. 5-1. Instrumentation for low-resolution ICP-MS.
 (a): nebulizer; (b): sampler; (c): ion optics; (d): quadrupole;
(e): electronics; (f ): detector; (g): RF-generator; (h): roughing pump; (i): turbo molecular pump: ( j):
quadrupole RF generator.

Duty cycles are still fairly low as ion packages in a time scale of ms are sampled but spectrum
development and acquisition still takes orders of magnitude longer. Despite high throughput, the power
of detection has as yet not been fully exploited. Dual-channel mass spectrometers, where the ion beam
is split inside the mass spectrometer are very useful for isotope ratio work. However, they still use
different detectors. Arrangements with the focal plane have also been introduced for plasma mass
spectrometry work. They are ideally suited for work with array detectors, which are certainly very useful
for isotope ratio work, as within a narrow mass range isotope signals are measured simultaneously,
together with their respective background signals. Such detectors are available as microchannel plates
coupled through a phosphor to photodiode array detectors.
PROCEDURE
Apparatus
Ø Inductively coupled plasma–mass spectrometer (ICP-MS) Elan 9000, Perkin – Elmer, USA.
Ø Auto sample AS-93plus. Tray as-90/as90b.try
Materials and reagents
− Watch glasses or equivalent.
− All reagents must be ultra-pure grade: HNO3, H2SO4, HCl,…
− Super pure water (18.2 MΩ -cm resistivity)
− Argon, super-pure grade (>=99.999).
Ø Standard solutions:
− The 2 mix standard solutions (1) and (2) containing selected heavy metals will be used for setting
up the calibration curve (10mg/L).
Sample digestion, preservation, and handling
− All samples must have been collected following the sampling plan in standard methods.
− All plastic containers must be pre-washed with detergents, acids, and distilled water. Both plastic
and glass containers are suitable for usage.
− Samples digestion: Place 0.0200 – 0.0500g of dry soil samples and to a Teflon vessel. Add 5ml of
concentration HNO3, (p.A Merck); 1ml of conc. H2SO4 (p.A Merck) and 0,5ml of spec-pure water
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to each vessel. A blank sample of reagent water is treated in the same manner along with spikes9and
duplicates (minimum three times) samples.
 Using the power mode or pressure mode of a microwave oven as follows:
− Power mode as following 3 steps:
− N0 1: Power: 30% - Time: 3minutes
− N0 2: Power: 55% - Time: 5minutes
− N0 3: Power: 40% - Time: 18minutes
− Pressure mode as following 5 steps:
− N0 1: Power: 40% - Pressure: 50psi - Maximum time: 5minutes
− N0 2: Power: 50% - Pressure: 90psi - Maximum time: 3minutes
− N0 3: Power: 60% - Pressure: 110psi - Maximum time: 3minutes
− N0 4: Power: 70% - Pressure: 130psi - Maximum time: 3minutes
− N0 5: Power: 80% - Pressure: 150psi - Maximum time: 15minutes
− At the end of the microwave program, allow the vessels to cool for at least 5 minutes in the unit
before removal to avoid possible injury if a vessel vents immediately after microwave heating. The
samples may be cooled outside the unit by removing the carousel and allowing the samples to cool
on the bench or in a water bath. When the vessels have cooled to room temperature, transfer the
sample solution to a volumetric flask to decrease by lower less 10% concentration of acids (solution
A).
− If the digested sample contains particulates that may clog nebulizers or interfere with the injection
of the sample into the instrument, the sample may be centrifuged, allowed to settle, or filtered. These
are unknown samples that will be analyzed by ICP-MS without separation or extraction.
Instrument setup
Ø Turn on the instrument following step by step:
− Firstly, switch UPS. Secondly, turn on Dust filter and Smell the carpet sweeper Device (N1)
− Turn on the argon gas (pressure>= 80 psi)
− Turn on Automat sequence: CB2 – System, CB3 – Roughing pump, CB4 – Electronic, CB1 – RF
Generator
− Waiting for pressure in vacuum pump (approximately 4 – 5 hours)
Ø The optimal parameters of the instrument should be fixed as follows:
Table 5.1. Experimental conditions of ICP/MS for determination of heavy metals
Gas flow rate Nebulizer 0.90 L/min
2
Makeup gas flow rate 2.0 L/min
0
Plasma gas flow rate 15.0 L/min
 Pressure vacuum pump (Quantitative ) 1.2 – 1.3x 10-5 Torr
Pressure vacuum pump ( Standby) 2.0 – 3.0x 10-6 Torr
Sample flush 40s
Sample flush speed -48 +/- rpm
Read delay 15s
Delay and analysis speed -26 +/- rpm
Wash 60s
Wash speed -48 +/- rpm
Cooling water power 1750W
ICP RF power 1000W
Lens voltage 5,75V
Analog stage voltage -1850V
Pulse stage voltage 1000V

Sweeps/reading 10
Readings/replicate 1
Replicates 3
Detector mode Dual
Other parameters Automatic

Software interface Elan:

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Calibration standards
Transfer an accurate volume, 1.0mL of the mix standard solution 1 (multi-elements) and 0.05mL
of standard solution 2 (containing Hg(II)) to the 50mL volumetric flask and bring to 50.0 mL solutions
with spec-pure HNO3 2%. The Std 3 will be obtained and prepared fresh daily. In all cases, standards
must be carried through the same digestion protocol as the samples to monitor digestion effectiveness.
Table 1. Calibration solution standards
Concentration (ppb)
Element
Std 1 Std 2 Std 3
Hg 1.0 5.0 10.0
Others 20.0 100.0 200.0

Express in Software Elan:

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Determination of selected elements in soil samples
Pipet 5.0 mL solution A (see 3) to volumetric flasks in 25mL by ultrapure water.
After the instrument has reached a maximum and returned to the baseline, remove the beaker,
rinse the dispersion tube with water, and proceed to the next standard and samples.

PRE-LAB ASSIGNMENT
1. Title and purpose of the experiment.
2. What species of heavy metals could be determined by this procedure?
3. Explain the analytical procedure used for the determination of heavy metals in soil samples
using ICP-MS in this experiment.
4. Figure out some techniques used to reduce polyatomic fragments in ICP-MS method.
5. What are the effects of the matrix in ICP-MS method? Why do we need to use an acidic matrix?
6. Compare the sensitivity and selectivity of ICP/MS method to other element analytical methods?

RESULTS AND DISCUSSION

- Setup a calibration curve by plotting the intensity of standard solutions (for each element) versus
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concentrations of standards. 3
- Measure cps of unknown samples and read concentrations from the calibration curve. If a sample
was diluted (or concentrated) before sample digestion, apply an appropriate factor.
- Calculate LOD of the instrument using calibration and instrument blank. Figure out the method
detection limit (MDL) based on method blank.
- Discuss on recoveries of soil samples (how to carry out? way of calculation?

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