Elemental analysis in waste oil
recovery and recycling
Oil analysis saves money and prevents equipment failure
Olaf Schulz SPECTRO Analytical Instruments
H
uge quantities of waste oil and related
wastes are generated each year. Properly
collected and processed, these wastes can
be a valuable energy source or be refined to
produce usable products such as new lubricating
oil. However waste oil is usually contaminated,
because of its previous use, with water and other
liquids, halogens and other elements including
heavy metals. In most countries it is regarded as
potentially hazardous waste and must be
handled, processed and stored appropriately. Its
transport, storage and ultimate uses are governed
by a variety of direct and indirect national and
international legislation and industry standards.
A worldwide specialist industry has developed to
collect, transport and process waste oil and to
market the products derived from it.
Elemental analysis is an essential part of the
environmental protection and quality control
procedures associated with the recycling of waste
oil. The two analytical techniques most frequently
used for elemental analysis in this industry are
Energy Dispersive X-ray Fluorescence (EDXRF)
spectrometry and Inductively Coupled Plasma —
Optical Emission Spectrometry (ICP-OES). This
paper describes these techniques and how the
range of instruments from Spectro Analytical
Instruments meet the current and future require-
ments for elemental analysis in the waste oil
recycling industry.
Waste oil: origins, uses and legislation
Although a major source of waste oil is used auto-
motive lubricants, the oil recycling industry has
developed so that a wide variety of wastes are
treated to produce usable product. A proposed
UK Quality Protocol lists over 80 different waste
classifications that are acceptable as inputs for
www.digitalrefining.com/article/1000641
processing to manufacture processed fuel oil, or
PFO. These can be as diverse as paint wastes and
drilling muds, and of course include the more
common materials such as waste engine and gear
oils, hydraulic fluids and machining fluids.
The quantities involved are considerable. The
EU consumes around 5 million tons of base oils
a year, of which roughly half becomes waste in
due course. The remainder is consumed in use
and lost due to spillage etc. Similarly in the US,
about half the annual demand of around 2.5
billion gallons becomes waste.
There are a number of legally approved routes
for the disposal of waste oil, each subject to
legislation. Regulations are being reviewed
continually, and some of these uses may become
restricted as legislation changes. The main legal
disposal routes are:
• Direct combustion/use as fuel
• Processing to produce secondary fuels
• Re-refining to produce new base oil and other
petroleum products.
The routes chosen in different countries vary
greatly and depend on factors such as local
energy policies, customs tariffs and the like. Of
the waste oil produced, approximately half is
used as fuel. Re-refining involves significant
investment in plant and in some countries a
premium price for the product. Currently some
countries are claiming re-refining rates of over
70% of waste oil collected while others are close
to zero. A significant proportion of waste oil is
burned or otherwise disposed of illegally: up to a
quarter of all lubricating oil produced is disposed
of in this way.
Direct combustion/use as fuel
Examples of plants that may be approved to
January 2011 1
 common practice and can mean that heavily
Concentration limits for the contaminants contaminated material can be “diluted” with
cleaner waste to keep emissions within limits.
Maximum Contaminant concentration [ppm] Waste oil can also be burned in space heaters
Arsenic 5
Cadmium 2 and so-called small waste oil burners (SWOBs)
Chromium 10 and is used as a heat source in processing road-
Lead 100 stone and asphalt. All these uses are subject to
Total halogens 1000 licensing and emission limits.

Table 1 Processing to produce secondary fuels

These fuels are known variously as recovered
fuel oil (RFO) or processed fuel oil (PFO). Until
burn waste oils include cement works, steelworks recently processing has involved basic clean-up
and waste incinerators. In the EU, this use is such as dewatering and processes such as filter-
covered by the Waste Incineration Directive, ing, settling or centrifuging to remove solid
which sets limits on the emissions to air of contaminants. RFO has been in use for many
substances generated during such combustion, years and various commercial specifications
and on emissions to water and any slag or ash apply, with limits on elements such as sulphur,
generated. Indeed, any slag or ash produced may halogens, nickel, vanadium and sodium. More
itself be classified as hazardous waste and be recently, environmental concerns have led to
subject to its own disposal controls. Because proposals for tighter controls on recovered fuels.
these emissions will depend on the design of the In the US, waste oil and recovered fuels will be
combustion system, such plants are usually categorised as either “on-spec” or “off-spec”. The
licensed individually and are subject to routine EPA considers that only certain contaminants in
monitoring and environmental audits to ensure used oil pose a significant threat to human health
that emission limits are met. Clearly it will be or the environment and has established maxi-
necessary to ensure that inputs to these plants mum concentration limits for the contaminants
remain within the limits of impurities that the shown in Table 1. Waste oil or RFO with less
design can handle, so it is usually necessary to than these concentrations is on-spec and can be
use known sources or to analyse the waste on burned in any combustion device. Off-spec RFO
receipt. Co-incineration, when mixtures of is regarded as waste and must be treated accord-
combustible wastes are burned together, is a ingly. Waste oil containing more than 4000 ppm
of total halogens it is classified as hazardous
waste and must be disposed of at a facility desig-
Recovered fuels nated for that purpose. The same distinction
between waste and commodity is found in a
Parameter Limit, Gas oil Limit, HFO Quality Protocol published by UK government
substitute [ppm] substitute [ppm} agencies. This gives specifications for levels of
Total halogen, as chlorine <5 150 heavy metals and other contaminants in fuels
PCBs <5 <5
Lead <5 25
that can be used as direct substitutes for two
Mercury <5 <5 existing grades of fuel, gas oil and heavy fuel oil,
Nickel <5 <5 described in British Standard BS2869:2006 as
Chromium <5 <5 Class D and Class G, respectively. Recovered
Copper <5 40
Zinc <5 300
fuels meeting these specifications may be burned
Arsenic <5 <5 without restrictions (see Table 2).
Cadmium <5 <5
Thallium <5 <5 Re-refining
Antimony <5 <5
Cobalt <5 <5
These limits, if adopted, will place new demands
Manganese <5 <5 on the processing and analytical resources of oil
Vanadium <5 <5 recycling companies. As mentioned above, the
proportion of waste oil that is re-refined varies
Table 2 widely from country to country. After initial

2 January 2011 www.digitalrefining.com/article/1000641

clean-up of the waste re-refining oil, re-refining
uses the same basic techniques that are used in
crude oil refining, namely distillation, hydrot-
reatment and various finishing processes. It
should be remembered that oil does not lose its
basic lubricating properties in use, but suffers
from fuel dilution, additive depletion and
contamination by soot and other combustion by-
products and wear metals. The objective of
re-refining is to recover the base oils that can
then be blended with additives to produce new
lubricating oils. Compared with other disposal
routes, re-refining involves considerable capital
cost and unless favourably treated by local tax
regimes can be more expensive than lubricating
oil derived from crude. It is however claimed
that re-refining yields energy benefits compared
to the refining of new crude oil and generates
less pollution than burning the waste as fuel.
These factors combined with volatile oil prices
and a desire by many countries to reduce
dependence on imported oil suggest that re-
refining may become a more popular disposal
route in the future. Furthermore, in the EU, the
new Waste Framework Directive, 2008/98/EC,
will allow member states that stipulate re-refin-
ing as the preferred disposal route to prevent the
export of waste oils for incineration elsewhere.
The disposal routes described above will all have
different analytical requirements. Most will
require a screening technique to avoid waste oil
being accepted for treatment that is contami-
nated to a degree that is beyond the capacity of
the treatment plant to remove or may lead to
emission limits being exceeded in the case of
incinerators. Toxic elements can be concentrated
in incinerator ash, so this may need to be
analysed too. Those producing secondary fuels
will also need to demonstrate that these fuels
meet the increasingly strict limits on heavy
metals and halogens. Re-refining plants that
produce finished lubricants may also need to
determine additive concentrations as part of
their quality control procedures. Typical concen-
tration levels for contaminants lie in the range
from 1 to 500 parts per million, and some addi-
tive elements can be at several thousand ppm.
For most elements, these concentrations are well
within the scope of spectroscopic techniques
such as EDXRF and ICP-OES. The choice of
technique will depend on the ultimate perform-
ance required. EDXRF will be ideal for screening
www.digitalrefining.com/article/1000641
applications and the determination of most addi-
tives. In markets where the newer, more
demanding limits are imposed, it may be neces-
sary to employ the higher sensitivities of
ICP-OES for the analysis of recovered fuels. In
any case, the sensitivity required for screening
applications will usually be considerably less
than that required to demonstrate product
conformity. The conventional way of expressing
an instrument’s ultimate ability to detect a given
element is limit of detection (LOD), but perhaps
a more useful guide is limit of quantitation
(LOQ) as it represents the lowest concentration
that can be reliably measured. Examples of LOD
and LOQ in oil matrices are given below for vari-
ous instruments. Both techniques can be used
when sample numbers are relatively small, but
when high sample throughput is required, the
relatively high speed of simultaneous ICP-OES
has made it the technique of choice in service
laboratories. The requirement for speed and the
need to measure many elements in each sample
means that sequential techniques like atomic
absorption spectrometry (AAS) and sequential
ICP-OES are usually considered too slow for high
throughput applications. When analysing raw
untreated waste, its heterogeneous nature can
give rise to significant sampling errors. Some
wastes may contain separate phases and this
needs to be taken into account in sampling
procedures.
EDXRF - basic principles
The technique works by irradiating the sample
with a beam of X-rays to induce fluorescence in
the atoms in the sample, which is then emitted as
X-rays of a lower energy. Each element emits
fluorescent X-rays of different and unique ener-
gies or wavelengths, whose intensity is
proportional to the concentration of that element
in the sample. X-ray detection systems have been
developed that can themselves discriminate
between the X-ray energies emitted, measure
their intensities and hence determine the concen-
tration of the different elements in the sample.
This technology is known as energy dispersive X-
ray fluorescence, or EDXRF. A more recent
development in EDXRF has been the advent of
instruments that polarise the X-radiation before it
impinges on the sample. This is done by reflecting
the X-ray beam from a suitable target, usually a
specially prepared and shaped crystal. This has
January 2011 3
 the effect of significantly reducing the scattering
of the primary (excitation) X-rays that would
otherwise occur at the sample surface with unpo-
larised X-rays. This is referred to as ED(P)XRF
and substantially lowers the detection limit that
can be achieved. The Spectro iQ II and Spectro
Xepos use the ED(P)XRF principle to reach very
low detection limits. Detection limits depend on
the measurement time employed, but most appli-
cations are completed in a matter of seconds. One
great advantage of XRF analysis is that the sample
can be analysed directly as a solid or liquid. The
technique is therefore non-destructive and can
involve little or no sample preparation. For this
reason it is a good technique for screening analy-
sis. It is most sensitive for the “heavy” elements,
so can be used for the determination of important
toxic metals like Pb. For some of the very “light”
elements like boron, used in some additives, XRF
is not suitable and ICP-OES would be the
preferred technique. Sample preparation for
EDXRF analysis is very simple. In most instru-
ments, the sample is irradiated from beneath, so
liquid samples are normally measured by simply
pouring them into a cup with a base of an X-ray
transparent material such as polypropylene and
the cup placed in the instrument for measure-
ment. Cement works are major consumers of
waste oil as fuel in their kilns and most already
have large WDXRF systems that are used to
control the production process, so it has often
been suggested that these instruments could be
used to screen incoming fuel. However this is
usually impractical, because the instruments are
usually fully occupied monitoring the continuous
production process. Furthermore these instru-
ments are often used with the optical system
under vacuum, so there is a risk of contaminating
the system if it is used for waste oil analysis.
Spectro xSort: ideal for screening
Many such plants therefore have separate
EDXRF instruments for screening purposes. The
xSort is a small, portable but sophisticated
EDXRF spectrometer especially suitable for oil
screening measurements. Complete with battery
pack, it weighs less than 4 pounds (1.7 kg).
Usually hand-held, for oil analysis the instru-
ment is used as a bench top unit mounted in its
“docking station”. The excitation using a minia-
turized low power X-ray tube is optimized to
realise short measurement times at maximum
4 January 2011
impulse throughput. Specially developed detec-
tor technology based on silicon drift detectors
(SDD), enable up to 10 times higher signal
throughput than conventional instruments,
allowing for a unique analytical flexibility and a
considerably accelerated signal processing.
Calibration of the instrument is automatic using
stored calibrations combined with Spectro’s
Intelligent Calibration Logic (ICAL). The xSort is
fitted with an automatic shutter that closes
between each measurement, partly to protect
internal components and partly to protect the
operator from possible exposure to X-rays. ICAL
ingeniously uses the shutter itself (i.e. when it is
closed) as an external standard to check the cali-
bration between measurements.
Spectro iQ - quantitative performance
The Spectro iQ II uses a low-power X-ray tube
and an advanced “C-Force” polarisation optical
system to ensure optimum excitation of the
elements in the sample. This results in signifi-
cantly improved analytical performance for light
elements such as Mg and Si, so the iQII will be
of particular interest to re-refiners and blenders.
The sample chamber can be flushed with helium
to further enhance the performance of these light
elements. An exceptionally powerful SDD —
technologically derived from that in the premium
performance Spectro Xepos spectrometer — is
used in the Spectro iQ II. High spectral resolu-
tion and good signal to background ratios are
the basis for freedom from spectral interferences
low detection limits.
Spectro Xepos - sensitivity and flexibility
Like the Spectro iQ II, the Spectro Xepos uses a
50 Watt end-window X-ray tube to excite the
samples and an advanced SDD detector. However
it also incorporates a target changer, with up to
eight polarisation and secondary targets. This
offers a wide choice of excitation conditions to
ensure optimum analytical conditions, making
the Xepos capable of even higher performance
than the Spectro iQ II. Particularly useful for
investigative work, Spectro’s Turboquant soft-
ware package allows standardless quantitative
analysis on totally unknown samples.
Oil analysis with EDXRF
The Spectro xSort is an economical route to
screening waste and used oil samples. There are
www.digitalrefining.com/article/1000641
two different versions available with different X-
Spectro xSort Ag tube LOD and LOQ [300s]
ray sources. One has a tungsten anode and the
other a silver anode. The silver anode gives
Element LOD [mg/kg] LOQ [mg/kg]
somewhat better sensitivity for the lighter S 18 60
elements. The rugged nature of this instrument Cl 4 13
makes it especially suited to on-site screening Ca 1.8 6
applications. The following LOD were obtained V 1.8 6
Cr 1.8 6
on a standard oil sample using an xSort with Ag Ni 1.4 5
anode X-ray tube. The results in Table 3 are Cu 1.4 5
given for measurement times of 300 seconds. Zn 1.4 5
The Spectro iQ II and Spectro Xepos are much As 0.5 2
Se 0.9 3
more powerful instruments and the following Br 1.8 6
results from the Spectro iQ II show the low cali- Mo 1.8 6
bration errors (high precision and accuracy) and Cd 14 47
low detection limits that can be achieved with an Sn 18 60
Sb 23 77
instrument in this class. The iQ II is suited to a Ba 65 217
wide range of screening applications and the Hg 5 17
analysis of re-refined lubricating oils. Pb 0.9 3
Bi 5 17
ICP-OES - accuracy, sensitivity and speed
ICP-OES is capable of meeting most of the Table 3
demands of waste oil analysis. It is a branch of
OES that uses an inductively coupled argon
Spectro iQ II LOD and LOQ
plasma as an emission source. There are many
different approaches to instrument design that
have implications for performance and ease of Element LOD [mg/kg] LOQ [mg/kg]
Mg 12 40
use, so a review of the fundamentals of ICP-OES Si 1.4 5
and the design of the Spectro Arcos and Spectro P 0.3 1
Genesis may be useful. S 0.2 1
ICP-OES works in a manner analogous to XRF, Cl 0.3 1
K 2.3 8
and relies on the fact that every element has a Ca 0.7 2
unique atomic structure, with a massive posi- Fe 0.8 3
tively charged nucleus and a number of electrons Cu 1.2 4
in orbits surrounding it. Each of these electrons Zn 0.9 3
Mo 0.8 3
exists at a precise energy level and under normal Ba 1 3
conditions, with no external influences, this is Pb 1.1 4
known as the “ground state”. If, however, the
atom is subjected to energy, e.g. in the form of Table 4
heat and respectively collisions with other atoms,
that energy can be absorbed and the electron(s) regions of the optical spectrum, between about
raised to a higher or excited state. This is an 130 nm and 780 nm. Because of the large number
unstable condition, and the electrons quickly of transitions possible in most elements, their
return to the ground state, at which point the emission profiles (spectra) can be very complex.
previously absorbed energy is re-emitted. If Over 4000 different emission wavelengths
enough energy is absorbed, an electron can be (referred to by spectroscopists as emission lines)
driven out of the atom completely, in which case have been identified for iron alone. Multi-element
the atom is said to be ionised. spectra can be very complex indeed, and ionised
The intensity of this radiation is proportional to atoms give rise to emission spectra of their own,
the number of atoms present (i.e. the concentra- to further complicate the issue.
tion), which is the basis of quantitative analysis For practical analysis with OES, several essen-
by OES. For practical analysis, the wavelengths tial components have to be provided:
usually employed lie in the ultra-violet and visible • An excitation source to provide the energy to

www.digitalrefining.com/article/1000641 January 2011 5

 determine
which the sample each electron in every
is introduced as element,
an aerosol. so the
In thecharacteristics
plasma of the energy absorbed
sthermally
Si and Al,atomized
and emitted will also be different for
and the atoms are excited to emit element- each element. If enough energy is ab-
ne S and P sorbed,
on as described above. an electron can be driven out of the atom completely, in which case
Ss the more the atom is said to be ionized.
heated to a certain point, the thermal energy becomes high ised, molecules are
zehasatoms
a sig-in it, to form what is known as a plasma. The ions and
dissociated and atoms
mic
in the range,
plasma cause it to become electrically conducting and it and ions, which are like-
ee to
to inductively
cope couple radio frequency energy into the plasma wise formed, are excited
anges and A typical configuration has the argon plasma sup-
continuously. to emit element-specific
utions.
artz Theand powered through an induction coil.
torch radiation as described
mes, flam-
above. For waste oil anal-
rized flam-
rch
like an ICP
ysis the ICP source has
dvantage of ICP-OES for oil analysis is that the very high tempera- another advantage, since,
ent should
in the “analytical zone” of the plasma (6-7000 K) can vaporize thanks to the very high
ed.
ven solid metallic particles in the oil – elements must be present temperatures reached in
al and in-
or ions to be excited and emit their characteristic radiation. a plasma, even solid
hods that
eded to maintain the plasma is provided by a radio frequency metallic particles in the
he use of
cally operating at 27 or 40 MHz. International regulations permit oil — elements can vapor-
fuels and
on at these frequencies whereas the use of other frequencies ise and atomise and are
These in-
expensive shielding. The radio frequency generator must be thus excited and emit
ble and able toFig 1: Excitation
sustain
Schematic the and Emission
plasma
diagram ofwhen
an ICP-its OES
electrical proper-
spectrometer their characteristic
cause of sample Because of the relationship
introduction. between
This is especially energy and
important withwavelength (frequency), and radiation.
es and solvents, since asthe
excite the energy
the presence
atomsemitted when
of organics
in the the
test electrons
places
sample. returns
a heavy
In ICP-OESto the ground Whenstate acangas is heated to a certain point, the
sma. Indeed some be in the form
ICP-OES systems
spectrometry of electromagnetic
thissuffer
is from radiation,
an instability
inductively each transition
when coupled thermal is giving riseenergy
to becomes high enough to ionise
radiation
analyze organicplasma at
samples(q.v)a discrete and precisely defined
and in extreme cases the plasma may wavelength, so each element gen-
the atoms in it to form what is known as a
uished. erates
• Optics a unique set of emission
to isolate wavelengths.
the specific The intensity
wavelengths forof this radiation
plasma (the is forth state of matter). The ions and
proportional to the number
the elements to be measured of atoms present (i.e. the concentration), which
free electrons in the plasma cause it to become
is• the basis of quantitative
A detector system to analysis
measure by the
Optical EmissionofSpectrometry.
intensity electrically Forconducting and it is then possible to
practical analysis,
the light emissions the wavelengths usually employed lie in the ultra-violet and
magnetically couple radio frequency energy into
visible regions of to
• Electronics theacquire
optical spectrum.
the detector Because of the large
signals and number
the of transi- to maintain it continuously. The
plasma
tions possible in most elements, their
to control the functions of the spectrometer emission profiles (spectra)
energy very
can be needed to maintain the plasma is
complex. Over 4000 different emission wavelengths
• A computer with software for calculation and provided
    (referred to by spectro- by a radio frequency generator typically
scopists
displayasofemissionemission lines)spectra
have beenand identified for iron alone. operating
concentration Multi-element at 27 or 40 MHz. These frequencies
values schematic diagram of an ICP-OES are chosen because international regulations
spectrometer permit limited radiation of these frequencies —
the use of other frequencies would require
The ICP source expensive shielding. The radio frequency genera-
In ICP-OES, the source is an inductively coupled tor must be extremely stable and able to sustain
argon plasma, an electrically powered high the plasma when its electrical properties change
temperature state of matter in which the argon because of sample introduction.
gas is fully ionised and the sample is introduced
as an aerosol. In the plasma the sample is vapor- Sample introduction
Liquid sample introduction in ICP-OES is usually
via a pumped nebuliser/spray chamber system,
with argon used as a carrier gas to transport the
aerosol produced by the nebuliser into the
plasma. The pumped nebuliser is capable of
handling quite viscous solutions, suspensions or
even slurries, which makes it very suitable for
used oil analysis. Only a relatively small propor-
tion of the total sample reaches the plasma: the
larger sample droplets produced by the nebuliser
tend to fall out of the gas stream and are lost.
The same may happen to a proportion of the
particulates in the original sample, which are
relatively heavy and also tend to fall out of the
Fig 3: Schematic View of ICP Torch

6 January 2011 www.digitalrefining.com/article/1000641

 values load on the plasma. Indeed some ICP-OES s
attempting to analyze organic samples and
even be extinguished.
gas stream. It is generally
considered that while particles 

of 10 microns or smaller will 

reach the plasma, any larger

size will not, although certain
nebulisers are capable of           

handling particle sizes up to

300 microns.
 

Optics and detectors for ICP-OES.

 



The optical system is the heart 



 

of the spectrometer, as it is here

 


 


that the individual emission
 ­ 



lines are separated and selected

for measurement. The ability to  

discriminate between adjacent




wavelengths is the resolving ‚

 
€





power or resolution of the opti- 

cal system, and is typically in
the picometer range — to cope
with the complexity of ICP
€ƒ„


spectra. There are several possi-

bilities to design an optical
ƒ

system. Common to all is that

they contain at least one disper-
sive component to separate the
radiation from the ICP source.
 

In the so called Paschen-Runge

design a reflecting “diffraction 

grating” is used for this Fig 3: Schematic

Fig 2: Schematic Diagram of an OES Spectrometer
purpose. The dispersed spec- Spectro Arcos and Spectro Genesis
Page 4/9
trum is spread out across an arc
defined by the physical geometry of the system. read electronically, allowing a complete ICP
In traditional instruments, individual emission spectrum to be collected in a matter of seconds.
lines are selected by very carefully positioned Many useful analytical lines are located in the far
slits positioned around this arc and pass through ultra-violet region of the optical spectrum. At
the slits to fall on detectors (usually photomulti- these wavelengths (below about 190 nm) the
plier tubes or PMTs) placed behind them. This atmosphere absorbs UV radiation almost totally,
traditional arrangement has several limitations, so to use these lines it is necessary to either
not least because of the difficulty of placing slits create a vacuum in the optical path or purge the
and detectors sufficiently close together to isolate system with an optically transparent gas. Since
closely adjacent lines, so more recent instru- argon is the gas used to support the plasma and
ments like the Spectro Arcos and Spectro Genesis is also transparent to the UV wavelengths of
use modern and flexible charge coupled devices interest, most modern ICP spectrometers have
or CCD detectors. These semiconductor devices an argon purge system.
are constructed as arrays of very narrow strips, ICP-OES instruments require periodic cali-
or pixels, each an independent detector that bration to give accurate results. A range of
effectively acts as its own exit slit. Such arrays synthetic oil standards containing the analytes
can be placed around the entire arc over which of interest at accurately known concentrations
the spectrum falls, giving continous coverage of are available, as Certified Reference Materials
the spectrum and a virtually unlimited choice of or CRMs, internationally recognised standards
spectral lines for analysis. CCD arrays can be that can be measured to calibrate and/or

www.digitalrefining.com/article/1000641 January 2011 7

 confirm that the instrument is generating
correct results.
There are several “interference effects” that
could lead to incorrect results when analysing oil
samples. Most of them can be dealt with by judi-
cious choice of instrument, sample treatment or
calibration technique.
A full treatment is outside the scope of this
White paper, but the main ones are:
• Spectral interferences As mentioned above, the
emission spectra from the plasma can be very
complex. This means that if the spectrometer has
low resolution, the instrument may be unable to
discriminate between closely adjacent lines from
different elements. This can clearly generate an
error, particularly if one element is present in
high concentration and the other as a trace.
Using a high resolution spectrometer like the
Spectro Arcos will help to minimise these effects.
Another way of improving the situation is to
choose an analytical line that has no potentially
interfering lines close to it. This may be difficult
or impossible with pre-selected fixed detectors
and is where the CCD detector array, with
complete spectral coverage, has real advantages.
• Sample effects Sample viscosities can vary
widely, so the efficiency of nebulisation and
transportation could vary from sample to sample,
or between synthetic standard and sample. The
wide use of surfactant additives in oils can also
have an effect. While modern pumped nebulisers
are less affected than older types, and diluting
the sample improves the situation, the internal
standard technique is also used to overcome this
problem. In this technique, an element not found
in the sample is added to it in known and
constant concentration. Any variations in the
measurement will be reflected in the intensity
values obtained for the internal standard, and
can be used to correct the measurements.
The Spectro Arcos and Spectro Genesis are
state of the art ICP-OES spectrometers, with
features that make them especially suited to oil
analysis.
The Spectro Arcos was designed to handle the
most demanding tasks in elemental analysis. Its
novel shape houses a unique optical system with
an unprecedented resolution of 8.5 picometers
in the analytically important range of 130 to 340
nm and 15 picometers at higher wavelengths.
High resolution is essential to deal with the very
complex spectra generated by the plasma,
8 January 2011
especially with samples containing higher
concentration levels of transition elements. This
is combined with no less than 32 linear CCD
detector arrays to continuously cover the entire
wavelength range relevant to ICP-OES from 130
to 770 nm. The CCD arrays in the Spectro Arcos
differ from those used in other ICP-OES instru-
ments in that they require no special subzero
cooling. The high-speed readout system can read
all 32 CCD detectors and calculate the complete
emission spectrum in less than two seconds. For
work in the far ultra-violet region of the spec-
trum, Arcos uses the Spectro-UV-Plus system.
This overcomes several of the disadvantages, like
contamination of the optical components, typical
of instruments that use vacuum or large volumes
of purge gas. In the UV-Plus system, the optical
enclosure is filled just once with argon, which is
circulated through a cleaning device by a small
membrane pump. Except for replacement of the
cleaning cartridge every twelve months, the UV-
Plus system is completely maintenance-free. This
ensures excellent long-term stability and achieves
substantial savings in operating costs. Over the
lifetime of the spectrometer this can mean
savings of up to one third of the initial instru-
ment purchase price when compared to a purged
system. A common problem with older ICP
systems is instability of the plasma when
subjected to varying sample loads. This can be
particularly true when analysing organic samples
such as oils. The Arcos uses an air-cooled “free-
running” RF generator running at 27.12 MHz
with a power output of 0.7 to 1.7 kW. Free
running generators can independently adjust
their resonant frequency so that the effective
plasma power remains constant even for strongly
varying loads. This is the reason for choosing the
27.12 MHz frequency, whose wider bandwidth
gives greater flexibility in this regard than the
most commonly used alternative, 40.68 MHz.
The design of the sample introduction system
provides a very short sample pathway to the
plasma, so signals stabilise quickly, and very
short flush times between samples. The Arcos
can be integrated with an autosampler/diluter
system under full computer control. With the
combination of the inherent speed of the spec-
trometer and optimised sampling routines,
sample throughput rates of up to 1000 a day are
easily realised. One aspect of automated analysis
is that any drift or instability in the system must
www.digitalrefining.com/article/1000641
 ICP-OES detection limits achieved with Spectro Arcos NIST SRM 1084a results (Spectro Arcos)

Element Wavelength [nm] LOD [ug/kg] LOQ [ug/kg] Element Certified Conc Measured Conc Recovery
Ag 328.068 1.1 3.7 [mg/kg] [mg/kg] [%]
Al 396.152 12 40 Al (104) 102 98.1
Ba 455.404 0.3 1.0 Ag 101.4 ±1.5 100.5 99.1
Ca 393.366 0.08 0.3 Cr 98.3 ±0.8 101.1 102.8
Cd 226.502 0.45 1.5 Cu 100±1.9 103.8 103.8
Cl 134.724 250 830 Fe 98.9 ±1.4 106.5 107.7
Cr 283.563 0.9 3.0 Mg 99.5 ±1.7 97.7 98.1
Cu 324.754 1 3.3 Mo 100.3 ±1.4 103.3 103
Fe 259.94 1 3.3 Ni 99.7 ±1.6 105.7 106
Mg 279.553 0.05 0.2 Pb 101.1 ±1.3 103 101.9
Mn 257.61 0.2 0.7 Sn 97.2 ±2.6 100.7 103.6
Mo 202.03 1.9 6.3 Ti 100.4 ±3.8 104.3 103.9
Na 588.995 12 40 V 95.9 ±9.4 102.4 106.8
Ni 221.648 2.1 7.0 S (1700) 1570 92.4
P 177.495 7.7 25.7 Si (103) 106.9 103.8
Pb 220.351 5.4 18.0
Si 251.612 2.9 9.7
S 180.734 11 37 Table 6
Sn 189.991 5.3 17.7
Ti 323.452 0.48 1.6
V 311.071 1.2 4.0
— truly “plug & analyse” without needing to first
Zn 206.191 0.6 2.0 develop a method.
These factory methods cover wear metals in oil
and additives in oil and other common environ-
Table 5 mental and industrial applications like water,
wastewater, industrial wastewater, soil, sewage
be identified and dealt with. Spectro’s ICAL soft- sludge and filter dust. Compliant to national and
ware automatically monitors operation of the international norms, they are delivered ready for
Spectro Arcos guaranteeing continuous optimum use with an application package that includes the
operating conditions. Furthermore quality sample introduction system, sample preparation
control samples can be measured at intervals to instructions and method documentation.
ensure the quality of results and provide an audit
trail of the instrument’s performance. It has been Used oil analysis by ICP-OES - examples
mentioned above that sequential techniques like There are several national and international
AAS and sequential ICP can be too slow for standard methods that include or recommend
routine oil analysis because of the large number the use of ICP-OES for the analysis of fuels and
of elements that need to be measured. For those lubricating oils by ICP-OES. These include:
wishing to grow to sequential ICP-OES but ASTM D 4951-02 ASTM 5708-02 ASTM 5185-
having limited budgets, the Spectro Genesis 02e2 ASTM 7040-04 ASTM 7111-05.
offers a real economic alternative to sequential To assess the performance of the Spectro
ICP and atomic absorption spectrometers, Arcos for oil analysis, experiments were
enabling those unfamiliar with ICP-OES to bene- conducted to determine the limit of detection
fit from the advantages of leading CCD ICP and accuracy that could be achieved under
technology. Genesis incorporates many of the standard conditions. Solutions for analysis were
technical features of the Spectro Arcos, including prepared in a base oil from organometallic
CCD detection, a 27 MHz free-running RF gener- standards and diluted in kerosene to overcome
ator and a low-maintenance, fast response viscosity effects. A Standard Reference Material
sample introduction system and ICAL intelligent (NIST SRM 1084a) “Wear Metals in Lubricating
calibration logic. The Spectro Genesis can be Oil” was also analysed. The limits of detection
coupled to an autosampler and can achieve achieved and the analytical results for the NIST
sampling rates of approximately 20 samples per SRM 1084a Standard are given in Tables 5-6.
hour. Of particular interest to those new to ICP- These are not the ultimate limits of detection
OES will be the fact that the Spectro Genesis is that could be obtained, but were obtained using
supplied with a complete set of factory methods compromise conditions chosen to give

www.digitalrefining.com/article/1000641 January 2011 9

 Spectro Genesis to analyse the same SRM, NIST
NIST SRM 1084a results (Spectro Genesis)
SRM 1084a. These results demonstrate the excel-
lent analytical performance that can be achieved
Element Certified Conc Measured Conc Recovery
[mg/kg] [mg/kg] [%]
using a modern ICP-OES spectrometer for oil
Al (104) 101.9 98.0 analysis.
Ag 101.4 ± 1.5 96.3 95.0
Cr 98.3 ± 0.8 100.03 101.8 Conclusion
Cu 100 ± 1.9 99.01 99.0
Fe 98.9 ± 1.4 101.04 102.2
The range of ICP-OES and EDXRF spectrome-
Mg 99.5 ± 1.7 102.5 103.0 ters from Spectro Analytical Instruments
Mo 100.3 ± 1.4 101.25 100.9 provides solutions for the determination of
Ni 99.7 ± 1.6 100.24 100.5 elements in waste oils, from high throughput
Pb 101.1 ± 1.3 104.2 103.1
Sn 97.2 ± 2.6 98.9 101.7
analysis in the service laboratory to rapid on-site
Ti 100.4 ± 3.8 103.7 103.3 screening.
V 95.9 ± 9.4 100.7 105.0
S (1700) 1680 98.8
Si (103) 100.3 97.4

LINKS
Table 7
More articles from: SPECTRO Analytical Instruments
comparable analytical figures of merit for all More articles from the following categories:
the elements.
Laboratory/R&D/Quality Control Base Oils
Safety, Health, Environment and Quality
SRM results
The results in Table 7 were obtained using the

10 January 2011 www.digitalrefining.com/article/1000641