A WHITE PAPER FROM

SPECTRO ANALYTICAL INSTRUMENTS

When results matter

Which Spectrometer
Optical Technology Offers
Superior Performance?
Echelle vs. ORCA

Introduction

The heart of any spectrometer is the optical approaches to optical design: echelle-based or
system. It’s important that laboratory managers Rowland Circle-based (as in Optimized Rowland
understand some salient facts about these Circle Alignment, or ORCA) technologies.
systems. Their challenge: choosing the appro-
priate instrument to perform elemental analyses This paper will discuss key advantages and
of samples for numerous applications in science disadvantages of both approaches. It will also
or industry — with high precision or maximum present reasons why the ORCA polychromator
sensitivity, or both. technology, though less widely used than ech-
elle technology, nevertheless offers objectively
To accomplish these tasks, many managers utilize superior performance in a variety of areas.
instruments that employ inductively coupled
plasma optical emission spectrometry (ICP-OES).
Today’s modern ICP-OES models take one of two
2

Conventional optical Unfortunately, for some applications

technology: echelle echelle-based systems struggle and fail
to provide fast, accurate analyses.
In the basic ICP-OES method, given spec-
Limitations built into their technology
tral lines are characteristically emitted by
create problematic performance in a
specific elements when excited within a
number of areas, including those below.
high-temperature argon plasma. Emitted
light is resolved into these separate lines
Light loss and stray light
by means such as diffraction gratings; the
As mentioned, echelle-based optical
light is finally directed onto a detector ar-
systems typically contain multiple reflec-
ray that quantifies light intensities at these
tive surfaces — including four to eight (or
different wavelengths. Thus differing
more) mirrors, prisms, or cross-dispersers.
elemental components of a sample can
be analyzed and measured.
Unfortunately, such a system can theoreti-
cally lose up to 15% of a given light signal
The optics used in the majority of ICP-
at each optical surface — and even more
OES instruments today employ diffraction
in the ultraviolet/vacuum ultraviolet (UV/
gratings of the echelle type. Echelle optical
VUV) spectral range. Although designers
systems were well suited to be utilized
take steps to limit such a high ratio, when
in conjunction with the two-dimensional
a system uses that many reflectors, these
semiconductor detectors available in the
problems still add up. Echelle systems can
1990s. Echelle systems display their results
typically use a larger opening angle than
in a two-dimensional array, with the spec-
ORCA systems, thus compensating for
trum broken down into short segments for
some reduction in light levels. However,
processing and visualized as a series of
some light loss remains to degrade the instru-
horizontal spectral orders ascending from
ment’s overall optical sensitivity.
infrared to ultraviolet. (Hence the name:
“echelle” is French for “ladder.”)
The problem becomes especially acute
in the UV/VUV range between 130 nm
Compared to previous technologies,
and 190 nm. This loss of sensitivity alone
echelle-based spectrometers combine the
impairs an echelle system’s performance
advantages of relatively high spectral res-
in trying to analyze elements such as
olution and relatively wide spectral range.
aluminum, lead, phosphorus, mercury,
Also, primarily due to optical paths that
sulfur, and the halogens.
are “folded” among multiple reflective
surfaces, echelle systems are relatively
Ironically, while echelle-based systems
small, occupying a compact footprint on
can feel the effects of too little light, they
the laboratory bench.
can also suffer from too much. Their
plethora of reflective surfaces inevitably
In laboratories worldwide, echelle-based
increases the amount of light scattered
instruments provide satisfactory perfor-
inside the optical system itself. The more
mance in a number of analytical situations.
surfaces used, the harder it becomes to
protect the detector from this stray light.
 3

Schematic of a typical ech-

elle system

Since spectrometers depend on precise Optical limitations

readings of light to determine the exact As an inherent characteristic of an echelle
emitted spectra of the element being system’s detector shape and processing
sampled, stray light boosts background technology, it “chops” continuous spectra
radiation, amplifies signal noise, and into smaller pieces using multiple spectral
degrades instrument sensitivity. orders. These pieces are then displayed
in a ladderlike arrangement called an
Example of an echelle spectrum echellogram for analysis and viewing.

Unfortunately, when a sample contains

certain common elements with prominent
emission lines at higher wavelengths, on
the echellogram these lines may appear
quite close together. Emission lines have
a natural width of 2-3 picometers (pm). In
this situation, it can be difficult or impos-
sible to distinguish one elemental
emission from its neighbor.

In practice, spectral interferences caused

by low resolution in the upper wavelength
range, as well as by stray light, make it
harder to perform elemental analyses in
4

line-rich matrices. Such crowded matrices In certain designs, tens of orders or even a
are characteristic of many common metals hundred or more orders may be present.
and most organic materials. Trying to use Problem: in some echelle systems, the
echelle-based systems in these applica- edges between particular orders and their
tions may produce unsatisfactory results. neighbors are not well separated. Adjacent
orders may differ in wavelength by such
small amounts that they introduce the com-
plication known as spectral order overlap.

Each affected echelle system design at-

tempts to compensate for this. However,
no such correction can be 100% success-
ful. The greater the overlap interference,
and the weaker the signal strength from
the analyte of interest, the lower the accu-
racy that can be achieved.

Users with echelle systems that encounter

overlap problems can attempt to select a
different emission line for their target ana-
lyte. But this too can present difficulties.

For instance, boron shows three sat-

isfactorily prominent lines at 249.77
At higher wavelengths, the technology’s low resolution makes it difficult to
nanometers (nm), 249.67 nm, and 182.64
separate closely spaced emission lines.
nm. However, the first two lines may well
encounter troublesome overlaps with iron
Spectral order overlap at 249.78 nm and 249.65 nm. Most unfor-
After a beam of polychromatic light tunately, the third line will often run into
passes a spectrometer’s diffraction echelle systems’ characteristically weaker
grating, multiple light rays emerge, with sensitivity in the 180 nm region. Result:
all wavelengths dispersed in slightly such applications as determining trace
different directions. In one direction, only levels of boron in steel can frustrate some
specific wavelengths where the optical echelle-based systems’ best efforts.
path difference is an integer multiple of
the wavelength are reflected, so all these Wavelength-dependent resolution
spectral orders appear at the same angle. A spectrometer’s resolution measures its
Separating these overlapping orders vital ability to distinguish the separation
requires a second dispersive component between adjacent wavelengths. Generally,
— a grating or prism with a dispersion echelle optical designs display their best
direction orthogonal to the dispersion resolution in a working range of emission
direction of the echelle grating. wavelengths between 190 and 240 nm.
 5

Away from that “sweet spot,” problems usable; below 190 nm, too much light is
arise. Optical aberrations inherent in absorbed by optical system components.
echelle technology mean that the image
focused on the detector loses sharpness, Go into even lower wavelengths and the
and thus resolution, toward the edges. problem becomes insurmountable. It’s
Away from the central focus, emission simply not practical to use an echelle-based
lines are much broader. spectrometer in the UV/VUV region from
130 to 165 nm. Sadly, there are problems
Thus, outside its zone of optimal reso- in higher ranges as well. Echelle-based
lution, echelle technology can struggle resolution continually degrades above
to deliver adequate performance. Its 300 nm.
sensitivity declines as wavelengths fall
below 190 nm. So, for example, operators As a practical consequence, again, it’s
conducting elemental analyses in soils harder to perform elemental analyses
with high aluminum concentrations will in line-rich matrices. These may require
find it hard to measure any trace (parts switching to other spectrometers that use
per billion) concentrations of lead. The different analytical techniques — such as
influence of a strong aluminum line makes atomic absorption spectroscopy (AAS) or
detection difficult or impossible using the ICP-mass spectroscopy — while incurring
lead line at 220 nm. Unfortunately, the additional time, trouble, and expense.
sensitive lead line at 168 nm might not be
Problematic radial-view performance
As outlined above, echelle-based systems
may have trouble trying to analyze trace
concentration levels of certain elements,
such as those in the lower UV/VUV range.
This difficulty often increases when the
echelle system is a model that features
radial-view plasma observation, rather
than axial-view.

A radial, cross-section view of the plasma

receives less light to process than an axial
view. (The radial view sees only a “slice”
across the plasma from side to side,
instead of a longer look from end to end
of the plasma’s entire axis.) It therefore
exhibits less sensitivity.

Away from the central focus, wavelength emission

signals begin to blur.
6

For example, in producing chlorine and Innovative optical

caustic soda, the widely used chloralkali technology: ORCA
electrolysis method depends on a mem-
Fortunately, there exists a totally different
brane cell process. Here processors must
approach to the ICP-OES optical system
rely on close analyses of feed brines to
than the conventional echelle-based tech-
detect certain trace-element impurities —
nology used by most makers.
most critically elements such as calcium,
magnesium, and nickel, which disturb the
This innovative yet well-proven alterna-
tive: Optimized Rowland Circle Alignment
(ORCA) technology. Rather than relying
on two-dimensional detectors, ORCA
systems take advantage of modern linear
detector advances. Such a system incor-
porates arrays of charge coupled device
(CCD) linear detectors specially fitted to
the focal plane using curved mirrors, with
a concave grating arrangement optimized
to limit light loss during diffraction. Prime
Plasma, radial view. ORCA characteristics: sensitivity and
uniform resolution over a wide spectral
process. (Example: for nickel, threshold
range, and exceptional stability.
levels are as low as 10 parts per billion
(ppb).) But echelle-based radial-view sys-
ORCA technology is used in a few of
tems have proven unsatisfactory in this
today’s leading spectrometers, such as the
application. For instance, they struggle
ARCOS, GENESIS, and SPECTROBLUE ICP-
or fail to detect the presence of nickel at
OES analyzers from SPECTRO Analytical
single-digit ppb levels in the brines’ high-
Instruments GmbH.
salt matrices.

With its optimized holographic master

So laboratories faced with these or simi-
gratings housed in a single cast-aluminum
larly challenging analyses may be forced
hollow-section optical chamber featuring
to supplement or replace their radial-view
32 line array detectors, ARCOS has a wave-
instruments with axial-view or even
length range from 130 nm to 770 nm, and
dual-view systems. However, these may
enables simultaneous capture of a sample’s
deliver lower stability and matrix compat-
complete spectrum relevant for ICP-OES
ibility than radial-view models. And both
technology within 4 seconds. It employs
axial- and dual-view approaches require
three separate, optimized optical systems
more complex technologies that add extra
to provide its full- wavelength coverage.
maintenance, cleaning, and other costs.
 7

Note that ORCA-based systems tend to Again, this contributes to a direct, high-
be slightly larger than their echelle-based luminosity optical path that uses only
counterparts. ORCA requires some extra first-order light. Within the ORCA optical
space to accommodate its long, straight, chamber, light loss is minimized, while
high-luminosity light paths. While sel- stray light is much reduced.
dom a problem, this may be an issue for
laboratories where benchtop footprint is a These advantages help maximize the
crucial limiting factor. light throughput so critical for accurate
analyses in certain wavelength ranges.
But otherwise, due to advantages inher- For example, unlike echelle systems,
ent in the design of its technology, ORCA ORCA-based systems exhibit the high
users report that it offers performance sensitivity needed for measurements in
exceeding that of echelle-based systems the UV/VUV range below 190 nm, which
in a number of areas, as discussed below. includes elements such as aluminum, lead,
sulfur, phosphorus, and chlorine. So these
Minimal light loss systems can accurately determine trace
Echelle-style folded optics require at least elements in these difficult matrices.
four to eight reflective surfaces. By con-
trast: in the critical UV range, for Superior optical performance
example, an ORCA system such as Unlike an echelle-based system, with its
ARCOS possesses only two reflective chopped spectra and folded optics, ORCA
optical surfaces (other than its grating) systems offer straightforward, linear
between the entrance slit and the detector. presentation and direct, high-luminosity

ORCA captures the entire spectrum.

8

light paths, as well as constant resolution integration time — as low as 10 seconds

over a wide spectral range. Light loss and for an ORCA-based system such as
stray light are both minimized. In addition, SPECTRO ARCOS.
these systems can furnish good sepa-
ration of spectral lines, with maximum No spectral order overlap
throughput of light (and thus of spectral The problem of spectral order overlap
information), plus simultaneous capture of becomes significant only when an optical
a sample’s complete relevant spectrum. system has difficulty distinguishing
between certain separate spectral orders.
Stability is improved. And sensitivity goes As mentioned, this overlap can degrade
almost off the charts: depending on the accuracy for some echelle-based systems
sample/matrix/wavelength, ORCA sys- in measuring certain elements where
tems can be up to 5 times more sensitive closely adjacent emission lines
than comparable echelle-based systems. may interfere.

Thus an ORCA-based system can more However, by design, ORCA-based optical

accurately process line-rich spectra — systems work exclusively with first-order
vital in many analyses of metals and light. Thus users employing ORCA sys-
alloys — which are often problematic or tems never encounter the problem, and
impossible for echelle-based systems. For can eliminate worries about spectral
just one example, users routinely apply order overlap.
ORCA-based systems in nuclear power
equipment manufacture, where fuel rod Consistent wavelength resolution
claddings must be analyzed for sub-ppm An ORCA-based system also avoids many
levels of boron in zirconium bases. of the optical aberrations and resultant
resolution problems occurring with
Generally, ORCA boosts measurement echelle technology. There is less of a
accuracy and helps reduce expensive detector “sweet spot” phenomenon,
rework. Also, ORCA often requires less outside of which resolution degrades.

ORCA-based systems dis-

play a constant resolution
over a wide wavelength
range.

Wavelength
 9

Instead, the system is able to focus light An optimized ARCOS optic provides
from the full spectrum more clearly access to additional wavelengths for
onto the detector array. ORCA visualizes the halogens — chlorine at 133/134 nm
spectral wavelengths in a lucid line of emission wavelength, bromine at 154,
elemental emission peaks and valleys, as and iodine at 161. Users report this
is evident on an ARCOS system’s display. capability is especially useful in analyzing
petrochemicals, pharmaceuticals, fertiliz-
Again, echelle-based systems achieve a ers, and high-purity chemicals. A tertiary
maximum-resolution working range of optic expands coverage up to 770 nm to
190 nm to 240 nm, with degradation at accommodate elements such as sodium
higher wavelengths and a lower spectral at 588/589 nm, lithium at 670 nm, and
working range typically limited to 165 nm. potassium at 766 nm. The system exhibits
constant, consistent resolution of 8.5 pm
By contrast, the ARCOS analyzer exhibits in the range of 130 nm to 340 nm, and of
a standard maximum-resolution working less than 16 pm from 340 nm to 770 nm.
range in the emissions wavelengths from
130 nm to 340 nm and 340 nm to 770 nm So it efficiently analyzes elements in line-
— delivering greater coverage both high rich matrices with fewer interferences,
and low. Its excellent performance down and requires fewer expensive, time-
to 130 nm (the system shows probably consuming re-analyses via AAS or ICP-
the industry’s best transparency in the mass spectrometry instruments. Example:
spectral range from 130 nm to 180 nm) in a high-aluminum sample, an ORCA-
especially opens up the capability to accu- based system can accurately measure
rately analyze elements such as aluminum lead in trace parts per billion amounts.
at 167 nm, lead at 168 nm, phosphorous at Lead’s ionic emission wavelength at
177 nm, and sulfur at 180 nm. 168 nm won’t suffer interference, despite

Consistent resolution at Consistent Resolution at

Cd 228 nm — 8.5 picometer Ag 338 nm — 9 picometer
Counts [cps]
Cd 228.802 Counts [cps] Ag 338.289 nm
700.0K
800.0K
1 ppm Cd

600.0K
700.0K

600.0K 500.0K

500.0K
400.0K 9 pm

400.0K

300.0K

300.0K
8 pm
200.0K
200.0K

100.0K
100.0K

338.283 338.292
228.796 228.804

0.0K 0.0K
228.76 228.77 228.78 228.79 228.80 228.81 228.82 228.83 228.84 228.85 338.23 338.24 338.25 338.26 338.27 338.28 338.29 338.30 338.31 338.32 338.33 338.84
Lambda [nm] Lambda [nm]
10

the presence of the aluminum spectral dual-view systems — thus avoiding their
line at 167 nm. lower stability and matrix compatibility,
as well as their more complex technologies
Uncompromising radial-view that add extra maintenance, cleaning,
performance and cost.
ORCA-based radial-view systems by
nature are designed to handle trace Other considerations
concentration levels of a wide variety of ORCA-based systems are constructed
elements — including some in the lower with sealed optical chambers using
UV ranges that prove so problematic for recirculating gas. Completely environ-
echelle-based radial models. Best-in-class mentally controlled, they’re built to
sensitivity and lowest detection limits eliminate atmospheric problems that
enable ORCA systems to “see” trace might affect measurement stability in
elements in radial view that others open, constantly purged echelle-based
require dual-view to analyze. systems. A SPECTRO ARCOS analyzer,
for example, employs an air-to-air optical
This means that owners of radial-view stabilization system that maintains the
ORCA-based systems often find them chamber at a constant temperature of
sufficient for their entire range of 15° C (59° F). The diffraction index of the
analytical needs. optics atmosphere holds steady, while its
chance of wavelength drift remains low.
So these laboratory managers may not be This high spectral stability contributes
required to purchase axial-view or even significantly to accurate results.

Limits of Detection (LOD) Comparison: Radial-Axial

10.00

1.00
LOD (µg/l)

0.10

0.01
58 61

1
67 5
M .784

40 2
16 04

V 771
45 42

20 5

25 3
18 8

22 8

23 2
32 5
21 4

Hg 754

07
Li 4.9

Sr .61
Sb 8.21

Si .83
As 8.06

Co 4.43

Ni .59
Cu 8.61
Cd 5.40

Na 7.

Pb 1.6
Ba 9.0

1.
7.
25
4.
18

1
6
9

31
32

n
Ag

LOD 3s — Radial (µg/L)

Element — Wavelength (nm) LOD 3 — Axial (µg/L)

 11

Conclusion
Most makers of ICP-OES analyzers have
retained echelle-based optical tech-
nology. However, ORCA-based optical
systems offer significant advantages in
several crucial areas. Laboratory manag-
ers should consider the likely profiles of
the analytical tasks they need to perform,
and make their choices accordingly.
 Kontaktaufnahme

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