EPSILON 5

Analysis of air filters

according to
EPA method IO-3.3

Introduction
The presence of toxic pollutants in the The measurement of the elemental
air has been a subject of research for composition of the particulate
many years in the United States and matter is a key factor in
countries around the world. In the understanding the long-term
United States, air quality standards are health effects of pollution.
governed by the “Clean Air Act” and Suspended particulate matter is typically
administered by the US Environmental pre-concentrated using high volume air
Protection Agency (EPA). One of the key samplers and collected on Teflon filters.
areas of concern for the US EPA is the The chemical analysis of the SPM on Epsilon 5: the essential element
Suspended Particulate Matter content these air filters is traditionally The Epsilon 5 is a fully integrated
(SPM) of air. Historically, the performed by energy-dispersive XRF energy-dispersive XRF analyzer,
measurement of SPM in air was (EDXRF) using EPA method IO-3.3. EPA consisting of a spectrometer, X-Y
concentrated on total suspended method IO-3.3 outlines the protocol for sample handler and software. It has
particulates with no preference to size the analysis of 44 elements on Teflon air a unique combination of features
selection. However, more recent filters, but significant advances in the including a three-dimensional,
research on the health effects of SPM in development of EDXRF instrumentation polarizing geometry, together with
ambient air has focused increasingly on and software have occurred since this a 600 W Gd- or Sc/W-anode X-ray
particles that can be inhaled into the method was published. This application tube and 100 kV generator, up to
respiratory system, i.e. particles of study demonstrates the performance of 15 polarizing and secondary targets
aerodynamic diameter of < 10 µm. the Epsilon 5 EDXRF analyzer according and a high-resolution PAN-32
These particles are referred to as PM10 to the EPA method IO-3.3, with the detector. Designed for accuracy,
(2.5 – 10 µm) and PM2.5 (< 2.5 µm). Not elemental range extended from 44 to 55 precision and low detection limits
withstanding chemical toxicity, it is now elements. the Epsilon 5 excels in the analysis
generally recognized that these particles of medium to heavy metals,
are a significant threat to health. targeting a wide range of elements
of environmental significance.

Epsilon 5 is ideal for the analysis of

particulate matter on air filters.
Filters are placed directly into the
spectrometer without additional
sample preparation.The absence of
sample heating permits long
measurement times required for the
detection of low concentrations of
pollutants in ambient air
monitoring.

The Analytical X-ray Company

 Measurement criteria and calibration
Polarization The air filters application used in this
study was set up according to EPA
The measurement parameters used for
this application are shown in table 1. The
method IO-3.3.The analytical measurement time per condition was 100
The optical path of the Epsilon 5
measurement parameters were optimized seconds, except for the CaF2 target 600
has a 3-dimensional or Cartesian
to accommodate the technological seconds. The measurement time for each
geometry. This geometry
improvements incorporated into the condition can be optimized according to
eliminates the scattered X-ray tube
Epsilon 5. specific needs.
spectrum by polarization, thereby
The method was set up and calibrated
reducing the spectral background
with 59 commercially available air filter
enormously. Backgrounds can be
standards and a blank sample from Elemental Secondary kV mA
an order of magnitude lower than
Micromatter Co. (Eastsound, WA). The range target
traditional direct excitation
standards were composed of pure Na - K CaF2 35 17
(2-dimensional) optics.
elements and compounds deposited on Ca - Sc Ti 70 8.5
40mm Nucleopore media. Ti - Cr, Ba - Nd Fe 80 7.5
Mn - Zn, Sm - Pt Ge 85 7
The calibration was established using a Ga - Rb, Au - Pb Zr 100 6
single standard and a blank for each Sr - Y, Bi - U Mo 100 6
element. A Fundamental Parameter (FP) Nb - Mo Ag 100 6
method was used to correct for the Rh - Cs Al2O3 100 6
difference in sample loading when Table 1. Analytical parameters used for the
analyzing unknowns. application setup

Performance
The Epsilon 5 software features a very analysis. Figure 1 shows a fitted spectrum
powerful deconvolution algorithm, which of air filter standard NIST 2783 obtained
analyzes the sample spectrum and with the Ge secondary target. The
determines the net intensities of element extremely low background is a
peaks, even when they overlap one consequence of the polarizing optical
another. The accuracy with which this is path.
carried out is essential to trace element
I(cps/ch)

4 5 5 7 8
Energy (keV)

2-dimensional optics

Figure 1. Spectrum of
I(cps/ch)

standard NIST 2783,

obtained using the Ge
secondary target

4 5 5 7 8
Energy (keV)

3-dimensional optics Precision

The total method precision is a shown in table 2. No drift correction was
combination of instrument precision applied during the precision studies. The
and stability of the sample during the repeatability and reproducibility are
measurement. The method precision can both excellent and for most elements
be reported for both short the short and long term precision are
(repeatability) and long term nearly identical. Comparison of the
(reproducibility) measurements. The relative RMS values with the counting
repeatability of the Epsilon 5 was statistical error (theoretically, the
assessed by measuring a single filter minimum possible error) shows the
sample (NIST 2783) 20 consecutive times excellent precision of the instrument
in a single day. The reproducibility was and the non-destructive nature of the
determined by measuring the same method for analyzing filter samples.
sample once per day over a 10-day Figure 2 gives a graphical representation
period. of the short and long-term stability of Cr
The repeatability and reproducibility and Cu.
data for a selection of elements are
NIST 2783 Si K Ti Cr Mn Fe Cu Pb
REPEATABILITY (20 consecutive measurements) Analytical
Mean µg/cm2 8.704 0.483 0.143 0.018 0.027 2.319 0.047 0.039
RMS 0.05 0.002 0.005 0.002 0.005 0.012 0.003 0.005 flexibility
RMS rel% 0.578 0.473 3.556 9.907 17.408 0.507 5.759 12.354
REPRODUCIBILITY (Measurements carried out over 10 days)
The Epsilon 5 can be “tuned” to get
Mean µg/cm2 8.704 0.482 0.143 0.018 0.028 2.327 0.047 0.036
the lowest detection limits for a
RMS 0.047 0.003 0.007 0.001 0.006 0.021 0.003 0.003
large number of elements. This
RMS rel% 0.538 0.601 4.849 5.521 21.731 0.879 6.877 8.948
flexibility is achieved using a set of
COUNTING STATISTICAL ERROR
programmable polarization and
CSE rel% 0.492 0.446 2.894 5.978 8.153 0.799 4.157 9.109
secondary targets. The basic
Table 2. Analytical precision for short and long-term measurements system is configured with 9 targets,
that cover the periodic table from
0.06
Na to U, however, an additional 6
Cu targets can be added for dedicated
0.05 applications.
Concentration (µg/cm2)

0.04

0.03
Cr
0.03

0.01 Figure 2.
1 day 10 days
Short and long term
0.00 stability measurements
0 5 10 15 20 25 30
of Cr and Cu in sample
NIST 2783

Accuracy
NIST 2783 Certified Measured
The accuracy of the method was
(µg/cm2) (µg/cm2)
determined by comparing results of the
K 0.53 0.48
NIST 2783 standard. The results of the
Ca 1.32 1.14
selected elements are shown in table 3
Ti 0.15 0.14
and show a good agreement with the
V 0.005 0.005
certified values.
Cr 0.014 0.016
Mn 0.032 0.018
Fe 2.65 2.32
Ni 0.007 0.007
Cu 0.040 0.043
Zn 0.18 0.18
Ba 0.034 0.025
Pb 0.032 0.030
Table 3. Comparison of measured versus certified
values for NIST 2783

Dual-anode Sc/W
Detection limits
X-ray tube
Detection limits are an important The detection limits obtained with the
measure of an instrument’s Epsilon 5 range from 20 ng/cm2 to less The dual-anode Sc/W X-ray tube
performance. The detection limits for than 1 ng/cm2. Across the majority of gives good performance for
this application were calculated from 50 the elemental range the detection limits measuring elements across the
replicate measurements of a Teflon are better or comparable with those periodic table. This tube is designed
blank sample and are based on 1 sigma quoted by the EPA. The high sensitivity to increase the sensitivity for light
(as specified in method IO-3.3). of the Epsilon 5 for measuring elements elements by using the scandium
Calculations are based on a across the periodic table is a direct result characteristic tube lines, while the
measurement time of 400 seconds per of the combination of the 100 kV dual- tungsten characteristic lines ensure
condition, which is chosen to give a anode x-ray tube, a wide range of good sensitivity for the medium to
better comparison with the values as secondary targets and lowered heavy element range.
reported by EPA. The detection limits for background due to the polarizing
55 elements are shown in figure 3 and geometry of the optical path.
compared with the detection limits as
reported by the EPA.
Sample changer 100.00

Epsilon 5

Detection limit (ng/cm2)

The Epsilon 5 is equipped with an USEPA method
integrated robotic sample changer. 10.00
The changer can load samples
individually or in a batch mode.
Samples can be added to the batch
without interrupting the ongoing 1.00
measurements.

0.10
Al P Cl Ca Ti Cr Fe Ni Zn Ge Br Sr Nb Rh Ag In Sb Cs La Pr Sm Gd Dy Er Yb Tl Bi U

Figure 3. Detection limits (1 sigma) for particulate matter on air filters using the Epsilon 5 compared
with those reported by the EPA (reports only elements up to La, except for Pb)

Conclusions
The Epsilon 5 is fully capable of analyzing particulate matter on air filters
according to EPA method IO-3.3 with a high degree of accuracy and precision
for a wide range of elements across the periodic table. The non-destructive
nature of the method means that it is possible to increase measurement times
in case an even higher degree of precision is needed. Furthermore, samples
can be measured repeatedly without damage, ensuring the longevity of

Printed in The Netherlands on 50% recycled, chlorine free paper. Data subject to alteration without notice. For reference purposes only. 9498 707 31511 PN4705
standards.

The advantages of the Epsilon 5 are clear. Measurements are accurate and
precise and the method benefits from simple, essentially hazard-free, sample
preparation. The stability of the instrument is such that individual calibrations
can be used for months. As a result, time-consuming re-standardizations are
Filter samples can be fitted in the
unnecessary and the resulting data are highly consistent over time.
sample cup using a special insert
that assures a good position of the
sample.

Equipment Configuration
Epsilon 5 energy dispersive X-ray fluorescence spectrometer and controlling software.

X-ray tube: Type: side-window tube

Anode: Sc/W
Window: Be (150 µm)
Rating: 25 – 100 kV, 0.5 – 24 mA,
maximum power 600 W
Internal water cooling
Detector type: PAN-32: Ge X-ray detector
Crystal: 30 mm2, 5 mm thick
Window: Be (8 µm)
Energy range: 0.7 – 100 keV
Resolution: ≤140 eV (2000 cps, Mn Kα)
Liquid nitrogen cooling
Polarizing optics: 3-dimensional design
Targets: Al,Ti, Fe, Ge, Zr, Mo, Ag, Ce2O3, Al2O3, CaF2

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