Environmental Instrumentation and Analysis Handbook - 2004 - Down - Application of XRF To The Analysis of Environmental

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12
APPLICATION OF XRF TO
THE ANALYSIS OF
ENVIRONMENTAL SAMPLES
John N. Driscoll
PID Analyzers, LLC
Walpole, Massachusetts
12.1 Introduction
12.2 Basics of XRF Spectroscopy
12.2.1 Detection Geometry
12.2.2 X-Ray Sources
12.2.3 Detectors
12.3 Sample Preparation
12.3.1 Sampling
12.3.2 Soils
12.3.3 Liquid Samples
12.3.4 Filter Paper
12.4 XRF Equipment and Operational Considerations
12.4.1 XRF Equipment
12.4.2 Operational Considerations for Tube-Excited XRF
12.4.3 Minimum Detectable Concentration
12.5 Errors in EDXRF
12.5.1 Total Error
Environmental Instrumentation and Analysis Handbook, by Randy D. Down and Jay H. Lehr
ISBN 0-471-46354-X Copyright # 2005 John Wiley & Sons, Inc.
251
10.1002/0471473332.ch12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/0471473332.ch12 by Universidade De La Coruña, Wiley Online Library on [19/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
252 APPLICATION OF XRF TO THE ANALYSIS OF ENVIRONMENTAL SAMPLES
12.5.2 Counting Errors

12.5.3 Systematic Errors
12.5.4 Random Errors
12.5.5 Average Absolute Error
12.6 Results and Discussion
12.6.1 EPA Results with SEFA-P
12.6.2 Results with Tube-Excited XRF
References
12.1 INTRODUCTION
This chapter is written from the perspective of an environmental professional. It

focuses on those aspects of X-ray fluorescence (XRF) that aid in the understanding
and selection of instrumentation for both field and laboratory methods. In addition,
it should be a useful resource for anyone who is responsible for interpreting data
collected in the field.
Energy-dispersive X-ray fluorescence (EDXRF) is a relatively new analytical
technique that began with the development of the lithium-drifted silicon detector.
Thirty years ago, it could be used to identify elements and estimate the quantity of
the element from the intensity of the peak (intensity vs. energy) in the spectrum. It
was not until the early 1980s that software was developed that could deconvolute
the peaks and correct for absorption and emission from neighboring elements. This
was the beginning of truly quantitative (corrected) results for XRF from complex
sample.
Energy-dispersive X-ray fluorescence has a number of advantages for environ-
mental analysis when compared to other spectroscopic techniques such as induc-
tively coupled plasma (ICP) or atomic absorption (AA):
1. Spectral or chemical matrix interferences can be eliminated through calibra-

tion and spectral deconvolution.
2. Samples can be analyzed for metals nondestructively and utilized for
additional measurements of organic compounds or inorganic ions.
3. Elements can be analyzed over a wide range from low-ppm to percentage
levels.
4. Qualitative and/or semiquantitative analysis requires little sample preparation
and reduces the cost per test.
5. Rapid analysis of a wide variety of environmental samples can be performed.
A comparison of these techniques is given in Table 12.1.

X-ray fluorescence has been used in the field or laboratory for a variety of envir-
onmental applications, including metals in soil,1–3 water,3 and air.4 The advantages
of XRF include ease of use, minimum sample preparation, and rapid on-site
analysis. The latter feature cannot be underestimated when a number of trucks
loaded with excavated soil are waiting for a proper destination.
BASICS OF XRF SPECTROSCOPY 253
Table 12.1 Comparison of EDXRF with Other Spectroscopic Methods for Metals
Technique EDXRF AA ICP

Sample preparation, water None Acid dissolution Acid dissolution
Sample preparation, Grind (if necessary), Acid dissolution Acid dissolution
soil/sludge sieve to 100 mesh
Range ppm to % ppb ppb
Multielement Yes No, generally single Yes
Ease of use Yes No skilled person No skilled person
Another advantage of XRF is that this technique is ideally suited for field screening
work4 as a result of the minimization of sample preparation and the portability.
With an X-ray tube and filters, XRF can be used for a variety of environmental ana-
lyses, including particulate matter in air, as well as metals in soil, and water. We
will be discussing some environmental applications in the following sections.
12.2 BASICS OF XRF SPECTROSCOPY
X-ray fluorescence is the characteristic emission resulting from the absorption of

high-energy radiation by atoms in the X-ray region. This technique is used for
the analysis of materials (heavy metals, sulfur, chlorine) in the environment (soil,
water, air particulate) and is based on fundamental principles of atomic spectro-
scopy.
What is the origin of the spectra? The data in Table 12.2 provide the electronic
configuration of some of the lighter elements. Note that the K shells are filled first,
then the L, and finally the M. Each of these elements has a different electronic con-
figuration. Therefore each will have different energy levels and will produce a dif-
ferent X-ray emission spectrum.
Inner electrons (K, L, or M shell) can be knocked out of their orbital by the high-
energy radiation from an X-ray tube or a radioactive source (109Cd, 55Fe, 241Am,
etc.). These energies have to be higher than the K, L, or M shell binding energies.
Vacancies in the K shell are replaced by electrons from the L or M shell with the
Table 12.2 Electronic Configuration of Some Light Elements
Element Z Ionization Potential (eV) K L M

Na 11 5.14 2 8 1
Mg 12 7.64 2 8 2
Al 13 5.98 2 8 3
Si 14 8.15 2 8 4
P 15 10.6 2 8 5
Figure 12.1 Energy level diagram.
resulting characteristic X-ray emission. Since we are dealing with atoms, absorption
and emission lines are at the same wavelength or frequency. A typical energy level
diagram for an atomic species is shown in Figure 12.1 and a typical X-ray spectrum
is shown in Figure 12.2.
Figure 12.2 Characteristic X-ray spectrum of soil.

sample
105°
x-ray x-ray
source detector
Figure 12.3 Typical XRF geometry.
12.2.1 Detection Geometry

The maximum intensity of fluorescence occurs at 90 from the incident radiation
source. Therefore, for XRF instrumentation, the source and the X-ray detector
are at angles of 80 –110 from each other. A typical geometry is shown in
Figure 12.3.
12.2.2 X-Ray Sources

The types of sources used for EDXRF instrumentation include both radioactive
sources (55Fe, 109Cd, 241Am, 57Co, etc.) and X-ray tubes. The former sources are
all beta emitters. A high-energy particle is emitted with an energy of 5.9 keV
(Mn corresponding to 55Fe) and is used for excitation. Typical source levels are
in the range 10–100 mCi. Instruments using these sources do require a license,
and licensing requirements vary from state to state. Most states require notification
prior to bringing an instrument into the state. The main advantages of a source-
excited instrument is that these sources are monochromatic; for example, the
55
Fe source produces a spectrum of the Mn Ka and Kb lines similar to those in
Figure 12.4. Another advantage is that the sources do not require any power but the
X-ray tube requires 10–20 kV and 10–20 W. This makes battery operation more
difficult because of the high-power utilization. In order to analyze heavy metals
in soil, at least two sources (109Cd and 241Am) are needed. The 55Fe is needed
for the lighter elements in the soil. The disadvantage is that the sources, particularly
109
Cd and 55Fe, do decay and have to be replaced every few years. An EDXRF
instrument based on radioactive sources was described by Driscoll et al.5
The emission spectrum for an X-ray tube is polychromatic or broadband rather
than monochromatic like the radioactive sources. A typical emission spectrum for
an X-ray tube with a Rh anode is shown in Figure 12.5. The count rate (counts per
second) or intensity and therefore the sensitivity of the tube-based XRF are consid-
erably higher than for the source base instrument. With the tube, the anode can be
changed (different tube), the excitation conditions can be optimized, and filters can
Figure 12.4 Effect of detector type on spectral resolution.
be used to compensate for the X-ray continuum and improve detection limits. Tube
lifetimes are generally in excess of 5000 h and low-power tubes (10 W or less) can
be quite stable. The clear disadvantage of the tube is its power consumption, which
makes the development of a battery-operated instrument more challenging. It
is possible to operate an instrument like the XR1000 off an inverter (converts
ID: NO FILTER + RH ANODE

LT = 100 S CPS: 16,730 DT = 60% FS: 1016 Log
Rh Anode
Std. 1
0.000 10.23 20.46 30.69 40.

KeV
Figure 12.5 Emission spectrum of a Rh anode X-ray tube.

12 V DC to 120 V AC). Thus a 12-V battery can be the source of power for this
instrument. A second choice is a gasoline-powered generator.
12.2.3 Detectors
Two types of detectors have been used in XRF instrumentation: proportional
counters, which are the more traditional, and cooled [by liquid nitrogen or electro-
nically (Peltier)] high-resolution semiconductor detectors, which have only been
used in the field very recently. The results obtained with the two types of detectors
can be quite different, as will be shown below.
The relative standard deviation (sQ ) of the pulse amplitude distribution for a
detector is given by
sQ C 1=2
¼
Q E
where Q ¼ distribution in pulse amplitude

C ¼ constant for particular fill gas, ¼ WðF þ bÞ
F, b ¼ constants that depend on ion chamber design
W ¼ energy required to form one ion pair
E ¼ energy deposited by incident radiation
If the standard deviation is multiplied by 2.35, the energy resolution (R) of the
proportional counter can be calculated. At 10 keV, the energy resolution of a pro-
portional counter is 12.5% or 1250 eV.6 The resolution is given by
FWHM
Energy resolution ðRÞ ¼
H0
where FWHM ¼ frequency width at half maximum

H0 ¼ peak centroid
The Si(Li) detectors have been used since the 1960s for detecting X-rays and
low-energy gammas (<100 keV). These semiconductor detectors are useful in
that dimensions can be kept smaller than proportional counters because solid den-
sities are 1000 times greater than for a gas. As ionizing radiation passes through the
semiconductor, many electron–hole pairs are produced along the track. The low
value of the ionizing energy required (3 eV) for a semiconductor detector (about
1
10 that of a proportional counter) creates 10 times the number of charge carriers
than a proportional counter and is one of the factors that leads to increased resolu-
tion for the semiconductor detectors. The resolution for a semiconductor detector
is about 1.5% at 10 keV or 150 eV. The effect of detector resolution is shown in
Figure 12.4, where the energy spectra of an 55Fe source are compared for a
Si(Li) detector (resolution 185 eV) and a proportional counter (resolution 1200 eV).
Figure 12.6 Comparison of a silicon Pin detector and a proportional counter spectrum for lead
paint.
For these tests, only the detector was changed and all the electronics, including
the MCA, were the same. The actual resolution of the proportional counter was
1250 eV, in agreement with the value calculated above. The Mn Ka and Kb peaks
at 5.9 and 6.4 keV are well resolved with the Si(Li) detector, which had a resolution
of 180 eV, also in close agreement with the predicted value. It is clear from the
spectra in Figure 12.6 that with the poor resolution (>1000 eV) of a proportional
counter, adjacent element peaks are difficult to detect. Typically adsorption edge
filters are used to compensate for this problem. However, these filters reduce the
count rate and greatly affect the precision and accuracy of the results. A compar-
ison of the detector characteristics is given in Table 12.3.
Table 12.3 Comparison of X-Ray Detector Performance
Detector Si(Li) Si Pin Gas Proportional

Resolution, eV 165 220–240 700–1200
Range Na–U Na–U Element range limited
Efficiency High Intermediate Low
Count rate High Intermediate Low
Cooling Liquid N2 Electronic—Peltier None
SAMPLE PREPARATION 259
Clearly, the accuracy depends on the resolution of the detector used and the
presence or absence of neighboring elements which may interfere. For the lead
paint sample, the peaks of lead and a neighboring element such as zinc are sharply
resolved for the solid-state detector. Note the significant quantity of zinc in this
paint sample. The spectrum for the XRF instrument with the proportional counter
is shown in Figure 12.6. The high concentration of zinc and its overlap with the lead
La peak make it difficult to quantify the lead peak.
The Si(Li) detector will provide the highest resolution, count rate, and efficiency
of the three detectors. The disadvantage of this detector is that it requires liquid
nitrogen to operate and 30–40 min to cool down. The Si Pin detector operates
over the whole range of elements Na–U, has an acceptable resolution of 230 eV,
and only requires about 5–10 min to cool down. The count rate and efficiency
are lower than the Si(Li) detector. The proportional counter is limited to only the
simplest applications where elements are not close together; otherwise significant
corrections and/or filters are required. If the user wants to cover a significant range,
more than one (two or three) proportional detectors (filters) would be required. The
count rate is considerably lower than the solid-state detectors, as explained earlier
in this chapter.
12.3 SAMPLE PREPARATION
12.3.1 Sampling
One of the first considerations in the field is to ensure that the samples taken are
representative of the site. This is particularly true for soil samples that are typically
nonhomogeneous.
Sometimes multiple levels of contaminants are present at the site, and it is not
unusual to find data such as that shown in Figure 12.7, which profiles the arsenic
Figure 12.7 Arsenic concentration (f ) depth in the soil.

concentration as a function of depth in soil at a hazardous waste site. There is no set

pattern to disposing of hazardous waste.
Even in a shovel full of dirt there can be a significant variation in the concentra-
tion over a range of a few inches. You have to ensure that you have a representative
sample (well mixed). The next consideration is that the sample must be homoge-
neous or all of the analyses will be incorrect whether in the field or in the labora-
tory! One should use a consistent technique in gathering and preparing the sample.
An example is the arsenic in soil shown in Figure 12.7. The standards and
unknowns should be of similar composition to minimize or eliminate matrix effects
from the samples. Bad standards can also affect the accuracy of the result. In the
software, it is important to be able to view the calibration curve and add or remove
standards. The accuracy of the results will depend upon the accuracy of the standards.
12.3.2 Soils
This is a key element for accurate XRF analysis. Samples to be analyzed must be
similar to standards (e.g., particle size, composition). In general, samples may have
to be sieved to a uniform particle size (sandy soils), ground with a mortar and pestle
(soils with a high clay content, sludge) to a uniform particle size, placed in a ball
mill or shatter box (for geological sample such as rocks), and so on. Soil samples
are analyzed directly after preparation by placing in a special low-volume polyethy-
lene sample cup fitted with a 0.15 film Mylar window and counting for 300 s. It is
essential that the standard(s) and the sample have the same surface characteristics
and similar composition. Particle size, compactness, and state (liquid, solid, etc.)
can affect the intensity of XRF.
Soils contain trace heavy metals, with the most common elements being Pb, As,
Hg, Fe, Cu, Zn, V, Ti, Cr, Mn, Cd, and Ni. The reasons for sieving the sandy soil
samples noted above are twofold: The majority of the metals are concentrated in the
fine particles and large particles can cause scattering.
12.3.3 Liquid Samples

Aqueous samples at ppm levels can be analyzed directly by placing in a special
low-volume polyethylene sample cup fitted with a 0.15 film Mylar window and
counting for 300 s. These samples can be analyzed directly without any pretreat-
ment. Heavy metals can be found in surface water, groundwater, rivers, lakes, or
ponds. Other environmental applications involve measurement of sulfur in oil,
diesel fuel, or gasoline; chlorine in process or liquid waste [polychlorinated biphe-
nyls (PCBs) or chlorinated hydrocarbons], and heavy metals in waste oil.
The detection limits are in the low- or sub- (heavy metals) ppm range. One pro-
blem with liquids is that X-rays are not completely absorbed so that these samples
may yield a large continuum background. Some software contains a background
subtraction algorithm than can eliminate the continuum and produce peaks for
low-ppm levels of metals in oil.
SAMPLE PREPARATION 261
Figure 12.8 Low-ppb levels of metals in tap water after preconcentration.
Metals in groundwater, lakes, and ponds should only contain background levels
of heavy metals that are generally low- or sub-ppb levels. These are usually ana-
lyzed by ICP or AA down to < 1 ppb, but XRF can generally go down to
< 1 ppm. What can be done about this? If we take 1 L of water and pour it through
1 g of ion exchange resin, then dry and analyze that resin, we can detect 1 ppb of
metals in water. A spectrum at low-ppb levels is shown in Figure 12.8. This process
takes only about 5 min and can be easily done in the field.
12.3.4 Filter Paper

Particulate matter in the air is collected on filter paper (FP) and can be analyzed by
XRF. One problem frequently encountered is that glass fiber contains trace metals
that vary from batch to batch and could interfere with the analysis of samples. Some
XRF software contains features such as a strip function (HNU Systems, XR1000
software) that will automatically subtract a blank value from each of the filter ana-
lyzers. The net difference will then be reported. Note that the blank FP should be
from the same batch as the FPs being analyzed since there can be considerable
batch-to-batch variations. The blank can also be useful for oil samples. A typical
XRF spectrum is shown in Figure 12.9.
A summary of the sample preparation for soil, water, and air samples is given in
Table 12.4. The sample concentration method is described elsewhere7 and is extre-
mely easy to execute in the field. It involves pouring the water sample (1 L if low-
ppb levels are to be detected) through 1 g of cation exchange material (in a funnel
with a plug of glass wool to keep the resin in the filter), drying, and measuring by
XRF. The standards are treated in a similar manner. This improves the detection
limit by about three decades. With a soil sample, one has to use acid dissolution
to get the metals into a liquid phase, but unless one takes an extraordinarily large
soil sample, there will be only about one order-of-magnitude improvement in the
detection limit.
Figure 12.9 XRF Spectrum of metal particulates (on filter paper) in ambient air.
Table 12.4 Sample Preparation for Environmental Samples
Water Oil Soil Air
Preparation None None Grind, sieve to Collect on filter

100 mesh paper
Analysis Direct Direct Direct Direct
Detection limit Low to sub-ppm Low to sub-ppm Low ppm mg/m3
Methods to Concentrate on ion Acid dissolution, Acid dissolution, Acid dissolution,
improve exchange resin then concentrate then concentrate then concentrate
detection limits on ion exchange on ion exchange on ion exchange
resin resin resin
Improvement 1000 : 1; low-ppb 10–20 : 1; mid-ppb 10–20 : 1; high ppb 10–20:1
levels
12.4 XRF EQUIPMENT AND OPERATIONAL CONSIDERATIONS
12.4.1 XRF Equipment

The major components of an XRF system are the source (X-ray tube or radioactive
source), the X-ray and high-voltage power supply, the sample compartment, the
XRF EQUIPMENT AND OPERATIONAL CONSIDERATIONS 263
detector and preamplifier, the amplifier, the multichannel analyzer (MCA), and the
microprocessor or computer.
12.4.2 Operational Considerations for Tube-Excited XRF

The accuracy and precision of XRF measurements depend upon the count
rate; the higher the count rate, the better the precision and accuracy; for a Si
Pin detector, a rate of >5,000 counts provides optimum results.
Choose XRF conditions so that the voltage is 1.5–2 the energy of the
heaviest element to be detected; that is, Fe Kb is 7.06 keV HV ¼ 10.5–14 kV.
Use the tube current to bring the value of the dead time to approximately
40–60%.
The anode should be higher in the periodic table than the K lines to be excited;
otherwise, the L line will have to be used for analysis.
Most common anode is Rh; it cannot be used to excite, for example, the K
lines of Sn (see the periodic table) and the L line interferes with Cl. The next
most common anode is W; the L line interferes with K lines of Cu and Zn.
Use vacuum or He if analyzing elements below Z ¼ 20 (Ca).
Vacuum, helium, or prepurified nitrogen must be used to eliminate argon in
the air, which absorbs X-rays.
Samples may have to be compressed into pellets if the major components to
be determined are light elements (e.g., limestone and cement).
XRF is very dependent upon the preparation of the surface of the sample
being analyzed.
12.4.3 Minimum Detectable Concentration

The minimum detectable concentration (MDC) is the concentration which produces
a sufficient number of peak counts that can be recognized, with a 95% confidence,
as a positive deviation above the normal variations in the background interference.
The minimum number of detectable counts that will yield a 5% probability of a
false-positive result is 1.64 2sB , where sB is the error in the background. The
MDC is given by
pffiffiffi
B
MDC ¼ 2:33
e
where e is the counting efficiency (i.e., counts per second per unit concentration),
as determined from a single measurement or the slope of the calibration curve, and
B is an estimate of the background interference error based on the background
counts or the blank counts obtained from the zero intercept of the calibration
curve.
12.5 ERRORS IN EDXRF
The most common errors encountered can have two very different meanings which
are frequently confused with each other:
1. Accuracy—the difference between the measured value and the true value.
2. Precision—the degree of agreement among replicate determinations made
under identical conditions.
12.5.1 Total Error

The evaluation of an analytical instrument or method often requires the determination
of the instrumental precision or reproducibility. Such determinations, however,
are often confusing because of terminology. This is particularly true for EDXRF
analyzers because a major source of random error is associated with counting
statistics which may be unfamiliar to many analytical chemists.
The total error in a measurement is the result of systematic and random errors.
Since XRF is a comparative technique, it is assumed the systematic errors have
been eliminated in the instrument calibration procedure. In this case, the total error
(sT) is given by the relation
pffiffiffiffi2
sT ¼ sc þ s2I þ s2p þ s2s
where sc is the counting error, sI represents the instrument-related errors, and sp is

the error related to procedure, such as sample preparation, nonhomogeneous, par-
ticle size differences, and other miscellaneous errors which would be present
regardless of what instrument is used for the analysis. The error in the concentration
supplied by the alternate reference method is ss.
Thus, the total error includes the X-ray analysis error and the error of the alter-
nate technique against which the X-ray method is being calibrated or compared.
12.5.2 Counting Errors

Counting errors are a fundamental phenomenon of the random nature of the radia-
tion process and are not a property of the instrument. They obey the normal laws of
random events and constitute the best possible precision attainable in an X-ray
experiment. The counting error, unlike other errors, can be predicted from a single
measurement. It depends only on the total number of accumulated counts and is
equal to the square root of the total counts. For example, if 10,000 counts were
accumulated p inffiffiffiffiffiffiffiffiffiffiffiffiffi
a 100-s ffi counting interval, the statistical counting error would be
100 counts ( 10,000). This represents the best precision that can be obtained in
a hypothetical 100-s counting interval and implies that the counts accumulated in
68% of a large number of 100-s measurements would fall within about
100 counts
of the true mean (10; 000).
ERRORS IN EDXRF 265
The statistical counting error can be minimized by counting for the longest
interval consistent with the requirements of the total analysis problem. However,
the error cannot be reduced by dividing this interval into segments and taking
the mean of the individual measurements. For example, the standard deviation of the
mean of eight 100-s measurements of the above sample would be
35 counts (100/8).
If the same sample had been counted continuously for 800 s, 8000 counts would
have been accumulated with a standard deviation of
285 counts (80,000). The per-
cent error, however, is identical in both cases (0.35%). The standard deviation of the
mean value can be improved by making more measurements, and the standard
deviation of a measurement can be improved by counting for a longer time.
The magnitude of the other types of random errors (instrumental and procedural)
must be evaluated experimentally by making a sufficient number of replicate mea-
surements to define their frequency distribution. One of the best methods of eval-
uating the total random error is to prepare and analyze a large number of replicate
samples of the same material. This will provide an accurate estimate of the preci-
sion of the total procedure but will not necessarily be an accurate estimate of the
instrumental precision because it will include sampling and sample preparation
errors, which may be significant. The instrumental precision or reproducibility
may be determined by calculating the standard deviation of a series of measure-
ments of the same sample as a function of time or sample position using long count-
ing intervals to minimize the counting error contribution. The procedural errors can
be estimated by subtracting the counting and instrumental errors from the total
errors.
12.5.3 Systematic Errors

Systematic errors yield values which deviate from the true value by a constant
repeatable amount and include errors such as calibration, environmental, technique,
and personal habit errors. These can be either avoided or corrected for and will pri-
marily affect the accuracy.
12.5.4 Random Errors

Random errors cause repeated Individual measured values to disagree and may be
caused by errors in judgment, fluctuating conditions, small disturbances, and count-
ing errors. These errors will determine the precision, and although they cannot be
avoided, they can be determined by statistical methods.
12.5.5 Average Absolute Error

The average absolute error is the sum of the absolute values of the deviations from
the mean divided by the number of measurements. The standard deviation
approaches 1.25 times the average absolute error as the number of measurements
approaches infinity.
12.6 RESULTS AND DISCUSSION
12.6.1 EPA Results with SEFA-P

The HNU source-excited fluorescence analyzer (SEFA-P) was used by an EPA
contractor at a number of Superfund sites in the United States.7 The SEFA-P is a
radioactive source-excited XRF instrument with a Si(Li) liquid nitrogen–cooled
detector. A SITE demonstration of the SEFA-P was conducted, and the instrument
was used to determine the concentrations of ppm to percentage levels of metals in
soils. The results compared favorably with an EPA-approved reference laboratory
method. It was found possible to analyze 30–50 samples in an 8–10-h day. With the
XR1000 and its automated 10-position sample tray, it should be possible to analyze
50–75 samples in the same time period.
12.6.2 Results with Tube-Excited XRF8

Clearly, there is a significant difference in performance between an instrument with
a solid-state detector and a proportional counter. In addition, many of the XRF
instruments with proportional counters utilize radioactive sources that produce
one-third to one-half the count rate produced by an X-ray tube, further reducing
the count rate, detection limits, and accuracy. The effect of count rate on the mini-
mum detectable concentration (MDC) was mentioned previously and is given as
pffiffiffi
MDC ¼ 2:33 B=count rate
where B is the background interference level.

Thus, the higher the count rate, the lower the detection limit. Of course, resolu-
tion will also have an effect on detection limits since the higher resolution detector
will produce sharper peaks, which will be more easily detected. This can be seen in
the XRF spectrum of lead paint shown in Figure 12.6. A table-top XRF analyzer,
the XR1000 (HNU Systems) is shown in Figure 12.10. This instrument has a small
footprint, Windows XRF software, and a Peltier (electronically cooled) Si Pin
detector and provides high performance in a compact package.
Resolution also becomes important for the detection of lighter elements, as
shown in Table 12.5. The energy spacing for adjacent lighter elements is about
one-half that for transition elements, as shown in Table 12.5.
Another area where detector resolution becomes important is in the use of soft-
ware for qualitative (auto identification) and quantitative results such as fundamen-
tal parameters and techniques (FPTs) and other software where corrections are
made for absorption and enhancement effects for neighboring elements. With broad
peaks, it becomes exceedingly difficult to apply these corrections. The calibration
curve for Mg in cement in Figure 12.11 was obtained with the HNU XRF analyzer.
Figure 12.11 has no interelement corrections. In Figure 12.12, the absorption/
enhancement correction for silicon was included. The difference in the calibration
curves shown in Figures 12.11 and 12.12 demonstrated the improvement in the
results when the corrections are used.
267
RESULTS AND DISCUSSION
Table 12.5 Comparison of Energy Level Spacing for Transition
Difference ¼ 0.53 KeV
Difference ¼ 0.253
Ka—1:487 KeV
Ka—1:740 KeV
Ka—6:93 KeV
Energy (KeV)
Ka—6:4 KeV
Figure 12.10 HNU model XR1000 table-top XRF.
Element
Co
Fe
Al
Si
Metals and Light Elements
Atomic Number
26
27
13
14
S1
0.28
MgO
Concentration [%]
0
0 Mg Ka Intensity [cpa] 25.41
Figure 12.11 Magnesium calibration curve with no corrections.
There are two different software programs that can be used: empirical and FPT.
The empirical method requires the use of multiple standards (minimum of three
plus one for each element used for correction) to bracket the unknowns. This soft-
ware uses a linear regression fit with a Simplex variation to minimize the error in x
and y coordinates. Standards (use the AA or ICP data as the actual concentration)
can be prepared by using the AA or ICP data from the same site. Note: If this pro-
cedure is used, a representative aliquot of the soil samples should be available. Now
the soil data by XRF should correlate with the AA or ICP data for the site. Some
S1
0.28
MgO
Concentration [%]
0
0 37.11
Mg Ka Intensity [cps]
Figure 12.12 Magnesium calibration curve with corrections.

RESULTS AND DISCUSSION 269
Figure 12.13 Comparison of AA and XRF results for soil samples.
site data in Figure 12.13 compares AA with XRF data. The correlation coefficient is
0.995. The empirical method is useful from ppm to percentage levels, but multiple
calibration curves would be required to cover this range. An accuracy of 98þ%
may be obtained, but this depends upon the accuracy of the standards, the count
rate, matrix effects, and other factors.
The importance of interelement corrections in environmental analysis can be seen
with the analysis of lead and arsenic. The Ka line of arsenic and the La line of lead
are both at 10.5 keV. If both are present, there are several options: (a) use interele-
ment corrections (will need standards with known arsenic and lead concentrations)
or (b) use the Kb line of arsenic and the Lb line of lead. The lower limit of detection
will not be as low with the b lines, but the interference will be eliminated.
The FPT standardized program can be used for high ppm to 100%. All of the
elements in the sample must be known and must add up to 100%. In this program,
corrections are made for detector efficiency, tube output, other elements (absorption
and enhancement), and so on. At least one standard is needed. Typical accuracy
ranges from 90 to 95%.
Driscoll and Johnson9 have shown the neural networks can be successfully
applied to qualitative and quantitative identification of elements such as lead (Pb)
and arsenic (As). the Pb La and As ka X-ray spectra overlap at 10.6 keV. Using a
single neuron and 15 inputs per element, they were able to predict the shape of the
As and Pb spectra (qualitative). For quantitative analysis 45 inputs were required
with three processing neurons to determine As and Pb concentrations in complex
soil mixtures. This technique has significant promise for improving algorithms used
in spectroscopic software.
In this chapter we have described a number of basic aspects of XRF in order to
provide the reader with a basic understanding of both XRF theory and sample pre-
paration. Should the reader be interested in learning more about XRF applications
or detectors and electronics, Ref. 1 and 6 are recommended.
REFERENCES
1. V. Valkovic, X-Ray Spectroscopy in the Environmental Sciences, CRC Press, Boca Raton,
FL, 1989.
2. Anonymous, Data Quality Objectives for Remedial Response Activities, RI/FS
Activities at a Site with Contaminated Soils & Ground Water, PB 88-131388, EPA,
Washington, DC, March 1987.
3. Anonymous, Data Quality Objectives for Remedial Response Activities, Development
Processes, PB 88-131370, EPA, Washington, DC, March 1987.
4. R. K. Stevens and W. F. Herget, Analytical Methods Applied to Air Pollution, Ann Arbor
Science Publishers, Ann Arbor, MI, 1974.
5. J. N. Driscoll, J. K. Marshall, E. S. Atwood, C. Wood, and T. Spittler, A New Instrument for
the Determination of Heavy Metals & Radioactivity at Mixed Waste Sites, Am. Lab., July
1991, p. 131.
6. G. F. Knoll, Radiation Detection and Measurement, Wiley, New York, 1989.
7. EPA, Superfund Innovative Technology Evaluation: Characterization and Monitoring
Program, http://www.clu-in.com/site/charmon.htm.
8. J. N. Driscoll, Field Analysis of Metals in the Environment by XRF, Int. Env. Tech.,
September/October 1998.
9. J. N. Driscoll and W. Johnson, Use of Neural Networks in XRF, Pittsburgh on Anal.
Chem. & Applied Spectroscopy, Paper 1968P New Orleans, LA, March 2002.

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10.1002/0471473332.ch12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/0471473332.ch12 by Universidade De La Coruña, Wiley Online Library on [19/01/2023].

12.5.2 Counting Errors

This chapter is written from the perspective of an environmental professional. It

1. Spectral or chemical matrix interferences can be eliminated through calibra-

A comparison of these techniques is given in Table 12.1.

Technique EDXRF AA ICP

12.2 BASICS OF XRF SPECTROSCOPY

X-ray fluorescence is the characteristic emission resulting from the absorption of

Table 12.2 Electronic Configuration of Some Light Elements

Element Z Ionization Potential (eV) K L M

Figure 12.1 Energy level diagram.

Figure 12.2 Characteristic X-ray spectrum of soil.

Figure 12.3 Typical XRF geometry.

12.2.1 Detection Geometry

12.2.2 X-Ray Sources

Figure 12.4 Effect of detector type on spectral resolution.

ID: NO FILTER + RH ANODE

0.000 10.23 20.46 30.69 40.

Figure 12.5 Emission spectrum of a Rh anode X-ray tube.

where Q ¼ distribution in pulse amplitude

where FWHM ¼ frequency width at half maximum

Table 12.3 Comparison of X-Ray Detector Performance

Detector Si(Li) Si Pin Gas Proportional

12.3 SAMPLE PREPARATION

Figure 12.7 Arsenic concentration (f ) depth in the soil.

concentration as a function of depth in soil at a hazardous waste site. There is no set

12.3.3 Liquid Samples

Figure 12.8 Low-ppb levels of metals in tap water after preconcentration.

12.3.4 Filter Paper

Table 12.4 Sample Preparation for Environmental Samples

Water Oil Soil Air

Preparation None None Grind, sieve to Collect on filter

12.4 XRF EQUIPMENT AND OPERATIONAL CONSIDERATIONS

12.4.1 XRF Equipment

12.4.2 Operational Considerations for Tube-Excited XRF

12.4.3 Minimum Detectable Concentration

12.5 ERRORS IN EDXRF

12.5.1 Total Error

where sc is the counting error, sI represents the instrument-related errors, and sp is

12.5.2 Counting Errors

12.5.3 Systematic Errors

12.5.4 Random Errors

12.5.5 Average Absolute Error

12.6 RESULTS AND DISCUSSION

12.6.1 EPA Results with SEFA-P

12.6.2 Results with Tube-Excited XRF8

where B is the background interference level.

Table 12.5 Comparison of Energy Level Spacing for Transition

Difference ¼ 0.53 KeV

Figure 12.11 Magnesium calibration curve with no corrections.

Figure 12.12 Magnesium calibration curve with corrections.

Figure 12.13 Comparison of AA and XRF results for soil samples.

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