Talanta 51 (2000) 717 – 725

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Thick-target PIGE analysis of plant materials

preconcentrated by dry ashing
K.-E. Saarela a,*, L. Harju a, J.-O. Lill b,c, J. Rajander a, A. Lindroos d,
S.-J. Heselius c
a
Laboratory of Analytical Chemistry, A, bo Akademi Uni6ersity, FIN-20500 Turku, Finland
b
Department of Physics, A, bo Akademi Uni6ersity, FIN-20500 Turku, Finland
c
Turku PET Centre, Accelerator Laboratory, A, bo Akademi Uni6ersity, FIN-20500 Turku, Finland
d
Department of Geology and Mineralogy, A, bo Akademi Uni6ersity, FIN-20500 Turku, Finland
Received 5 July 1999; received in revised form 14 October 1999; accepted 8 November 1999

Abstract

Plant materials were dry ashed at 550°C and analysed using particle-induced prompt gamma-ray emission (PIGE).
The analyses were performed with an external beam of 3 MeV protons incident on the target. Seven biological
certified reference materials were analysed and used for the evaluation of the method for Na, Mg, Al, P and Mn. The
elemental concentration to detection limit ratios were greatly enhanced by dry ashing of the biological materials. The
concentrations of the elements in ashes were clearly above the values at which reliable analyses can be made. The
method was applied to samples of spruce and pine. Due to the low ash content of the wood samples, the sensitivity
of the method was radically improved. The detection limits for the five elements studied in spruce wood were in the
range 0.014–2.5 mg g − 1. The set-up and the beam current used enabled simultaneous particle-induced X-ray emission
spectrometry (PIXE) analyses, with the sensitivity optimised for heavier trace elements. © 2000 Elsevier Science B.V.
All rights reserved.

Keywords: PIGE; Dry ashing; CRMs; Plant materials

1. Introduction excited nucleus is produced by a nuclear reaction,

Particle-induced g-ray emission (PIGE) is an
analytical technique based upon the measurement
of g-ray emission from a sample irradiated with
ions from a particle accelerator [1,2]. In PIGE an
* Corresponding author. Tel.: +358-2-2154-140; fax: +
358-2-2154-479.
E-mail address: ksaarela@abo.fi (K.-E. Saarela)
normally a (p,p’ g), (p, g), (p,n g) or (p,a g)
reaction. The g-ray emitted in the de-excitation is
detected and the nucleus can be identified from
the g-ray energy. However, this nucleus can be a
product of different nuclear reactions. It is there-
fore difficult to identify the target nucleus and
furthermore to relate the detected g-yield to the
concentration of a nuclide or an element in the
sample. The g-ray yield changes rapidly with the

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PII: S 0 0 3 9 - 9 1 4 0 ( 9 9 ) 0 0 3 2 6 - 4
718 K.-E. Saarela et al. / Talanta 51 (2000) 717–725
incident particle energy. Therefore thick-target g-
ray yields have been measured and tabulated for
different particle energies [3 – 6]. Collected data
can be found in the book by Bird and Williams
[1].
A flexible experimental set-up for external-
beam particle-induced X-ray emission (PIXE)
analyses of thick solid samples has been devel-
oped at the Accelerator Laboratory of A, bo
Akademi University [7]. The PIXE technique has
been employed mainly in the analysis of biological
materials. In recent years the sensitivity has been
optimised for the analyses of heavier trace ele-
ments [8–11]. Biological samples were also dry
ashed prior to the analyses in order to increase the
sensitivity for these elements [8]. The gain for
different biological materials was related to the
ash content of the material studied [11]. In the
PIXE analyses the sensitivity was hampered espe-
cially by the high content of potassium. The spec-
tral background in PIGE is, however, not
expected to be negatively affected. This is due to a
low g-ray yield for elements like K and Ca. The
gain in PIGE can therefore be greater.
Light elements that can be determined with
PIGE are often difficult to analyse with other
methods. The instrumental methods generally
used, demand the often laborious step of sample
dissolution. Dissolution of ashes is often trouble-
some and is, e.g. in the case of aluminium, a
principal source of error in quantitative analyses
[12]. Dry ashing with modern programmable fur-
naces does not require constant operator attention
and is therefore not a laborious step in the analyt-
ical procedure. If the ash can be analysed without
dissolution the enrichment can be effectively
benefited.
The use of external-beam PIGE spectrometry
has been rather limited [13] and biological appli-
cations are limited to a few studies of mainly
biomedical samples. In the present work PIGE is
evaluated as a complementary technique to thick-
target PIXE performed with 3 MeV protons. The
elements Na, Mg, Al, P and Mn are analysed in
dry ashed plant materials with PIGE. The method
is evaluated by seven biological certified reference
materials (CRMs) and applied to the analyses of
wood materials. Data on the elemental concentra-
tions in wood are of great industrial importance.
Results obtained by PIXE-analyses of trunk wood
have been earlier reported by our group [9,10].
2. Experimental
2.1. Instrumental set-up
Most of the set-up was earlier used in thick-
target PIXE analyses and is described in detail
elsewhere [11]. The set-up includes a photo-multi-
plier (PM) tube monitoring light from the beam
path. The current from the PM-tube is integrated
over the acquisition time and used for normalising
peak areas in the obtained spectra [14]. The parti-
cle beam of the A, bo Akademi MGC-20 cyclotron
was collimated to a diameter of 1 mm. An Intrin-
sic Germanium Planar (IGP) detector was used
for detecting X-ray emission from the irradiated
sample and a High-Purity Germanium detector
(Model: GMX-25195-S) for measuring the g-ray
emission. The resolution (FWHM) for the HPGe
detector was 2.6 keV at 1332 keV (60Co) at mea-
suring conditions. The g-detector was placed 35
mm behind the target at an angle of 45 degrees
with respect to the beam path (Fig. 1). Every
sample was irradiated for about 11 min with a
beam of 3 MeV protons. The beam spot was
changed every 90 s. The recorded spectra were
analysed using the SAMPO90 computer program
[15].
2.2. Sampling of trunk wood
Samples of wood were taken in 1994 from a
polluted area, Harjavalta (x= 22° 10% 12¦ E, y=
61° 21% 27¦ N), where a Cu–Ni smelter has been
active for about 50 years. For Harjavalta, PIXE
results reported earlier by our group [10] showed
elevated concentrations of heavy metal ions. The
other sampling site, Merimasku (x= 21° 48% 49¦
E, y=60° 29% 48¦ N), represents a relatively un-
polluted area in the Turku archipelago. The sam-
ples from Merimasku were taken in 1997. Mainly
Norway spruce (Picea abies) was studied in this
work. Discs were cut of the stem within 0.5 m
above the ground. In the laboratory, the sampling
 K.-E. Saarela et al. / Talanta 51 (2000) 717–725 719

was made by cutting or drilling the disc in a spectroscopically pure graphite. The obtained pel-
sectorial pattern in order to get a representative lets were 1.5 mm thick with a polycarbonate
sample of the trunk [9,10]. backing of 0.5 mm. A pure graphite pellet was
also prepared and irradiated for an equally long
time as the samples to determine the spectral
2.3. Dry ashing and sample preparation background for the set-up.
The CRMs and the wood samples were dried at
2.4. Calibration
105°C in order to obtain the concentrations on
dry matter basis. The dry ashing of the biological
Experimentally obtained calibration constants
materials was performed with a Nabertherm Pro-
KZ for the elements are used for quantification of
gram Controller S 27 oven to 550°C. Amounts of
both the nonashed and the ashed samples. These
1–3 g of the CRMs and 10 – 20 g of the wood
constants reflect the experimental conditions, in-
samples were weighed for the dry ashing. The
cluding, e.g. geometry and the stopping power of
temperature was increased very slowly, especially
the two types of samples analysed. The stopping
in the range 200 – 350°C, to ensure a complete
power in a sample is related to the atomic num-
charring. The pyrolysis is an important step of the
bers of the matrix elements. No stopping-power
procedure and a prerequisite for an ashing tem-
corrections are performed in this work. The cali-
perature not exceeding the adjusted furnace
bration constants KZ are calculated from the peak
temperature.
areas YZ according to
Both the ashes and the original biological mate-
rials were pressed to pellets on a backing of KZ = C ZY·QZPM

Fig. 1. Set-up for external-beam PIXE/PIGE analyses of thick samples. The particle beam enters from the right and the g-ray
detector is down to the left.
720 K.-E. Saarela et al. / Talanta 51 (2000) 717–725
Fig. 2. PIGE-spectra of nonashed and dry ashed Wood Fuel
(NJV 94-5).
where CZ is the certified concentration of the
element Z and QPM the integrated charge on the
target. Elemental concentrations in the ashed
samples are calculated from the ash content. As-
suming constant isotopic ratios for the elements
the g-ray yield from a certain nuclide can be
considered representative for the element.
The following CRMs are used for calibration
and evaluation of the method: Pine Needles SRM
1575 and Tomato Leaves SRM 1573 from Na-
tional Institute of Standards and Technology
(NIST), Energy Grass (Phalaris arundinace L.)
reference material NJV 94-4, Energy Forest
(Salix) NJV 94-3, Wood Fuel NJV 94-5 and
Energy Peat (Carex) NJV 94-1 from the Swedish
University of Agricultural Sciences and Wheat
Flour ARC/CL-3 from the Agricultural Research
Centre of Finland.
3. Results and discussion
3.1. Spectrum interpretation and background
contributions
In Fig. 2 the PIGE spectra for both nonashed
and ashed Wood Fuel are given. For simplicity
only the peaks of Mn-55 (126 keV), Mg-25 (585
keV), P-31 (1266 keV), Al-27 (171, 844 and 1014
keV) and Na-23 (440 and 1636 keV) are marked.
These peaks are a result of nuclear excitation by
inelastic scattering and correspond to transitions
to the ground state except for the 171 keV peak of
Al and the 1636 keV peak of Na, which feed the
transitions to the ground states. The peaks from
Mg and Mn are lost in the background of the
spectrum of the biological sample.
The aluminium line at 171 keV (more precisely
170.68 keV) corresponds to a transition between
the 1014 keV (1014.43 keV) and the 844 keV
(843.76 keV) energy levels and has the lowest
yield of these three lines. The lower yield is partly
compensated by the higher detector efficiency in
this spectral region. No background peak was
observed at 171 keV. At 1014 and 844 keV there
were contributions from the aluminium in the
surrounding constructions, like the beam line, as
the set-up was originally designed for thick-target
PIXE. The background contributions to the Al
lines in Wood Fuel were 40% of the peak areas
for the biological material but only 1% of the
peak areas for the ashes. The background contri-
bution was subtracted from the peak areas in the
calculations of the concentrations.
The yield at 440 keV from Na-23 was higher
than at 1636 keV. However the measurement of
background radiation revealed a peak at 440 keV.
This background contribution was 0.6–4.0% for
the ashes compared to 8–60% for the biological
materials.
3.2. Determined calibration constants
Calibration constants KZ determined and used
in this work are presented in Table 1. The con-
stants were determined both for ashed material
(KZ,ASH) and nonashed material (KZ,BIO). In the
calculation of the elemental calibration constants,
 K.-E. Saarela et al. / Talanta 51 (2000) 717–725 721

CRMs with high certified concentration and small
confidence intervals were used. The elemental
concentrations in the ashed CRMs were calcu-
lated from the ash content obtained in the dry
ashing process and used in the calculation of
calibration constants for the ashed material
KZ,ASH.
The ratios of KZ,BIO to KZ,ASH are also included
in the table. This ratio will be independent of the
concentration of the analyte element in the origi-
nal sample. The KZ,BIO/KZ,ASH ratios, mostly in
the range 1.1 – 1.3, reflect the poor counting
statistics for some of the nonashed samples, the
interference from the background radiation and
the matrix effects. The type of calibration stan-
dard should be similar to that of the sample.
KZ,BIO should be used when analysing biological
samples and KZ,ASH for analyses of ashed samples.
3.3. Validation of the method for quantitati6e
analyses
The results of the PIGE determinations of Na,
Mg, Al, P and Mn in the seven biological CRMs
are shown in Table 2, where quantification was
done by using the g-lines with the highest KZ-val-
ues in Table 1. The results were obtained in single
PIGE determinations. The certified or recom-
mended concentrations and their intervals are in-
cluded in Table 2. Consensus values compiled by
Roelandts and Gladney for Na and Mg in Pine
Needles and Na in Tomato Leaves are included as
well [16]. All five analyte elements were certified
only in one of the seven CRMs analysed. For
most elements and lines, results obtained with
combined dry ashing and PIGE analyses agreed
with the certified values. Manganese and also in
some cases, magnesium and aluminium, were im-
possible to detect without preconcentration. Re-
sults obtained for all five elements without
preceding dry ashing differed greatly from those
reported. The discrepancies can be attributed to
the low concentrations in nonashed materials and
to the background contributions discussed in
chapter 3.1.
From the results in Table 2 it can be concluded
that no major losses of any of the above men-
tioned elements occur during the dry ashing. Ac-
cording to Bock [12] no Mg or Al will be lost
during dry ashing at 550°C. When the sample
results in an alkaline ash it can safely be ashed up
to 800°C without loss of phosphorous. According
to Gorsuch [17] upper limits of 500–550°C seem
to be advisable for manganese. Losses of sodium
will be, to some extent, a function of both the
chemical form in which the element occurs and

Table 1
Calibration constants (Kz) for biological materials and corresponding ashes (Energy Forest, Na, Wheat Flour, Mg and P, Pine
Needles, Mn and Al)a

Nuclide Energy (keV) Biological sample Ashed sample Ratio KZ,BIO/KZ,ASH

Concentration KZ Concentration KZ

Na-23 440 0.029 3.14 1.81 3.69 0.85

Na-23 1636 0.029 0.637 1.81 0.561 1.13
Mg-25 390 0.562 n.d. 61.8 0.0222
Mg-25 585 0.562 0.0477 61.8 0.0381 1.25
Mg-25 975 0.562 n.d. 61.8 0.0101
Mg-26 1809 0.562 n.d. 61.8 0.00111
Al-27 171 0.545 0.0880 22.1 0.0457 1.92
Al-27 844 0.545 0.251 22.1 0.190 1.32
Al-27 1014 0.545 0.314 22.1 0.265 1.19
P-31 1266 2.09 0.0699 230 0.0553 1.26
Mn-55 126 0.675 n.d. 27.4 0.0445
Mn-55 931 0.675 n.d. 27.4 0.0325

a
Elemental concentrations are in mg g−1 by dry weight. n.d., not determined.
 722
Table 2
Elemental concentrations in CRMs obtained by PIGE analysesa

Element /Energy Obtained con- Energy Forest Wood Fuel Energy Peat Energy Grass Pine Needles Tomato Leaves Wheat Flour
(keV) centration NJV-94-3 NJV 94-5 NJV 94-1 NJV 94-4 SRM 1575 SRM 1573 ARC/CL-3

Ash (%) 1.603 1.221 3.963 6.762 2.466 19.410 0.909

Na certified 29 94.3 40 912 (80 9 56) (300 9150) 36 9 16b 4809 100b
440 by preconc. 39.7 32.2 240 31.6 495 4.4

K.-E. Saarela et al. / Talanta 51 (2000) 717–725

1636 by preconc. 35.9 32.5 239 28.6 516 4.0
440 direct analysis 37.5 23.1 243 31.4 311 17.0
1636 direct analysis 31.8 11.1 182 23.7 248 24.9
Mg certified 340 9 36 300 9 18 770 9 89 880 974 1180 9120b (7000) 562 9 10
585 by preconc. 339 294 844 963 1090 5730
585 direct analysis 361 357 719 742 4092
Al certified (20 9 15) 260 9 32 900 979 1800 9 170 545 9 30 (1200)
171 by preconc. 32.8 273 992 1740 1380 11.6
844 by preconc. 18.0 269 997 1490 1220 8.3
1014 by preconc. 17.7 269 957 1490 1180 7.8
171 direct analysis 198 419 978 642
844 direct analysis 296 664 1230 893
1014 direct analysis 345 703 1440 979
P certified 500 9 100 210 9 28 450 979 1090 9 90 1200 9 200 34009 200 2090 9 140
1266 by preconc. 639 203 406 1235 1050 3600
1266 direct analysis 813 571 642 1310 1270 2760
Mn certified 60 911 210 9 38 36 9 3.8 160 9 16 675 9 15 238970 12.87 90.34
126 by preconc. 86.4 203 48.3 159 242
931 by preconc. 60.2 190 44.8 123 306

a
Certified concentrations are in bold face and recommended within brackets, the underlined concentrations were used for calculating the calibration constants (Table
1) and for quantification, all concentrations are in mg g−1 by dry weight.
b
Consensus values according to Roelandts and Gladney [16].
 K.-E. Saarela et al. / Talanta 51 (2000) 717–725 723

Table 3
Concentration to detection limit ratios (C/DL) in the biological CRMs, Energy Forest (Na, Mg, P, Mn) and Wood Fuel (Al) and
in their corresponding ashesa

Element Energy (keV) Nonashed material Dry-ashed material

C DL C/DL C DL C/DL

Energy Forest
Na 440 29 1.4 20.4 1800 4.1 439
Mg 585 340 165 2.1 21 000 405 52
P 1266 500 94 5.3 31 000 237 131
Mn 126 60 3740 723 5
Wood Fuel
Al 1014 260 21 30 21 000 89 237

a
Concentrations are in mg g−1.

the nature of the material in which it is found [17].
Ashing temperatures of both 450 and 550°C have
been recommended for biological material [12].
3.4. Limits of detection and quantitati6e
determination
The enrichment obtained by dry ashing clearly
improves the accuracy of the analyses. The
concentration to detection limit (C/DL) ratios for
some energy lines of elements in both the nonashed
Energy Forest and Wood Fuel CRMs and the
corresponding ashes are reported in Table 3. The
detection limits were determined according to
general practice as three times the square root of
the background area below the peak divided by the
calibration constant [11].
As a limit of quantification (LOQ) 10 times the
square root of the background (or ca 3.3× DL) has
been given [18]. Many of the concentrations in the
biological CRMs were too low to fulfil this
criterion. In Energy Forest the C/DL ratio 2.1 for
magnesium is too low for reliable quantification.
For the ashes the concentrations clearly exceed the
limits of quantification.
Table 3 clearly shows that the C/DL ratio has to
be considered when directly analysing biological
materials with thick-target PIGE. The detection
limits for the ash matrix are higher than for the
corresponding biological material. However, by
using dry ashing the over-all sensitivity of the
method is radically improved, due to the high
preconcentration factor obtained.
3.5. Analysis of trunk wood
The generally low ash content of spruce and
pine wood makes this type of sample especially
suitable for the analytical method described. The
results of the analyses of some trunk wood sam-
ples by combined dry ashing and thick-target
PIGE are given in Table 4. Elemental lines given
in Table 3 were used for analytical determina-
tions. The concentrations of Na, Mg, Al, P and
Mn are given for the nonashed material on dry
matter basis. Without enrichment by dry ashing
the concentration levels of the elements observed
were too low for quantification.
Quite few data have been published on the
content of light elements in wood. This holds
especially for spruce wood. For the phosphorous
concentration of spruce Young et al. [19] and
Bailey et al. [20] report 50 mg g − 1, which is close
to the values obtained in this work.
The data for P and Mn from simultaneous
PIXE-analyses are also given in Table 4 for com-
parison. For manganese good agreement was ob-
tained for the two methods. A systematic error
can be seen for the samples from Merimasku as
PIXE gave somewhat lower concentrations.
Larger deviations were obtained for phosphorous
between the two methods. The phosphorous con-
724 K.-E. Saarela et al. / Talanta 51 (2000) 717–725

centrations were close to the limit of quantitative
determination for the PIXE method (LOQ = 53 mg
g − 1) [11]. The PIXE analyses of phosphorous are
affected by escape peaks, low detector efficiency
and intense bremsstrahlung [21].
By considering the ash percentage, the detection
limits for the whole analytical procedure can be
calculated. For the seven spruces analysed the mean
ash concentration was 0.347 weight%. The detec-
tion limits for Na, Mg, P, Mn and Al in ashes of
plant materials can be seen from Table 3. When
using thick-target PIGE in combination with dry
ashing the following detection limits were obtained
for spruce wood: Na 0.014 mg g − 1, Mg 1.4 mg g − 1,
Al 0.3 mg g − 1, P 0.8 mg g − 1 and Mn 2.5 mg g − 1.
Hall [22] reported working detection limits for
tree-rings obtained by thin-target PIXE/PIGE and
different sample preparation techniques. The detec-
tion limits achieved for Na, Mg, Al and P in the
present work with the thick-target technique are
clearly lower than those reported by Hall [22].
4. Conclusions
Particle-induced g-ray emission (PIGE) analyses
of plant materials were performed at conditions
optimised for external-beam thick-target particle-
induced X-ray emission (PIXE) analysis. The sam-
ples were analysed as thick targets. The elements
Na, Mg, Al, P and Mn were determined with the
method. The PIGE analyses of low concentrations
of elements are problematic due to contributions
from background radiation. However, by dry ash-
ing the materials to 550°C prior to the analysis, the
contributions from the background became negligi-
ble.
The method was evaluated using seven certified
reference materials. Experimental calibration con-
stants and detection limits were determined for the
five elements in the nonashed and ashed sample.
Good agreements were obtained between certified
values and the results from the PIGE analyses of
the ashes. No significant losses of the elements
studied were observed. The concentrations in the
ashes were clearly above the limits of quantitative
determination (LOQs).
In plant materials like wood the concentrations
in nonashed samples are well below the LOQs. In
ashed samples the detection limits for PIGE are
somewhat higher than in nonashed samples. How-
ever, considering the preconcentration factor, the
detection limits for the whole method were greatly

Table 4
Thick-target PIGE analyses of wood samples preconcentrated by dry ashinga

Sample Ash (%) PIGE PIXE

Na Mg Al P Mn P Mn

Harja6alta
Pine 0.223 28.7 86 3.1 53 43 71 61
Spruce 1 0.322 18.5 70 2.5 35 22 41 17
Spruce 2 0.330 5.3 76 4.7 30 38 12 69
Merimasku
Spruce 1 0.320 3.0 107 6.4 23 23 17
Spruce 2 0.513 9.9 187 9.8 41 62 37 49
Spruce 3 0.319 5.5 95 9.9 21 31 30 22
Spruce 4 0.313 9.6 104 7.7 27 16 49 12
Spruce 5 0.314 5.4 120 5.8 72 24 85 19
Mean spruce 0.347 8.2 108 6.7 36 31 42 29
RSD (%) 21 64 36 40 50 50 57 73

a
The samples were collected from Harjavalta and Merimasku in SW Finland. The concentrations in the two last columns were
determined with PIXE. All concentrations are given as mg g−1 by dry weight.
 K.-E. Saarela et al. / Talanta 51 (2000) 717–725
enhanced by the dry ashing. In spruce samples the
average ash content was 0.347% by dry weight
and a detection limit of e.g. 0.014 mg g − 1 for
sodium can be achieved.
Acknowledgements
The financial supports provided by The Foun-
dation of A, bo Akademi and The Foundation for
Research of National Resources in Finland are
gratefully acknowledged.
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