Analytica Chimica Acta 402 (1999) 267–274

Radioluminescence detector for the flow injection determination of

phosphorus as vanadomolybdophosphoric acid
Andrew M. Leach, Daniel L. Burden, Gary M. Hieftje ∗
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA
Received 8 February 1999; received in revised form 25 June 1999; accepted 7 July 1999

Abstract
A radioluminescent light source has been used in a detector for the flow injection (FI) determination of phosphorus by
means of the vanadomolybdophosphoric (VMP) acid spectrophotometric method. A comparison with previous studies in
which lamp-based instrumentation was utilized proves that radioluminescence (RL) is a viable alternative source. RL enables
the design of compact, inexpensive light sources for spectroscopic studies. Through the selection of a radioisotope and
scintillation medium, the spectral and temporal characteristics of the source can be chosen independently. In this study, a
broadband radioluminescent source provided detection limits similar to those of conventional lamp-based detectors while
increasing the dynamic range of the method. Possible interferences caused by the use of a broadband light source have been
explored as a function of the spectral region employed. ©1999 Elsevier Science B.V. All rights reserved.
Keywords: Radioluminescence; Flow injection; Vanadomolybdophosphoric acid; Absorption

1. Introduction an RL source based upon a 1 mCi 90 Sr radioisotope

The recent trend toward the miniaturization of
instrumentation has inspired the development of com-
pact, inexpensive light sources and detectors. One
technology that has expanded because of this trend
is the field of radioluminescence (RL). RL is the
generation of light through the absorption of energy
from radioactive decay particles by a light-producing
medium. RL was first employed as a source for pre-
cise photometric measurements because of the high
stability of the RL emission intensity [1]. The stability
of RL sources has recently been compared to conven-
tional light sources [2]. The emission intensity drift of
∗ Corresponding author. Tel.: +1-812-855-2189;
fax: +1-812-855-0958
E-mail address: hieftje@indiana.edu (G.M. Hieftje)
was about 200 and 400 times less than that of an Hg
lamp and a light emitting diode, respectively [2]. The
high stability of RL sources makes possible the devel-
opment of single-channel, non-ratioing instruments,
thus reducing size, complexity and cost. Moreover,
the shallow penetration depth of most decay particles
permits the design of extremely small light sources
(cm3 –␮m3 ). The desire to exploit RL for spectro-
chemical sensing is further enhanced by the broad
spectral (200–800 nm) and temporal (sub-nanosecond
pulses possible) characteristics of RL sources. Addi-
tionally, radioluminescent light sources require no ex-
ternal power supply. Interest in compact, stable light
sources has led to the recent use of RL in steady-state
absorbance [3] and fluorescence [4] sensors as well
as in time-resolved fluorescence measurements [5].
RL has also been applied to the measurement of tran-

0003-2670/99/$ – see front matter ©1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 9 9 ) 0 0 5 3 6 - X
268 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274
sient signals in an absorbance-based detector in liquid
chromatography [6] and in process monitoring [7].
In the present report, we will demonstrate the use of
relatively low-activity RL as an alternative to conven-
tional sources used commonly in flow injection (FI)
absorbance detectors.
To date, the application of RL to the analy-
sis of flowing analyte streams has been limited to
high-activity radioisotopes coupled with inorganic
scintillation crystals. Malcolme-Lawes et al. [6] per-
formed a series of experiments that utilized 10–15 mCi
radioisotope sources for the absorption-based detec-
tion of organic molecules in a high-performance liq-
uid chromatography (HPLC) system. More recently,
Rinke and Hartig [7] employed 10 and 100 mCi
sources in a similar HPLC study.The purpose of the
current investigation is to show that a radiolumines-
cent source composed of a relatively low-activity
(1 mCi) radionuclide and an organic plastic scintillator
could serve as an alternative light source for conven-
tional FI instrumentation. Organic scintillators offer
several advantages over inorganic crystals, including
fast temporal response and low cost. The choice of a
low-activity radioisotope is especially important when
the use of a plastic scintillator is being considered.
Compared to inorganic scintillation crystals, plastic
scintillators are more susceptible to damage caused by
the high energy and flux density of ionizing particles
form the radioisotope. Throughout the light produc-
tion process, the scintillator is bombarded by ionizing
particles, at a rate dependent upon the activity of the
source. The energy of the ionizing particles and their
flux on the scintillator lead to the inevitable deterio-
ration of the scintillation medium, a process known
as radiation damage. The use of a plastic scintillator,
which is relatively easily damaged by high energy
particles such as those from 90 Sr, makes the choice
of low radioisotope activity especially important.
Although high-activity isotopes provide a relatively
high average scintillation emission intensity, the cor-
responding high rate of bombardment by ionizing
particles quickly leads to light loss by progressive
radiation damage. Zorn and co-workers [8–10] have
extensively studied the resistance of plastic scintilla-
tors to radiation damage. Radiation-damage resistant
plastic scintillators have demonstrated the ability to
withstand radiation dosages of greater that 10 Mrad.
In experiments performed in our laboratory using the
beta particle emitter 90 Sr and the plastic scintillator
Pilot U, similar radiation dosages were required to
produce a significant loss in emission intensity. The
long-term stability of the plastic scintillator was mea-
sured by monitoring steady-state emission intensity
as a function of exposure time to the radioisotope.
A rapid loss of emission intensity (approximately
2% h−1 ) has been experienced when a 10 mCi 90 Sr
radioisotope was coupled with Pilot U plastic scin-
tillator. With a low-activity source (1 mCi 90 Sr), ra-
diation damage can be slowed down (approximately
0.5% h−1 ), producing a light source with an extended
service lifetime.
To demonstrate the viability of RL as a light source,
the determination of phosphorus in solution via FI
analysis has been demonstrated. The determination
of phosphorus in environmental [11–14], commer-
cial [15,16], and physiological [17] systems has been
performed by several analytical methods, including
spectrophotometry and amperometry. The most com-
monly employed method involves the spectrophoto-
metric measurement of the formation and reduction
of blue molybdophosphoric acid in the presence of
excess molybdenum. Although the molybdenum-blue
method offers good sensitivity, the reduction process
is time-consuming and can make automation some-
what complicated. A second photometric method
relies on the formation of a hetropoly vanadomolyb-
dophosphoric (VMP) acid species. In the VMP acid
method, the combination of vanadomolybdate and
phosphorus causes an increase in absorbance that
is directly proportional to the original phosphorus
concentration. The VMP acid determination of phos-
phorus has been validated by many studies since
its introduction for the first time by Misson [18] in
1908 and is currently the basis of several standard
methods [19,20]. In a study performed by Michelsen
[21], the maximum sensitivity of the VMP method
was reported to occur at an absorption wavelength of
315 nm. In subsequent experiments, elevated back-
ground and interferent absorption have caused the
VMP method to be limited to wavelengths longer
than 390 nm [22]. The VMP acid method has been
automated by means of FI for the determination of
phosphorus in plants and phosphate-rich rocks. FI
improved the reproducibility and sample throughput
of the method. Røyset [14] utilized 400 nm light to
achieve a phosphorus detection limit of 0.1 ppm and a
 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274
Fig. 1. FI manifold used for the determination of phosphorus via the VMP acid method. Numbers in the peristaltic pump lines refer to
flow rate in ml min−1 .
dynamic range of 1.3 orders of magnitude. Basson et
al. [12] confirmed that the use of longer wavelengths
(460 nm) extended the range of the VMP method to
higher phosphorus concentrations, but at the cost of
poorer detection limits.
The present study shows that a broadband radiolu-
minescent light source can provide adequate detection
limits and an even broader dynamic range than can
be achieved with conventional light sources used in
similar FI experiments. The long-term stability of the
radioluminescent light source provides better repro-
ducibility and makes possible extended-duration stud-
ies without the need for repeated calibration.
2. Experimental
2.1. Reagents
The vanadomolybdate reagent was prepared
through the following five-step process. Ammonium
molybdate tetrahydrate (79.9 g, Mallinckrodt) was
dissolved in 200 ml of hot (80◦ C) deionized water.
Ammonium metavanadate (4.00 g, J.T. Baker) was
dissolved in 200 ml of hot (80◦ C) deionized water.
The ammonium metavanadate solution was added to
520 ml of 25.8% (w/v) nitric acid. The ammonium
molybdate solution was then added to the acidic am-
monium metavanadate solution during stirring and
the combined volume was diluted to 1 l. The vanado-
molybdate reagent is yellow in color and stable for
approximately 2 weeks.
Phosphate calibration solutions were prepared
by dissolving potassium dihydrogen phosphate
269
(15.3395 g, Aldrich) in 1 l of deionized water, resulting
in a stock solution containing 3491 ppm phosphorus.
Calibration solutions were produced by volumetric
dilution of the phosphate stock with deionized water.
Individual stock solutions with interferent con-
centrations of 5000 ppm were generated for Fe2+ as
Fe(NH4 )2 (SO4 )2 ·6H2 O, F− as NaF, Cl− as NaCl,
Cu2+ as CuSO4 , and Ni2+ as NiSO4 ·6H2 O. Stock so-
lutions were diluted serially to generate a calibration
plot.
2.2. FI apparatus
Fig. 1 shows the FI manifold used in this study.
Two peristaltic pumps (Perkin–Elmer) and a Rheodyne
model 7010 injection valve (100 ␮l injection volume)
were used for flow production. Deionized water was
used as the injection carrier stream. Vanadomolybdate
reagent and phosphorus injections were combined by
means of an Omnifit three-way microfitting (0.8 mm
i.d.). Mixing occurred in a 1 m knitted mixing column
fabricated from 0.8 mm i.d. Teflon tubing.
2.3. RL absorption detector
Fig. 2 shows the RL detector coupled with the
FI manifold described above. RL was produced by
the combination of an encapsulated 1 mCi 90 Sr (Iso-
tope Products, model GFS 3) source and a Pilot U
plastic scintillator (NE Technologies). The radioiso-
tope 90 Sr (28.3 years half-life) decays through the
release of a beta particle (0–0.546 MeV) to pro-
duce 90 Y. In turn, 90 Y is a short-lived isotope (64 h
270 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274
Fig. 2. Diagram of the RL absorption detector coupled with an FI capillary.
half-life) which further decays to 90 Zr through re-
lease of a beta particle with an energy distribution of
0–2.274 MeV. The average energy of the particles re-
leased through the combined 90 Sr and 90 Y decay pro-
cesses is 1.0 MeV. Pilot U produces broadband emis-
sion from 365 to 500 nm with an emission maximum
at 391 nm [23]. The combination of Pilot U and 90 Sr
has been reported to produce an average of 10 000
photons MeV−1 [24]. The scintillator was shaped
to incorporate a 13 mm long cylinder (10 mm dia-
meter) for light production followed by an integrated
waveguide, resulting in a tapered emission window of
1 mm × 5 mm.
RL produces light in an isotropic fashion within the
scintillation material. In order to promote propagation
of light towards the sample cell, white Teflon tape was
wrapped around all sides of the scintillator to serve
as a diffuse reflector. All sides were tape-covered ex-
cept for the emission window and the opposite side,
which was in contact with the encapsulated radioiso-
tope. Light from the radioluminescent source passes
through a 0.8 mm × 5 mm aperture before encounter-
ing a cylindrical glass flow cell 1 mm in diameter
(3.93 ␮l detection volume).
A long-pass optical filter was used to select the
spectral region employed for the absorption mea-
surements. Two filters were used independently to
monitor analyte and interferent sensitivity as a func-
tion of wavelength (>400 nm with a Melles Griot 03
FCG 055 filter, and >450 nm with an Andover Corp.
ANDV 5387 filter). Elimination of all filters allowed
the entire Pilot U emission spectrum to be used for
absorption. Based upon the emission spectrum of Pi-
lot U and the transmittance of the long-pass filters,
62.5 and 9.9% of the scintillator’s total emission
intensity was passed by the 400 and 450 nm filters, re-
spectively. A photomultiplier tube (PMT, Hamamatsu
R-928) was employed for light detection. Lead glass
(0.3 in thick) was placed between the flow cell and the
photomultiplier tube to intercept stray beta particles
and bremsstrahlung X-rays that could strike the PMT
and cause elevated background signals. Although the
encapsulated design of the 90 Sr source eliminated the
possibility for radioactive contamination, the entire RL
system was surrounded by additional lead shielding to
minimize operator exposure to beta particle and X-ray
emission. Current amplification and low-pass filtering
(12 dB, 0.3 Hz) was accomplished with a Stanford
Research Systems model SR570 low-noise current
amplifier. Data were recorded on a LabVIEW soft-
ware strip chart recorder implemented on a Macintosh
computer.
2.4. VMP acid spectra
Solutions containing the vanadomolybdate reagent
and known concentrations of phosphorus were used to
generate spectra on a Hewlett Packard 8450A UV–VIS
photodiode array spectrophotometer. 1 cm quartz
cuvettes were employed.
 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274 271

Fig. 3. Increase in absorbance upon addition of phosphorus to vanadomolybdate reagent. Absorbances are relative to the highest ab-
sorbance recorded. (a) Vanadomolybdate blank; (b) vanadomolybdate reagent + 34.7 ppm P; (c) vanadomolybdate reagent + 105 ppm P; (d)
vanadomolybdate reagent + 347 ppm P.

3. Results and discussion
3.1. Dynamic range and detection limits
VMP acid exhibits a concentration-dependent ab-
sorption spectrum from 360 to 520 nm (Fig. 3). The
current study exploits the inherently broadband emis-
sion of the plastic scintillator Pilot U to increase dy-
namic range while maintaining sensitivity. A typical
calibration trace showing the triplicate injection of in-
creasing concentrations of phosphorus is shown in Fig.
4. From this group of data, the detection limit can be
found as the concentration that produces a peak am-
plitude equal to three times the standard deviation of
the background. The standard deviation of the back-
ground is calculated using 25 s segments of detec-
tor response in the absence of analyte. The phospho-
rus detection limit calculated when the entire Pilot U
emission spectrum was utilized was 0.4 ppm, with a
linear range of two orders of magnitude. The same
detection limit and dynamic range were found when
the source emission spectrum was restricted to wave-
lengths longer than 400 nm. When the spectral range
was limited to wavelengths longer than 450 nm, the
phosphorus detection limit was elevated to 4 ppm and
the dynamic range extended to 105 ppm.
A phosphorus detection limit of 0.1 ppm and a lin-
ear range of 1.3 orders of magnitude were reported
by Røyset [14], who used a commercial photometer
equipped with an 18 ␮l flow cell and a 200 ␮l injec-
tion loop. Since the detection limit in an FI absorbance
measurement is inversely related to both optical path
length and injection volume, it is not surprising that
the detection limit achieved with the radioluminescent
light source was higher (worse) than that obtained with
the conventional source. The enhanced linear work-
ing range achieved with the radioluminescent source
can be attributed to broadband RL emission combined
with the wavelength-dependent sensitivity of the VMP
acid method.
272 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274

Fig. 4. Absorbance trace for the FI detection of phosphorus via the VMP acid method. Triplicate injections of phosphorus were detected
by using a radioluminescent light source that employed the entire emission spectrum of the Pilot U scintillator (365–500 nm). Numbers
above peaks represent phosphorus concentration in ppm. The enlarged inset displays the absorption peaks of the lowest concentrations that
were examined (0.35 and 1.05 ppm, respectively).

3.2. Reproducibility and sample throughput
A series of 10 replicate injections at a known con-
centration was used to determine the reproducibility
of the new detector. Over a phosphorus concentration
range from 6 to 35 ppm, a relative standard deviation
of less than 1% was calculated. In addition, the cur-
rent study demonstrates the possibility of analyzing
144 samples per hour with baseline resolution (25 s
per sample).
3.3. Interferences
A complete study of interferences in the determina-
tion of phosphorus via the VMP acid method has been
performed by Kitson and Mellon [16]. Past studies
have documented that spectral interferences caused
by the presence of matrix ions have a strong wave-
length dependence. Interferences have been shown
to decline with an increase in excitation wavelength.
One of the potential concerns explored in the current
study was the possible increase in interference caused
by the use of a broadband light source. To test this
possibility, a group of commonly recognized inter-
ferent ions was selected. Interferent solutions were
combined with the vanadomolybdate reagent via FI
in the absence of phosphorus. The ion Fe2+ was se-
lected as a representative of those that reduce excess
molybdate to molybdenum-blue, resulting in an in-
crease in absorbance. Other similarly behaving reduc-
ing ions include sulfide, thiosulfate and thiocyanate.
Chloride and fluoride ions were explored for possible
color-bleaching effects, which were reported to result
in a negative absorbance. Chloride produced no inter-
ference up to a concentration of 1000 ppm, whereas
a negative change in absorbance was measured upon
injection of fluoride. Additionally, blue-colored solu-
tions of Cu2+ and Ni2+ were examined for possible
interferences, although no significant absorbance
was measured up to concentrations of 1000 ppm. As
 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274 273

Fig. 5. Effect of source spectrum on the magnitude of Fe2+ interference in the VMP acid method. The wavelength range employed for
each measurement, indicated on the left side of each trace, was selected by means of suitable optical filters. Absorbance trances are offset
to simplify comparison. (a) Represents 50 ppm Fe2+ , (b) represents 100 ppm Fe2+ , (c) represents 500 ppm Fe2+ , (d) represents 1000 ppm
Fe2+ , (e) represents 15.7 ppm phosphorus.

expected, spectral interferences caused by both Fe2+ presence of fluoride follows a similar pattern. In com-
and F− exhibited a strong dependence upon wave- parison with a study performed with a conventional
length. By limiting the Pilot U scintillator to emission light source limited to 390 nm [22], the broadband
wavelengths longer than 400 nm, the measured inter- radioluminescent source restricted to wavelengths
ference produced by Fe2+ was reduced by over 50% longer than 400 nm produced only slightly greater
(Fig. 5). Further limitation of the scintillator emis- spectral interference (10%) due to its broad emission
sion to wavelengths longer than 450 nm resulted in band.
the complete elimination of interference by Fe2+ . As
Table 1 reveals, the interference resulting from the
4. Conclusion
Table 1
Ion interference as a function of spectral region employed for
determination A relatively low-activity radioluminescent light
Interferent Interferencea
source is an acceptable alternative to a conventional
lamp for the determination of phosphorus via the
Entire spectrum >400 nm >450 nm 390 nm [10] VMP acid method. The broadband radioluminescent
Fe2+ 0.0142 0.0078 0.0005 0.007 source employed in the current study produced com-
F− −0.001 −0.0009 NAb NAb parable phosphorus detection limits (0.4 ppm), but a
a Expressed as equivalent absorbance compared to 1 ppm phos- dynamic range (two orders of magnitude) superior to
phorus. those of conventional sources (1.3 orders of magni-
b NA signifies data were unavailable. tude). Spectral interference resulting from the use of
274 A.M. Leach et al. / Analytica Chimica Acta 402 (1999) 267–274
a broadband light source was elevated slightly com-
pared to that with conventional lamp-based instrumen-
tation. Reduction of these interferences was possible
by performing the analysis at longer wavelengths.
The performance of the radioluminescent light source
in this study showed potential for further use as a
substitute for conventional sources. Enhanced perfor-
mance as an absorbance detector could be achieved
by expanding the flow cell path length. In accordance
with Beer’s law, an increase in path length should
yield a directly proportional improvement in detection
limit. The long-term stability of the radioluminescent
source offers the possibility of extended-duration
studies.
Acknowledgements
Supported in part by the US Department of Energy
grant DE-FG02-98ER14890 and the Merck Research
Laboratories.
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