J Radioanal Nucl Chem (2017) 312:461–470
DOI 10.1007/s10967-017-5252-8
UV–Vis spectroscopy with chemometric data treatment: an option
for on-line control in nuclear industry
Dmitry Kirsanov1,2 • Alisa Rudnitskaya3 • Andrey Legin1,2 • Vasily Babain2,4
Received: 3 March 2017 / Published online: 22 April 2017
Ó Akadémiai Kiadó, Budapest, Hungary 2017
Abstract Chemometrics can be very useful for the clas-
sical field of UV–Vis determination of metals in aqueous
solutions. A conventional approach consisting of using
selective bands in a univariate mode is often not applicable
to the real-world samples from e.g. hydrometallurgical
processes, because of overlapping signals, light scattering
on foreign particles, gas bubble formation, etc. And this is
where chemometrics can do a good job. This paper over-
views certain contributions to the field of multivariate data
processing of UV–Vis spectra for seemingly simple case of
metal detection in aqueous solutions. Special attention is
given to applications in nuclear technology field.
Keywords UV–Vis spectroscopy
Chemometrics

Metals
On-line control
Process analytical technology

Nuclear technology
& Dmitry Kirsanov
d.kirsanov@gmail.com
1
Institute of Chemistry, St. Petersburg State University,
Universitetskaya nab. 7/9, St. Petersburg, Russia 199034
2
Laboratory of Artificial Sensory Systems, ITMO University,
Kronverkskiy pr. 49, St. Petersburg, Russia 197101
3 (PLSR) remain the most popular.
CESAM and Chemistry Department, Aveiro University,
Campus Universitário De Santiago, 3810-193 Aveiro,
Portugal
4
Three Arc MiningInc., Stary Tolmachevsky per. 5, Moscow,
Russia 115184
Introduction
Origins of chemometrics are usually placed in the 1960s
when computing became largely available for the scientific
community. Accessibility of the computers stimulated the
development of theoretical chemistry involving complex
calculation, e.g. molecular modelling or quantitative
structure–activity relationship, as well as applications of
statistics to analytical chemistry in particular to the treat-
ment of complex instrumental signals. Thus, the advent of
analytical instruments generating for each sample a large
number of measurements, which were often collinear and
non-selective, was another catalyzer for the introduction of
chemometrics. The term ‘‘chemometrics’’, which came to
designate a combination of statistics, computationally
intensive multivariate methods and experimental design
applied to analytical chemistry, was coined by Wold in
1972 [1]. Since then various methods and applications of
chemometrics have been developed. Multivariate calibra-
tion, structure–activity modelling, pattern recognition,
classification, discriminant analysis, and multivariate pro-
cess modelling and monitoring were identified as areas,
where chemometrics has been the most successful [2].
Further evidence of chemometrics success is its widespread
use in the industry as it was introduced for process moni-
toring in all kinds of manufacturing processes, from
petrochemical to pharmaceutical and food. Though
numerous chemometric methods and algorithms have been
developed in the course of the years, Principal Component
Analysis (PCA) and Partial Least Square regression
One of the most striking examples of usefulness of
chemometrics is Near-Infrared (NIR) spectroscopy. NIR
spectroscopy was first introduced in the 1950s but was
scarcely used till 80s. It was deemed a ‘‘sleeper among
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spectroscopic techniques’’ due to its presumably high
potential but very limited practical applications [3]. Indeed,
NIR spectra typically contain broad and overlapping bands
influenced by various physical, chemical and structural
parameters. NIR spectra are, thus, information-rich but
non-selective, and univariate approach taking into account
a single band at a time is not applicable. On the other hand
multivariate analysis techniques allowed extracting ana-
lytical information from NIR spectra and opened up new
horizons for its application as a process control tool in
industry [4–6]. Other spectroscopic techniques such as
inductively coupled plasma-optical emission/atomic
absorption spectroscopy (ICP-OES/AAS) [7], ICP-mass
spectrometry (ICP-MS) [8], laser-induced breakdown
spectroscopy (LIBS) [9] and Fourier Transform mid-in-
frared spectroscopy (FT-MIR) [10] also benefited from the
use of chemometrics.
UV–Vis spectrophotometry is considered as a simple
technique useful for analysis and characterization of indi-
vidual compounds but with limited applications in the field
of complex media analysis. The analysis of multicompo-
nent samples by UV–Vis is hindered by the lack of sen-
sitivity and selectivity due to overlapping bands of the
components, thus preventing the use of this method for on-
line control of industrial processes. The application of
chemometrics to the resolution of overlapping spectra of
complex mixtures in order to increase the potential of UV–
Vis spectroscopy seems to be a natural next step [11]. The
purpose of this review is to demonstrate how the use of
chemometrics to the processing of UV–Vis spectra may
advance applications of this method to the practical tasks.
We will discuss briefly the use of UV–Vis spectrometry for
metal quantification in aqueous solutions and then we will
make a special focus on nuclear technology related appli-
cations, since it is there where one needs fast and reliable
answer about content of various metals in on-line mode.
Various organic substances can be quantified from UV–Vis
spectra with the help of chemometrics as well, however we
will not focus on these applications. In no way this review
is claiming to embrace all the literature available on the
topic; we will rather be concentrated on certain selected
publications, which we believe reflect the current situation
and trends in the field.
Detection of metals with chromogenic ligands
with UV–Vis spectroscopy and chemometrics
In spite of moderate sensitivity, UV–Vis spectroscopy is
still a very widely applied technique. Direct metal analysis
with UV–Vis spectroscopy is possible and generally would
be suitable for on-line implementation in technological
process control, however its application is only limited to
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J Radioanal Nucl Chem (2017) 312:461–470
colored metal solutions, so the number of potential analytes
is quite small. Another concern regarding direct UV–Vis
quantification is that detection limits are rather high in this
case.
Traditional approach to analysis of metals with UV–Vis
relies on the use of chromogenic ligands, which upon the
binding reaction with target analyte yield intense colored
complexes. Though this procedure allows for significant
decrease of detection limits of the method, it is normally
effective only when determination of single metal is
required. Chromogenic ligands are usually not highly
selective and spectra that they form with different metals
are often highly overlapping, which leads to the decrease of
analysis precision or even make it altogether impossible.
One of the ways of dealing with it is to perform separation
and/or masking prior to determination. This approach is
quite laborious, which diminish UV–Vis attractiveness as
simple and fast technique, while also invalidate it as a
potential method for on or in-line analysis.
As an alternative, chemometrics can be used to cir-
cumvent insufficient selectivity and carry on multicompo-
nent analysis without sample preparation.
A very nice example from one of the first demonstrations
of the potential of chemometrics in this field is reported in
the work of Otto and Wegscheider [12]. The authors
demonstrated that simultaneous quantitative analysis of
iron, cobalt, nickel, copper and palladium in mixtures at low
concentrations (down to 10-6 M) using visible spectroscopy
of diethyldithiocarbamate chelate complexes of these met-
als is possible. Multilinear regression (MLR) was compared
with PLSR (projection on latent structures) and the latter
one displayed superior performance ensuring relative errors
below 6%. There is also a quote by authors we would like to
reproduce here, since it is very appropriate and consistent
with the scope of this review: ‘‘The successful simultaneous
determination of five metal ions by means of their DEDTC
(diethyldithiocarbamate) complexes raises the question of
whether there are some reagents out of hundreds proposed
for spectrophotometric single component analysis that are
more suitable for SMA (spectrophotometric multicompo-
nent analysis) of metals than is DEDTC. In this context the
existing one-wavelength based photometric methods have
to be revisited with respect to their performance in the
whole spectral range.’’ Indeed, with popularization of
chemometrics, promoted by appearance of several tutorial
reviews on multivariate calibration (see e.g. [13, 14])
numerous studies emerged revisiting the UV–Vis methods
and their capabilities in the new ‘‘multivariate’’ context.
The example of classical study in this research direction is
described in the work [15], where 2-(5-bromo-2-pyridy-
lazo)-5-diethylaminophenol (Br-PADAP) was applied as a
coloring agent for simultaneous determination of Fe, Cu,
Zn, Co and Ni in aqueous media and for quantification of
J Radioanal Nucl Chem (2017) 312:461–470
Fe, Cu and Zn in blood serum as well. Spectrophotometric
data in visible range were processed with PLSR. The
authors did intensive research on establishing optimal
parameters for analysis and studied several possible
interferences.
Another typical study of this kind was reported in Ref.
[16] where the authors used MLR to process visible spectra
in the range 390–480 nm for simultaneous determination of
cadmium, copper and zinc. Colored complexes of the metals
were obtained using 1,5-bis(di-2-pyridylmethylene)thio-
carbonohydrazide. Estimated linear determination ranges
were 0.1–1.7 lg/ml for Cd, 0.1–1.3 lg/ml for Cu and
0.2–1.2 lg/ml for Zn. Strong interference from Co(II),
Ni(II), Fe(III), Hg(II) and Hg(I) ions was observed since
these metals also form colored complexes with the ligand.
As a demonstration, diverse spiked samples and reference
materials were analyzed. Later the same authors reported on
simultaneous determination of iron, cobalt, nickel and
copper using the same chelating agent but applying principal
component regression (PCR), PLS1 and PLS2 for process-
ing of the visible spectra (390–510 nm) [17].
Analysis of metals with UV–Vis characteristic
absorption spectra and chemometrics
Distinct characteristic bands of the electronic transitions in
some metals allow for reliable UV–Vis quantitative con-
centration assessment even without dyes. In this case,
univariate approach to UV–Vis spectra often fails in
complex mixtures due to broad overlapping peaks of
components. Once again, performance of UV–Vis spec-
troscopy can be significantly improved by chemometric
data processing. One of the first examples of such combi-
nation was reported in 1987 [18]. In this study eight rare
earth elements (Pr, Nd, Sm, Eu, Dy, Ho, Er and Tm) where
simultaneously determined by spectrophotometry in
350–850 nm wavelength range with repetitive spectral
subtraction method (RSSM). The results were compared
with those from derivative spectra and from correction
factor methods and were shown to have higher precision.
Besides, the application of the suggested method to quan-
tification of these metals in monazite and xenotime ores
was presented. The study of Carey and Wangen [19]
describes application of PLSR to simultaneous quantifica-
tion of plutonium and nitric acid using visible absorption
spectra (500–880 nm). Although the determination of Pu in
this range is quite straightforward, the analysis of nitric
acid is more challenging since it has only a minor contri-
bution to the spectra of the mixture. Both analytes were
successfully quantified in concentration ranges
1.99–29.9 g/L of Pu and 0.44–3.08 mol/L of HNO3. The
same authors also reported on the application of PCA and
463
nearest neighbor classifier to evaluate the effects of fluoride
and oxalate on the Pu spectra [20]. Simultaneous deter-
mination of Ce, Pr and Nd using PLSR is described in Ref.
[21]. The spectra of mixtures were recorded in
290–800 nm range. Although the experimental design of
model mixtures was not optimal (lanthanide concentrations
were varied only over two–three fixed levels), the resulted
models allowed for determination of concentrations in
commercial rare-earth product with significantly greater
precision than the conventional univariate calibration
method. The authors also tried to evaluate samarium con-
centration but in the real sample it was too low and out of
calibration range.
In the works of Meinrath quantitative spectroscopic
speciation of various hydrolysed U(VI) solutions has been
demonstrated using factor analysis [22, 23] The same
author with co-workers successfully applied computer-as-
sisted target factor analysis combined with Monte Carlo
simulations and resampling techniques (i.e. threshold
bootstrap methods) to the speciation of lanthanides in
solutions employing UV–Vis spectroscopy data. Interac-
tions of Nd(III) with various ligands including polyox-
ometalates [24], nicotinic acid N-oxide, derivatives of
carboxylated pyridine N-oxide and Arsenazo III have been
studied [25–27]. Interaction of hexavalent uranium with
pyridine carboxylic acid N-oxide derivatives was also
studied [28]. Aforementioned works specifically focused
on application of the resampling techniques to the error
propagation and uncertainty estimation of the measure-
ments in the situations when classical error progression
approximations are not applicable, of which use of multi-
variate methods for resolution of the overlapping UV–Vis
spectra was selected as a case study.
The report [29] addresses the problem of overlapping
peaks of europium, terbium and yttrium in the presence of
perchloric acid. This overlapping seriously hinders indi-
vidual analysis of rare-earth elements in mixtures. The
authors proposed the approach based on Kalman filter and
absorption coefficient matrix obtained from MLR for
simultaneous quantification of all three metals in the
complex sample of phosphor powder.
Somewhat similar idea was exploited in the work [30]
where the authors studied the data set of UV–Vis spectra
(180–800 nm) for four metal ions (Fe, Ni, Co, Cu) in
aqueous solutions.. Calibration models in order to predict
content of the metals in test solutions were obtained using
MLR and K-matrix approach. The latter allowed obtaining
better results in metal quantification while also providing
information of real spectral features. These results are
however come with a caveat that K matrix approach works
well only in relatively simple cases when spectra obey
Beer’s law and the level of noise and unidentified com-
ponents is negligible.
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Using PCA and target transformation factor analysis
(TTFA) resolution of the visible spectra (300–500 nm)
obtained in solutions of modified calixarene ligand and rare
earth ions Eu3?, Dy3?, and Tb3? was achieved [31]. The
stoichiometry of the complexes was established and cor-
responding stability constants were calculated.
The authors of the work [32] reported on feasibility
study of simultaneous determination of several lanthanides:
Ce, Pr and Nd using 200–1000 nm spectral measurements.
In order to provide for quantitative assessment of concen-
trations PLSR and correlation constrained MCR-ALS were
employed. While it was possible to determine Nd and Pr,
the quantification of Ce posed certain problem due to
strong overlapping of Ce band with HNO3 band under
experimental conditions.
The significant part of the applications in this section is
devoted to the analysis of lanthanides and actinides. This is
easy to explain taking into account that these elements
have direct relation to nuclear fuel cycle where the problem
of development of fast and reliable methods suitable for
on-line control is really urgent.
Towards on-line control with UV–Vis
spectrometry
There is a great interest in on-line determination of metals
coming from the nuclear technology field. Timely, prefer-
ably on-line, monitoring of the industrial process and
detection of deviations from the normal operating condi-
tions is of paramount importance for the nuclear technol-
ogy and, in particular, reprocessing of the spent nuclear
fuel (SNF). Excellent review of analytical problems related
to the PUREX process, was done in two works [33, 34].
Similarly to other industrial processes, continuous moni-
toring provides possibility to enhance performance and
minimize losses by timely correcting deviating processes.
Currently the whole new paradigm is evolving to address
these issues (process analytical technology—PAT) [35]. In
the case of radiochemical processes, such monitoring
would also serve to critically improve safety due to better
accountability of fissile materials. Currently, process con-
trol at the spent nuclear fuel processing facilities is prin-
cipally done in the laboratory using inductively coupled
plasma mass spectrometry [8] and thermal ionization mass
spectrometry [36] with prior sample preparation using
isotope dilution [37] or separation using high-performance
liquid or ion chromatography [38]. While these techniques
are highly accurate and selective, they are resource inten-
sive and have extended analysis times which may result in
the time lags of about 15–20 h between sampling and final
result—obviously, too long. Such prolonged analysis times
are particularly unacceptable in the light of demands of
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J Radioanal Nucl Chem (2017) 312:461–470
non-proliferation policy, which require information about
plutonium concentration as soon as possible.
Peculiar analytical problems in nuclear chemistry are
caused by radioactivity of analysed solutions, which can
sometimes exceed 1010 BkL-1. Consequently, analytical
tasks such as sampling and sample handling, which are
very simple and trivial with non-radioactive solutions,
become extremely complicated and time consuming. It is
worth to note that direct contact of operator with radioac-
tive samples have to be minimized or, ideally, excluded.
Thus, the urgent need of the on-line nondestructive moni-
toring of radiochemical processes is indisputable.
Separation technologies currently employed for repro-
cessing of spent nuclear fuel, including the PUREX and
UREX? processes, are based on liquid–liquid extraction.
Uranium, plutonium and neptunium are extracted from the
aqueous solutions of the spent fuel using organic solvents,
while fission products remain in the aqueous phase [39].
The next step consists in extraction of minor actinides from
raffinates of PUREX-process [40, 41]. The distribution of
each element between aqueous and organic phases and,
consequently, efficacy of separation and purification is
governed by the major process variables such as acid
concentration, organic ligand concentration, reduction
potential and temperature. Element distribution should
remain within established limits, corresponding to the
normal operating conditions (NOC), ensuring stable pro-
cess functioning.
On-line measurements of the solutions’ composition
would allow maintaining process parameters within NOC
and timely correct the deviations. Primary analytes of
interest to be monitored during SNF reprocessing are
metals, mainly actinides and lanthanides, and nitric acid.
Instrumentation to be usable for the on-line monitoring
of the processing of the spent nuclear fuel must be robust,
require little maintenance and tolerate harsh process con-
ditions such as high radioactivity levels and high acid
concentrations. Nondestructive optical techniques, primar-
ily UV–Vis, Raman and IR spectroscopy comply with
requirements enumerated above and are convenient tools
for metal quantification in solutions. Often mentioned
drawback of UV–Vis spectroscopy is that characteristic
absorption allows only for rather high detection limits, but
spent nuclear fuel processing deals with rather high con-
centrations so it is not an issue. Detection limit of direct
UV–Vis spectroscopy for actinides is about 0.1 g/L, while
concentrations of uranium in technological solutions varies
in the range of 1–300 g/L, plutonium of 0.1–20 g/L and
nitric acid of 0.1–3 mol/L. Such concentrations of uranium
and plutonium are high enough to be detected by UV–Vis
spectroscopy. Requirement of very low detection limits for
the analytical instruments currently employed for spent
nuclear fuel analysis is dictated by the necessity to dilute
J Radioanal Nucl Chem (2017) 312:461–470
samples due to their high radioactivity. Dilution of thou-
sand to ten thousand times or even more are typically done,
otherwise handling of the samples is too dangerous. Use of
on-line or in-line techniques such as UV–Vis spectroscopy
eliminates this problem. Applications of UV–Vis spec-
troscopy for the process control in nuclear technology will
be discussed in more details below.
Application of UV–Vis spectroscopy in nuclear
technology. Univariate approach: detection using
single wavelength
Possibility of implementation of on-line control of the
continuous treatment process using spectroscopic tech-
niques also has been intensively studied since 1970s [42].
However, the first attempt to apply UV–Vis spectroscopy
for the quantification of rare earth metals in the presence of
the nitric acid dates back to 1941 [43]. In this work
transmittance spectra of lanthanum, cerium, praseody-
mium, neodymium, samarium, europium and gadolinium
in the solutions of nitric acid were measured in the range
from 350 to 1000 nm. All metals but gadolinium had
absorption bands in the studied spectral range, which were
partly overlapping. Simultaneous determination of Pr, Nd
and Sm in the mixed solutions was possible using three
absorption bands and parameters characterizing molar
absorptivity of these metals for accounting for the mutual
interferences.
Initially gamma- spectrometry and X-ray fluorescence
methods were proposed for organization of on-line control
of liquid spent nuclear fuel processing [44]. Later on,
several applications of the optical methods such as Raman
[45, 46], UV–Vis/NIR [47] and UV–Vis [48, 49] spec-
troscopy to the detection of inorganic and organic com-
pounds including actinides have been reported. Micro-
electro-mechanical system (MEMS) has been developed
and tested for the spectrophotometric detection of neody-
mium in the concentration range from 18 to 230 g/L at the
constant background of 3 M nitric acid [47]. Spectropho-
tometric determination of uranium in the presence of
varying concentration of nitric acid required use of two
wavelengths to account for the dependence of the uranyl
molar absorptivity on the nitrate concentration [48]. Use of
two bands at 426 and 416 nm allowed for determination of
both uranyl in the concentration range from 20 to 200 g/L
and nitrate in the concentration range from 3 to 5 M with
relative standard deviations of 5 and 15%, respectively.
Detailed study of the effect of nitrate on uranyl speciation
resulting in the significant changes in the U(VI) visible
spectra with changing nitrate concentrations was reported
in. Alterations of uranyl UV–Vis spectra in the concen-
tration ranges from 0.01 to 1.26 M of uranium and from
0.01 to 8 M of nitric acid were studied, however, no
465
attempt to quantify uranium and nitrate was made. Similar
research was presented in another work [50].
The potential of UV–Vis spectroscopy can be quite
limited in comparison with other techniques, especially
when resulting spectra are treated in traditional univariate
way. UV–Vis spectroscopy and Time Resolved Laser
induced Fluorescence Spectroscopy (TRLFC) have been
compared in Ref. [51] to determine the uranium concen-
tration in nitric acid solutions. The authors concluded that
both methods are capable of achieving this goal though at
different concentration levels: linearity range was ca. from
1 mM to 0.2 M for UV–Vis and from 0.09 to 6 mM for
TRFLC. They also noted that TRLFC was superior in that
it could qualitatively detect uranium presence in the solu-
tions in the absence of calibration. This conclusion, how-
ever, was made without using any chemometric methods
for spectra treatment.
Further limitations of univariate approach were evi-
denced [52, 53]. Optic fiber aided method was proposed in
the work [52] for determination of ruthenium in the solu-
tions mimicking aqueous streams of nuclear reprocessing.
While nitric acid and other metals as zirconium and
strontium did not interfere with analysis, negative influence
of uranium was observed. Thus, uranium has to be sepa-
rated from solution prior to ruthenium determination,
which renders this approach inapplicable to on-line anal-
ysis. Direct detection of U, Nd and Pd in 3 M nitric acid
solutions by reflection absorption spectrophotometry was
discussed in Ref. [53]. Unfortunately, the authors did not
account for the influence of nitric acid concentration on the
metals’ spectra. It is, however, well known that bands in
uranium spectrum are sensitive to nitric acid concentration.
It was therefore becoming obvious early on, that use of
single wavelength for quantification of the constituents of
spent nuclear fuel is not feasible due to the interferences.
Besides influence of nitrate on the uranyl speciation and
overlapping spectra of rare earth metals discussed above,
such effects as redox reactions of actinides [54, 55] and
formation of cation–cation complexes [56] affect specia-
tion of the metals and their UV–Vis spectra. Selectivity can
be improved by prior separation of the metals in the mix-
tures or by use of ligands capable of forming colored
complexes with metals such as e.g. arsenazo. It should be
noted, though, that addition of reagents to the sample is
hardly compatible with on-(in-)line measurements. Alter-
native approach can consist in the use of chemometrics
instead of ligands for the resolution of overlapping optical
spectra. Recently reported application of the UV–Vis
spectroscopy together with chemometric data treatment to
the analysis of the nuclear technological solutions are
discussed below.
Early attempts to analyse actinides and nitric acid in
aqueous (and organic) solution in on-line mode were taken
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in the 80-th, when fiber optic technic became available
[57]. For example, report about uranium detection in
aqueous and organic phases by UV–Vis spectroscopy in
extraction experiments in hot cells was presented in 1986
[58]. However the accuracy of results was quite poor,
because mathematical treatment of spectra was not
employed.
Multivariate approach: detection using whole
spectra and chemometrics
First attempt to combine UV–Vis spectroscopy with
chemometrics for analysis of actinides dates back to 1988.
In the studies [59, 60] UV–Vis spectroscopy with optic
fiber and PLSR for data treatment was tested for simulta-
neous determination of uranium and nitrate.
PLSR modelling was used for the analysis of the model
solutions of uranium (VI) [61] and plutonium(III)/(IV) [20]
in nitric acid. Calibration models for determination of both
uranium(VI) and nitrate were made using absorption
spectra in the spectral range from 380 to 500 nm. Con-
centration ranges typical for the PUREX process were
selected and were of 1–30 gL-1 for uranium and 0.02–3
molL-1 for nitric acid. Prediction of uranium(VI) and
nitrate was possible with Root Mean Square Errors
(RMSE) of 0.2 gL-1 and 0.07 molL-1, respectively. Sim-
ilar approach was applied to the simultaneous quantifica-
tion of Pu(III) and nitric acid [58]. Furthermore, influence
of different concentrations of nitric acid, oxalate and flu-
oride on visible spectra of Pu(IV) have been studied using
PCA and Nearest Neighbor classification.
Interest to the applications of chemometric techniques to
the processing of the UV–Vis spectra of aqueous solutions
of spent nuclear fuel has resurfaced recently and a series of
reports on this topic have been published [62, 63].
UV–Vis spectroscopy in combination with PLSR was
applied to the quantification of Np and Pu in the model
solutions simulating feeds obtained from the PUREX
process [64]. All model solutions contained fixed back-
ground of uranyl (50 g/L) and nitric acid (2 M), while
concentration of Np and Pu changed in the range from 0.05
to 1.55 g/L. Mean Relative Errors (MREs) of determina-
tion of neptunium and plutonium in the tests were 7.1 and
4.4%, respectively. This work was continued in the model
solutions of more complex composition and employing
both UV–Vis and IR spectra for the actinides’ quantifica-
tion [65]. The background solution of aqueous phase con-
tained all typical fission products in their common
concentration. Determination of uranium, neptunium and
plutonium both in aqueous and organic phases was per-
formed using optical spectra and PLSR. The content of all
key components can be determined with mean relative
errors not exceeding 10%.
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J Radioanal Nucl Chem (2017) 312:461–470
Analysis of uranium, nitric acid and nitrous acid was
studied in Ref. [66] using spectra acquired in the range
from 300 to 500 nm and MLR for calibration. Quantifica-
tion of all three analytes was possible not only in aqueous
but also U(VI)–nitric acid–30% TBP/kerosene system. The
authors of this study point out the advantages of on-line
monitoring by spectroscopy: ‘‘No need for radiochemical
separation process; absence of radioactive liquid-waste
from the analytical process; simplification of the analytical
process and decrease of radiation levels of the analyze and
reliability of measurement results as the form of samples
will not be changed by radiochemical separation.’’
Raman and Vis–NIR spectroscopy have been applied to
the detection of uranyl nitrate, plutonium in both IV and V
oxidation states, neptunium(V) and neodymium in the
spent nuclear fuel [61]. Aqueous solutions of the com-
mercial fuel ATM-109 and ATM-105 and model feed
solutions were prepared on varying background of nitric
acid and extracted using dodecane solution of
tributylphosphate. Spectra of resulting aqueous and organic
phases were recorded. Model feed solutions were
employed for identification of the characteristic bands of
each of the solution constituents. Raman spectra were used
of quantification of uranyl and nitrate while Vis–NIR
spectra for determination of total Pu, Np(V) and Nd(III).
Results were found to be in agreement with ICP-MS
measurements. In the following work, possibility of
determination of Pu(IV), Pu(VI), Np(V), the Np(V)-U(VI)
cation–cation complex, and Nd(III) in fuel solutions using
Vis–NIR spectra was demonstrated [67]. Similar tasks can
be addressed also using Vis–NIR and Raman spectroscopy.
For example, the analysis of aqueous solutions containing
different concentrations of nitric acid, sodium nitrate and
neodymium at varying temperatures was studied in Ref.
[68]. A model based on the PLSR and spectroscopic data
was developed and its capability to follow up changes of
the chemical composition of the process stream was
demonstrated. While both Raman and NIR spectra allowed
quantification of NO3- and H? concentrations, only NIR
was usable for determination of Nd(III). In the reports
[69, 70] the method was suggested for strong acid solution
monitoring using Raman spectroscopy.
A step further has been undertaken in the work [71]
bringing application of spectroscopy closer to the real
process control in nuclear technology. Measurements were
made in the aqueous and organic phases in the counter-
current solvent extraction testing set-up equipped with
optical Vis–NIR and Raman probes, which were installed
inside centrifugal contactors. A series of solutions,
sequentially increasing nitric acid and uranyl nitrate con-
centrations, were fed into the centrifugal contactor flow
loop system and spectra were collected upon each con-
centrations change. Calibration models were produced
J Radioanal Nucl Chem (2017) 312:461–470
Fig. 1 a Raw optical spectra
recorded during the reduction
process in Pu(IV) solution.
Color corresponds to process
time: red—start (t = 0 min),
blue—finish (t = 5 h).
b Example of restored
concentration profiles reduction
of Pu and Np. (Color
figure online)
using spectra measured in the model solutions. Combina-
tion of Raman spectroscopy techniques with chemometrics
allowed to perform online and real time monitoring of
changes in the concentrations of uranyl nitrate, nitric acid
and total nitrate in the concentration range from 0 to 0.6 M,
0 to 6 M and 0 to 7.2 M, respectively. In the first tests
involving online measurements in the laboratory equip-
ment, which were reported in these works, simple solutions
containing only nitric acid and uranyl nitrate were used.
Vis–NIR probe was also installed in the testing equipment
and spectra of other spent nuclear fuel compounds in
simulated solutions and respective calibration models have
been established. Thus, applications of both Raman and
Vis–NIR spectroscopy for online monitoring of spent
nuclear fuel processing is the next logical step.
Unfortunately, in the works discussed above data treat-
ment is described very briefly and schematically. Apart
from mentioning what methods were used, very little
information is provided. Such important issues as spectra
pre-treatment, temporary drift, validation of calibration
models, were not addressed at all.
467
Another research was aimed at on-line determination of
actinides (Np and Pu) during their reduction at certain
PUREX stage [72] The experimental solutions were closely
mimicking the composition of real industrial media and
spectral measurements (184–1000 nm range) were taken
during the reduction of metals with hydrazine, which leads
to gas bubbles formation and disturbs the spectra signifi-
cantly. Figure 1 a shows the typical view of the spectra
obtained during Pu(IV) to Pu(III) reduction and one can see
baseline curvature, strong baseline drift, excessive noise
and out of scale spectrometer readings. To make these data
suitable for further processing the authors applied asym-
metrical least squares procedure. Consecutive application
of MCR-ALS allowed for getting the concentration profiles
of reduced and oxidized actinides during the process
(Fig. 1 b).
Reprinted from Chemometrics and Intelligent Labora-
tory Systems, vol. 146, B. Debus, D. Kirsanov, C.
Ruckebusch, M. Agafonova-Moroz, V. Babain, A. Lum-
pov, A. Legin, pp. 241–249, Copyright [72] with permis-
sion from Elsevier.
123
468
A quite challenging problem of simultaneous quantifi-
cation of cerium and nitric acid in aqueous solutions was
addressed in Ref. [73]. The complexity of this case is due
to the fact, that in the studied wavelength range
(200–1000 nm) cerium has only one broad absorbance
band which is overlapping with nitric acid signal and thus
Lambert–Beer law is not suitable for direct quantification
of the components. This issue invalidates the use of con-
ventional PLSR and initial attempt of cerium quantification
failed [32], so the authors have suggested a suitable alter-
native based on Non-Linear Multivariate Curve Resolution
(NL-MCR), which yielded accurate determination of cer-
ium and nitric acid concentrations in new samples.
Conclusion
UV–Vis spectroscopy is a very simple, accessible and
convenient analytical instrument for quantitative detection
of metals. This can be done in two different ways: using
chromogenic ligands and using characteristic absorption
of an analyte. In the context of process control in nuclear
industry the latter option appears to be very attractive,
since it makes UV–Vis spectroscopy fully applicable for
on-line monitoring purposes. With the development of
optic fiber spectroscopic probes the benefits of UV–Vis
for nuclear industry are even more pronounced as fiber
probes allows for remote measurements and radiation
exposure minimization. UV–Vis spectroscopy can be
criticized for low sensitivity and low selectivity, however
when dealing with real technological solutions the first
drawback is not relevant due to sufficient concentration of
most of analytes in technological streams and the second
drawback caused by overlapping of spectral signatures of
different components can be elegantly circumvented by
the application of modern chemometric tools (the latter
however requires the fulfillment of certain conditions,
formulated by Manne [74]). The literature survey shows
the distinct growing interest to this combination of UV–
Vis and chemometrics especially in the nuclear technol-
ogy research domain. While at the moment most of the
applications were performed in controlled laboratory
environment we see no essential limitations for imple-
mentation of this approach at industrial sites. It is
important to note that most of the studies reported so far
applied only very basic chemometric procedures like PCA
and PLSR and even with these simple tools the results
obtained are quite convincing. With transition to indus-
trial sites and application of more sophisticated and tai-
lored multivariate methods UV–Vis can definitely become
one more success story of chemometrics along with NIR
spectroscopy.
123
J Radioanal Nucl Chem (2017) 312:461–470
Acknowledgement This work was partially financially supported by
Government of Russian Federation (Grant 074-U01).
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