Analytica Chimica Acta 1181 (2021) 338904

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Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

High-precision and on-line measurement of dissolved organic matter

in Electro-Fenton process based on dual wavelength analysis with
combination of fluorescence emission and ultraviolet absorption
spectroscopy
Yuchao Fu, Wanxiang Li, Haochen Li, Meizhen Huang*
Department of Instrument Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The dual wavelength analysis

combining fluorescence emission and
ultraviolet absorption spectroscopy is
proposed.

The on-line dual wavelength analyzer
is simple and suitable for on-line
monitoring dissolved organic matter
in EF process.

The dual wavelength analysis can
achieve higher precision
(R2 ¼ 0.9882, RMSE ¼ 0.0131 mg/L)
than conventional method.

This research can be referenced for
monitoring the water treatment
during the Fenton process.

a r t i c l e i n f o a b s t r a c t

Article history: Electro-Fenton (EF) process is a significant water treatment method for the degradation of dissolved
Received 5 May 2021 organic matter (DOM) in water and has been widely studied and applied in the past decade to degrade
Received in revised form various dissolved organics. During water treatment, in order to monitor the degradation efficiency, it is in
11 July 2021
dire need to develop rapid and accurate methods that are favorable to assay on-line and on-site to
Accepted 1 August 2021
Available online 4 August 2021
provide feedback in a timely manner. UVeVisible absorption spectroscopy and Excitation-Emission
Matrix (EEM) fluorescence spectroscopy techniques are most potential to realize on-line DOM mea-
surement, but the measurement accuracy is unsatisfactory because of the obligatory involvement of iron-
Keywords:
Electro-Fenton process
containing interferents. This study aims to simplify the measurement system complexity while over-
Dissolved organic matter coming the effect of iron-containing interferents during the measurement. An intrinsic relationship
High precision between the measured DOM concentration and the ultraviolet absorption at l1 and the light intensities
On-line of the fluorescence emission at l2 is derived theoretically and proved, based on which the influence of
Dual wavelength analysis iron ions and their complexes on the spectrum can be eliminated, thus the content of DOM in the
Electro-Fenton process is accurately determined. The proposed dual wavelength analysis with combi-
nation of fluorescence emission and ultraviolet absorption spectroscopy can achieve high precision
(R2 ¼ 0:9882, RMSE ¼ 0:0131 mg=L). Furthermore, the on-line measurement design, called ultraviolet

* Corresponding author.
E-mail addresses: fourier@sjtu.edu.cn (Y. Fu), mzhuang@sjtu.edu.cn (M. Huang).

https://doi.org/10.1016/j.aca.2021.338904
0003-2670/© 2021 Elsevier B.V. All rights reserved.
Y. Fu, W. Li, H. Li et al.
absorption-fluorescence emission dual wavelength analyzer, only includes one ultraviolet LED and two
photodetectors. Its structure is simple and suitable for on-line monitoring DOM in EF process.
1. Introduction
Electrochemical Advanced Oxidation Processes (EAOPs) are
green solutions for water treatment [1]. They are environmentally
benign without requiring excessive chemical reagents and destroy
persistent or toxic organic matter in water by in situ generation of
hydroxyl radicals via electrochemistry [1]. The Fenton process is
another advanced oxidation process (AOP) [2]. It is a widely studied
and applied catalytic method for water treatment due to its
cleanliness and the high efficiency to degrade the vast majority of
refractory organic pollutants [3]. Electro-Fenton (EF) process
combines the advantages of electrochemical processes and Fenton
processes [4]. As a highly efficient, well environmentally compat-
ible, and low-cost water treatment technology, it has been broadly
welcomed and drawn tremendous attention from both academia
and industry. The key to the Electro-Fenton technique also lies in
recyclable generation of hydroxyl radicals (HO$) as a powerful
oxidant in situ [4]. Hydroxyl radicals have an ability to degrade
numerous complex dissolved organic matters (DOM) indiscrimin-
ately, mineralize them and thereby purify water quality [5,6]. Hy-
droxyl radicals are produced by the oxidation-reduction reaction
between ferrous ions and hydrogen peroxide in the Fenton process
(Eqð1Þ). The reactants of H2 O2 and Fe2þ required for the Fenton
process are generated by electrochemical processes, in which
ferrous ions and hydrogen peroxide are regenerated at the cathode
via electron transfer (Eq ð2Þð3Þ)[4].
H2 O2 þ Fe2þ þ Hþ / Fe3þ þ H2 O þ HO$ (1)
O2 þ 2H þ þ 2e / H2 O2 (2)
Fe3þ þ e / Fe2þ (3)
In Electro-Fenton processes, external addition of molysite is
generally required to provide ferrous or ferric ions catalyst [3,7].
Studies in recent years proved that ferrous or ferric ions can be
provided by multistep complex fibrosis treated graphite felt cath-
ode doped with iron particles or, in this work, initially the Fe3 O4
nanoparticles embedded graphite felt cathode (Fe3 O4 @GF).
[3,8e10] Graphite felt cathode has the advantages of excellent
chemical resistance, good electrical conductivity and favorable
stability [5,11]. Moreover, due to an open and porous surface,
graphite felt exposes more catalytic active sites and shorten diffu-
sion paths which is conducive to H2 O2 production [12,13]. The
functional graphite felt electrodes doped with iron or iron oxides
mentioned above can further improve the degradation efficiency of
the EF process. In the EF process, to prevent the loss of iron ion
caused by iron precipitation, polyphosphate derivatives such as
tripolyphosphate (TPP) need to be used as chelating agents to form
complexes with Fe2þ =Fe3þ in place of the hydroxide ions
[9,10,14,15]. Because hydroxyl groups will destroy the organic
chelating agents and be consumed, replacing the organic chelating
agents such as Ethylene Diamine Tetra acetic Acid (EDTA) with
tripolyphosphate as ligand can avoid the influence on the forma-
tion of hydroxyl groups, realistically improving the efficiency of the
Electro-Fenton process. And the chelates of TPP maintain the re-
action activity of complexed ferrous ions and complexed ferric ions
2
Analytica Chimica Acta 1181 (2021) 338904
© 2021 Elsevier B.V. All rights reserved.
at a circum-neutral pH (Eqð4  6Þ) [9,14].
Fe2þ  TPP þ O2 þ H þ / Fe3þ  TPP þ HO2 , (4)
Fe2þ  TPP þ HO2 , þ H þ / Fe3þ  TPP þ H2 O2 (5)
Fe2þ  TPP þ Hþ þ H2 O2 / Fe3þ  TPP þ HO$ þ H2 O (6)
The major purpose of the EF process is to degrade DOM in water.
In order to monitor DOM concentration in the EF process,
oxidation-reduction titration method and reverse phase high-
performance liquid chromatography (RP-HPLC) are commonly
employed [16,17]. However, these methods are complicated, time-
consuming, and require sampling for laboratory measurement
and analysis, which are not suitable for on-line and efficient
monitoring [16,17]. Hence nondestructive and efficient spectro-
scopic techniques have also been explored for applications. For
instance, Tingting Lian used UVeVisible absorption spectroscopy
directly to determine the RhB content in the EF process [8]. Three-
dimensional Excited-Emission Matrix (EEM) fluorescence spec-
troscopy is a rapid and sensitive technique for the analysis of DOM
content and is also commonly used to observe the content variation
of DOM in water [18e20]. This technique has been used success-
fully to characterize organic matter in seawater [21e24], freshwater
[25e28] or estuarine water [3,6,29]. Also, it has been used to
monitor riverine organic matter and diesel pollution [30,31], eval-
uate drinking water treatment processes [32e34] or detect pesti-
cides [35]. However, in the Fenton process, the presence of iron ions
and their complexes absorb light in the UVeVisible spectral region
which covers the waveband of excitation light and DOM fluores-
cence emission. Therefore, when spectroscopic techniques are
adopted to monitor the DOM content in the EF process, the iron-
containing interferents would cause a certain error in the quanti-
fication and the measurement accuracy would be unsatisfactory.
While UVeVisible absorption spectroscopy and EEM fluores-
cence spectroscopy are utilized to characterize dissolved organic
matter, the DOM concentration is generally reflected simply by
measuring absorbance at 254 nm as an index to evaluate the effi-
ciency of water treatment [19]. According to the absorption and
fluorescence spectrum characteristics of DOM, a LED with a central
wavelength around 280 nm can also be used as an excitation light
source because the DOM content can be measured on-line by
detecting the emitted fluorescence of different categories of DOM
under the 280 nm excitation light source [36]. DOM produces three
main categories of fluorescence emission under the 280 nm ultra-
violet excitation light [36]. Generally, as listed in Table 1, the fluo-
rescence in the range of lEm < 380nm is attributed to protein-like
fluorescence signal (e.g., tryptophan, phenol, tyrosine, aniline de-
rivatives); the fluorescence in the range of lEm > 380nm is attrib-
uted to humic-like fluorescence signal, which is always associated
with fluorophores combining two aromatic rings and electro-
donating groups (e.g., aminonaphthol, 4-phenoxyphenol). In
addition, there is fluorescence from a small amount of artificial
polycyclic aromatic hydrocarbon (PAHs) in natural water with
fluorescence emission in the range of 320e400 nm. Protein-like
DOM in water has a bearing on biochemical oxygen demand
(BOD), toxicity, etc., and also related to the generation potential of
Y. Fu, W. Li, H. Li et al.
Table 1
Excitation and emission of the DOM in water.
Type Substance
The protein-like fluorophores Tryptophan
Tyrosine aromatic amino acids
The humic-like fluorophores Humic acids
Fulvic acids
Anthropogenic DOM fluorophores Polycyclic aromatic hydrocarbons (PAHs)
toxic disinfection byproducts (DBPs) indirectly during water
treatment such as chlorination and disinfection [19]. Tri-
halomethanes (THMs) and haloacetic acids (HAAs) are two main
classes of hazardous compounds, which are strictly controlled in
many countries. [26, 37] Researches also show that the fluorescence
intensity emitted by dissolved organic matter and apparent oxygen
utilization (AOU) are linearly related in the mesopelagic and abyssal
layers [38].
As has been mentioned above, ferric and ferrous ions are the
main reactants participating in the Electro-Fenton process. Since
ferric ions and ferrous ions absorb light in the wide UVeVisual
spectral region, when spectrometry is applied, the presence of
iron ions and their complexes can seriously interfere with the re-
sults of quantitative spectroscopic analysis (Fig. 1). As a result, the
aforementioned ultraviolet absorption spectroscopy and fluorim-
etry analysis, which are widely applied, fail to accurately quantify
the concentration of DOM on the aspect of Electro-Fenton process
for water treatment. In order to address this issue, our research
details a more accurate analytical chemistry methodology of the
determination of the DOM concentration, which involves with a
mathematical model established and data treatment. Specifically, a
dual wavelength analysis method with combination of fluorescence
emission and ultraviolet absorption spectroscopy was proposed for
on-line and high-precision determination of DOM content in the
Electro-Fenton process. With the comprehensive utilization of
absorbance and fluorescence emission information at two wave-
lengths, the precise relationship between the measured DOM
concentration and the light intensity of the two channels was
derived and the influence of iron ions and their complexes on the
spectrum is eliminated, thus the content of dissolved organic
matter in the Electro-Fenton process was accurately quantified.
And based on this idea, an analyzer was designed instead of a
Fig. 1. The absorption spectra of tryptophan,tripolyphosphate,iron ions and their
complexes.
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Analytica Chimica Acta 1181 (2021) 338904
Excitation wavelength Emission wavelength
(lEx =nm) (lEm =nm)
225e280 350
225e280 310
230e300 380e460
320e380 400e500
220e300 320e400
straightforward utilization of commercial instrumentation, which
is a prototype of ultraviolet absorption-fluorescence emission dual
wavelength analyzer, and the design of the dual wavelength
analyzer prototype is simple and portable. It is suitable for on-line
detection of DOM content in the EF process. Tryptophan is one of
the essential amino acids for life and a representative protein-like
DOM present in water [36]. Tryptophan taken as an example in
the experiment, the established prototype of dual wavelength
analyzer was used to carry out an on-line and highly-precise
monitoring the changes of tryptophan content during the EF
process.
2. Methods and sensor design
2.1. Methods
When using nondestructive and efficient spectroscopic deter-
mination technologies to analyze the concentration of dissolved
organic matter, the traditional common methods are ultraviolet
absorption spectroscopy and fluorimetry analysis. However, due to
the absorption of the excitation light and the fluorescence emitted
from the DOM fluorophore by the iron-containing interferents, the
influence of the iron-containing interferents cannot be excluded
using only ultraviolet absorption spectroscopy or only fluorimetry
analysis. By selecting one wavelength at the absorption band and
one wavelength at the fluorescence band, the comprehensive
analysis decouples the absorption part of the spectrum by iron-
containing interferents, so as to obtain an accurate quantitative
relationship with regard to dissolved organic matter.
The ultraviolet absorption spectroscopy quantitative analysis
method is based on the Beer-Lambert law for the determination of
DOM concentration. As shown in Fig. 2, assumed that the DOM
concentration in water is cTrp , the reference incident light intensity
is I0 at the wavelength of l1 and the wavelength of the output light
is still l1 with the intensity of Il1 . According to the Beer-Lambert
law, it can be written:
Fig. 2. Quantitative analytical model diagram of ultraviolet absorption spectroscopy
and fluorimetry analysis.
Y. Fu, W. Li, H. Li et al.
cTrp ¼ z1 ,Al1 ; (7)
Al1 ¼ ln Tl1 ; (8)
Where the z1 is an instrument constant to be calibrated, obtained
by calibration with standard solutions. Tl1 is the excitation light
transmittance to be measured through the water, i.e., Tl1 equals Il1
divided by the reference incident light intensity I0. The reference
incident light intensity I0 can be measured by the detector at l1
when the sample is pure water.
The fluorimetry quantitative analysis method is based on that
under the irradiation of UV light, the dissolved organic matter emits
fluorescence quantitatively at a specific wavelength [39]. As shown
in Fig. 2, the wavelength of fluorescence emission is l2 and the
fluorescence emission intensity in the receiving direction is Il2 . In
order to eliminate the effect of light source fluctuation during the
measurement, hl2 is defined as the fluorescence conversion effi-
ciency. hl2 equals Il2 divided by the reference incident light in-
tensity I0. And let Bl2 be:
Bl2 ¼ ln hl2 ; (9)
When the fluorimetry quantitative analysis method is applied to
analyze the DOM concentration, the DOM concentration cTrp is
proportional to fluorescence conversion efficiency hl2 at a certain
range of concentration. Then the fluorimetry quantitative analysis
method can be written as:

tional Pharmaceutical Group Corporation. Sodium tripolyphos-
ln z2 ,cTrp ¼ Bl2 ; (10)
Where the z2 is also an instrument constant to be calibrated, ob-
tained by calibration with standard solutions.
Formally, by combining Eq:ð7Þ and Eq:ð10Þ at a certain propor-
tion, the dual wavelength analysis method with combination of
fluorescence emission and ultraviolet absorption spectroscopy
method can be obtained:


ln k2 ,cTrp þ k3 ,cTrp ¼ k1 ,Al1  Bl2 ; (11)
Where the ki ði ¼ 1; 2; 3Þ are instrument constants to be calibrated.
Eq:ð11Þ is the key formula of the proposed analytical method. The
following rigorous mathematical derivation gives the proof that the
iron-containing interferents can be overcome. Assuming that the
optical path of the excitation light is b, the molar extinction coef-
ficient of the dissolved organic matter is εf 1 at the wavelength of l1 ,
the fluorescence quantum yield is 4f 2 at the wavelength of l2 , the
fluorescence emission of the dissolved organic matter intensity is If ,
the iron equivalent concentration of the iron-containing interfer-
ents is cd , the molar extinction coefficient is εd1 at the wavelength
of l1 and εd2 at the wavelength of l2 . According to Beer-Lambert
law and the law of fluorescence emission intensity, the following
formulas can be listed:
 
Al1 ¼ b, 2:303,εf 1 ,cTrp þ 2:303,εd1 ,cd ; (12)
If ¼ 2:303,b,4f 2 ,εf 1 ,cTrp ,I0 ; (13)
 
If
ln ¼ 2:303,b,εd2 , cd ; (14)
Il2
Solving the above equations, it can be obtained:
4
Analytica Chimica Acta 1181 (2021) 338904
  ε ε
ln 2:303,4f 2 ,εf 1 ,b,cTrp þ d2 ,εf 1 ,b,cTrp ¼ d2 ,Al1  Bl2 ;
εd1 εd1
(15)
Denote the constant parameter in Eq:ð15Þ as:
εd2
k1 ¼ ; (16)
εd1
k2 ¼ 2:303,4f 2 ,εf 1 ,b ; (17)
εd2
k3 ¼ ,ε ,b ; (18)
εd1 f 1
Thus, the dual wavelength analysis formula (Eq:ð11Þ) is ob-
tained. Generalizing the dual wavelength analysis method, the
mathematical model and subsequent calculations present a refer-
ence method, which not only can eliminate the interference of iron
species, but also can be applied to many similar application sce-
narios, where the fluorimetry quantitative analysis is interfered by
interferents during the measurement.
2.2. Chemical reagents
Tryptophan is reagent grade (>99%), purchased from Beijing J&K
Scientific Ltd. Iron chloride hexahydrate (>99%) and sodium hy-
droxide (96%) are obtained from Aladdin reagent (Shanghai) Co.,
Ltd. Iron (II) sulfate heptahydrate (AR) and sulfuric acid (98%) are
purchased from Chemical Reagents Shanghai Co., Ltd., China Na-
phate (Na5 P3 O10 , 98%) is sourced from Shanghai Meryer Chemical
Technology Co., Ltd. The nanoparticle size of iron oxide (II,III) is
around 20 nm (>99.5%), purchased from Shanghai Macklin
Biochemical Co., Ltd. Graphite felt is purchased from Beijing Jing
Longte Carbon Technology Co., Ltd. The above chemical reagents
are used as received without any further purification.
2.3. Bench-scale Electro-Fenton experiment
Fig. 3 shows a schematic diagram of the Bench-scale Electro-
Fenton experimental device established to simulate the EF reaction
process. It is used to monitor the DOM content in the EF process on-
line, including an Electro-Fenton reactor, a process control unit and
a dual wavelength on-line analyzer for DOM fluorescence. Through
the electrochemical mechanism, H2 O2 and Fe2þ are repeatedly
generated in the EF reactor to provide reactants for the Fenton
process. The anode is fabricated with an inert metallic platinum
sheet electrode. Graphite felt electrode doped with iron oxide
nanoparticles is utilized as cathode. Before the experiment, the
electrodes are soaked with 0.1 M diluted sulfuric acid. Electrolysis is
carried out with a constant current density. The effective volume of
the EF reactor is 500 mL. A small gas-pump pumps oxygen into the
reaction tank at an average flow rate of 600 mL/min prior to the
electrolysis and all over the process to keep the water saturated
with oxygen. A constant magnetic stirring keeps at a rate of
400 rpm. A pH meter probe is installed in the EF reactor to deter-
mine the pH on-line during the reacting process, which is not
shown in the figure. The water sample in the EF reactor is sent into
the dual wavelength on-line analyzer for real-time analysis through
the process control unit and is returned to the reactor after
measurement.
The experimental water matrices are taken from a Zhiyuan Lake
located on the campus of Shanghai Jiao Tong University, which
sources mainly from natural precipitation and seepage flow and is
rich in species diversity. The water matrices filtered through a
Y. Fu, W. Li, H. Li et al.
Fig. 3. The schematic diagram of the Bench-scale Electro-Fenton experimental device and the Electro-Fenton process.
0.45 mm glass fiber filter paper, the turbidity of the water matrices is
about 3 NTU, which can be used in experimental study.
The cathode of the Electro-Fenton process employs a graphite
felt electrode doped with iron oxide nanoparticles. Ferrous ions and
hydrogen peroxide can be cyclically produced on the cathode of
Fe3 O4 @GF, and the hydroxyl radical generated by their reaction
attacks the DOM in water to degrade it without selectivity, thus the
water quality can be purified [5,6]. The intimate contact of the
embedded Fe3 O4 nanoparticles and the graphite felt electrode is
able to accelerate the conversion rate of Fe3þ and Fe2þ , which is
beneficial to accelerating the chemical kinetics of the Electro-
Fenton reaction process [3,8e10]. The pH value during the exper-
iment is adjusted by the addition of dilute sulfuric acid. The sodium
tripolyphosphate (STPP) is added into the EF reactor, which acts as
the electrolyte and chelating agent. Not only is it able to enhance
the electrical conductivity, making it possible for the Fenton pro-
cess to proceed in a near neutral environment, it also has the ability
to reduce the oxido-reducing potential of Fe3þ /Fe2þ [40]. STPP is
considered to be a safe substance and can be retained in water as a
class of nutrients after wastewater treatment [41].
2.4. Design of dual wavelength analyzer
An ultraviolet absorption-fluorescence emission dual wave-
length analyzer for dissolved organic matter is designed. The
wavelength of LED light source and detection wavelength of the
dual wavelength analyzer are determined according to the fluo-
rescence emission spectrum of the DOM to be measured and the
absorption spectra of various species in water during the EF
process.
The absorption spectra of tryptophan, Fe2þ , Fe3þ , STPP,
Fe2þ  TPP and Fe3þ  TPP are shown in Fig. 1. Considering that
tryptophan is a kind of protein-like DOM, fluorescence in range of
lEm < 380nm can be emitted under the irradiation of UV light at
l1 ¼ 270nm. In addition, the iron-containing interferents has a
similar molar extinction coefficient near l2 ¼ 315nm, so l1 ¼
270nm and l2 ¼ 315nm are preferably selected as the detection
wavelengths of the dual wavelength analyzer.
The structure diagram of the ultraviolet absorption-
fluorescence emission dual wavelength analyzer for DOM is
5
Analytica Chimica Acta 1181 (2021) 338904
shown in Fig. 4. The LED light is driven by a constant current source,
maintaining stable irradiation with an effective radiation power of
2 mW. The 270 nm light goes into the measured water sample in
parallel after collimation. Parallel light goes out in the original di-
rection is filtered passing through a 270 nm narrow band filter and
is focused by a lens. Then it is received by the photodetector,
measuring the light intensity Il1 at the wavelength of l1 ¼ 270nm.
Tryptophan photoluminescence radiates in all directions. This
portion perpendicular to the excitation light is received by another
photodetector after being filtered through a 315 nm narrow band
filter and being focused, measuring the fluorescence emission in-
tensity Il2 at the wavelength of l2 ¼ 315nm.
In order to ensure that the tryptophan quantitative analysis
concentration to be analyzed is within the linear region of the Beer-
Lambert law, linearity of the absorbance dependence on concen-
tration measured by the dual wavelength analyzer is tested shown
as Fig. 5(a). Within the tryptophan concentration range analyzed in
this paper (10 mg/L), the linear correlation between the absor-
bance at the wavelength of l1 ¼ 270nm and the concentration
reaches more than 0.999. In this range, the mathematical model
(Eq:ð11Þ) is theoretically accurate while the non-linearity due to the
limitation of the Beer-Lambert law may need to combine with our
previous research to solve [39].
3. Result and discussion
3.1. Calibration
Before applying Eq:ð11Þ to on-line measurement of dissolved
organic matter in the EF process, it is necessary to calibrate the
constants of ki ði ¼ 1; 2; 3Þ in the formula. First, a series of trypto-
phan standard gradient solutions mixed with random concentra-
tions of iron-containing interferents are prepared, and the
concentrations of these standard solutions cTrp are known. Then,
the dual wavelength analyzer is used to measure the Il1 and Il2 of
these standard solutions. Subsequently, Al1 and Bl2 can be calcu-
lated respectively. Finally, at 95% confidence level, Levenberg-
Marquert algorithm is used to solve the nonlinear least square
problem to fit the Eq: ð11Þ. After the calibration, the Eq:ð11Þ can be
applied to analyze the content of dissolved organic matter during
Y. Fu, W. Li, H. Li et al.
Fig. 4. The structure diagram of the ultraviolet absorption-fluorescence emission dual wavelength analyzer for dissolved organic matter.
Fig. 5. Model establishment and calibration. (a) The linearity of the absorbance
dependence on concentration measured by the dual wavelength analyzer. (b)The fitted
surface of ultraviolet absorption-fluorescence emission dual wavelength model.
6
Analytica Chimica Acta 1181 (2021) 338904
the on-line monitoring in Electro-Fenton process.
The standard solutions are tryptophan solutions of different
concentrations ranging from 1:2 mg=L to 10 mg=L, which are also
containing random concentrations of Fe2þ ; Fe3þ and STPP.
Fe2þ  TPP and Fe3þ  TPP will be naturally generated in the solu-
tion for 2 h at 25  C before measurement. Concentrations ranged
from 0:01 mmol=L to 0:10 mmol=L for randomly promiscuous Fe2þ ,
from 0:01 mmol=L to 0:08 mmol=L for randomly promiscuous Fe3þ ,
and from 0:25 mmol=L to 3:90 mmol=L for randomly promiscuous
STPP. Detailed concentration configuration is shown in
Supplementary Material Table S1. A total of 17 groups are config-
ured. The tryptophan concentrations cTrp of these standard solu-
tions are known Il1 and Il2 are measured by the dual wavelength
analyzer and furthermore Al1 and Bl2 are calculated. The surface of
Fig. 5(b) is the fitted surface of Eq:ð11Þ obtained after ki ði ¼ 1; 2; 3Þ
calibrated with standard solutions. It precisely portrays the rela-
tionship with tryptophan concentration only by the information at
these two wavelengths, l1 ¼ 270nm and l2 ¼ 315nm, and get rid
of the possible iron-containing interference present in the EF pro-
cess. While only the fluorescence at l2 ¼ 315nm is used to describe
the tryptophan concentration, the lower the tryptophan concen-
tration is, the more susceptible it will be to interference from iron-
containing interferents.
3.2. Quantitative analysis results of standard solution
The feasibility of the analytical methodology needs to be vali-
dated from theoretical derivation to experimental verification. The
standard solutions are quantitatively analyzed by the ultraviolet
absorption spectroscopy quantitative analysis, the fluorimetry
quantitative analysis and the dual wavelength analysis method
respectively. Fig. 6(a-c) shows the results of the three quantitative
analysis methods. According to the result of the ultraviolet ab-
sorption spectroscopy quantitative analysis, DOM content could no
longer be accurately quantified by the ultraviolet absorption
spectroscopy quantitative analysis (Fig. 6(a)) due to the serious
interference of UV absorption by iron-containing substances,
whose analysis result is R2 ¼ 0:0904; RMSE ¼ 2:5695. The result of
the fluorimetry quantitative analysis is slightly superior than that
by the ultraviolet absorption spectroscopy quantitative analysis
(Fig. 6(b)): R2 ¼ 0:8294; RMSE ¼ 1:1118, which is barely depict the
variation trend accurately. The dual wavelength analysis is capable
of quantifying the tryptophan concentrations with high precision
Y. Fu, W. Li, H. Li et al.
Fig. 6. The standard solutions analyzed quantitatively and the Electro-Fenton degra-
dation reaction monitored on-line by the ultraviolet absorption spectroscopy
7
Analytica Chimica Acta 1181 (2021) 338904
under random interference and result is accurate and reliable
(Fig. 6(c)): R2 ¼ 0:9942; RMSE ¼ 0:2060, which illustrates that the
analytical approach can accurately monitor the changes of DOM
under the interference of iron-containing interferents in EF process.
3.3. On-line monitoring of the EF process
Graphite felt electrode embedded with Fe3 O4 nanoparticles
provide iron source for the EF process. In addition, it provides
abundant active centers from the nanoparticle embedded structure
with abundant cracks, which helps to improve the degradation rate
of the EF reaction. The Electro-Fenton degradation reaction was
monitored on-line by the ultraviolet absorption-fluorescence
emission dual wavelength analyzer. The ultraviolet absorption
spectroscopy quantitative analysis, the fluorimetry quantitative
analysis and the dual wavelength analysis method are utilized to
analyze the measured data respectively. The results are shown in
Fig. 6(d) and how the proposed methodology compares with those
previously reported for the analytes in question is addressed. Initial
concentration of tryptophan is cTrp0 ¼ 3:5mg=L and the initial pH of
the solution is 4:7. Concentrations cTrp are determined and recor-
ded every 5 min. Degradation of tryptophan by Electro-Fenton
process follows pseudo first order chemical reaction kinetics,
whose apparent reaction rate constant is
kapp ¼ ð4:496 ±0:150Þ  102 min1 (the red dash line in Fig. 6(d)).
Data points in green and orange are the analytical results
monitored on-line by the ultraviolet absorption spectroscopy
quantitative analysis and the fluorimetry quantitative analysis
respectively. It is totally unable to monitor the DOM content
changing quantitatively by the ultraviolet absorption spectroscopy
quantitative analysis in the presence of varying iron-containing
interferents. The fluorimetry quantitative analysis can roughly
monitor the variation trend of DOM degradation without being able
to achieve accurate unbiased quantification. The dual wavelength
analysis method proposed in this paper is represented by the blue
data points in the figure. Taking a negative logarithm of its ordinate,
the linear fitting goodness of R2 ¼ 0:9882 can be achieved while
Root mean square error of on-line monitoring is
RMSE ¼ 0:0131 mg=L (Fig. 6(d). inset). In the process of this on-line
monitoring, it also demonstrates that the Fe3 O4 nanoparticle
embedded in carbon felt electrode changes the iron content in the
water, meanwhile it is proved from another perspective that the
complexes Fe2þ TPP contributes to the oxidation of DOM. The re-
sults show that the analytical model established by Eq: ð11Þ can not
only accurately quantify the standard solution but also monitor the
DOM content variation trend online in the EF process with high
precision and no bias.
4. Conclusion
In this paper, a new spectral chemometric method of dual
wavelength analysis with combination of fluorescence emission
and ultraviolet absorption spectroscopy, which is capable of on-line
measuring dissolved organic matter with high precision in the
Electro-Fenton process, is proposed. The absorption of excitation
light and fluorescence by iron-containing interferents have been
taken into consideration comprehensively. The intrinsic
quantitative analysis, the fluorimetry quantitative analysis and the dual wavelength
analysis method respectively. (a) The ultraviolet absorption spectroscopy quantitative
analysis monitoring at l1. (b) The fluorimetry quantitative analysis monitoring at l2. (c)
The dual wavelength analysis. (d) The Electro-Fenton degradation reaction monitored
on-line by the ultraviolet absorption spectroscopy quantitative analysis, the fluorim-
etry quantitative analysis and the ultraviolet absorption-fluorescence dual wavelength
analysis respectively.
Y. Fu, W. Li, H. Li et al.
relationship between the measured DOM concentration and the
light intensity of two wavelengths is derived and the influence of
iron ions and their complexes on the spectrum is eliminated. With
two suitable wavelengths (l1 ¼ 270nm and l2 ¼ 315nm) selected,
standard solution experiment and a Bench-scale Electro-Fenton
experiment were performed on the designed ultraviolet
absorption-fluorescence emission dual wavelength analyzer. The
results show that the analytical model established by Eq: ð11Þ can
not only accurately quantify the standard solution but also monitor
the DOM content variation trend online in the EF process with high
precision and no bias.
Compared with the conventional methods, the dual wavelength
analysis method can achieve higher precision on the premise of
simplifying the measurement conditions. This analytical chemistry
methodology can bring a certain reference value to a wide range of
researchers working on the Fenton process and water treatment.
Meanwhile, the mathematical model and subsequent calculations
built in the research present a spectral chemometric techniques,
which not only can eliminate the spectral interference of iron
species, but also can be applied to many similar application sce-
narios where the fluorescent substance is interfered by interferents
during the measurement.
CRediT authorship contribution statement
Yuchao Fu: Conceptualization, Methodology, Data curation,
Writing e original draft, Writing e review & editing. Wanxiang Li:
Visualization, Software, Validation, Writing e original draft, Su-
pervision, Writing e review & editing. Haochen Li: Validation,
Writing e original draft, preparation, Supervision, Writing e re-
view & editing. Meizhen Huang: Investigation, Project adminis-
tration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the Key research and development
program of Guangdong Province (No. 2020B1111020001) and the
National Natural Science Foundation of China (No. 61775133).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.aca.2021.338904.
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