Environmental Engineering and Management Journal September 2014, Vol.13, No.

9, 2167-2172
http://omicron.ch.tuiasi.ro/EEMJ/

“Gheorghe Asachi” Technical University of Iasi, Romania

BORON-DOPED DIAMOND ELECTRODE-BASED ADVANCED

TREATMENT METHODS FOR DRINKING WATER

Florica Manea1, Agnes Jakab1, Magdalena Ardelean1, Aniela Pop1, Ilie Vlaicu2
1
“Politehnica”University of Timisoara, 2 Vasile Parvan Bd., 300223, Timisoara, Romania
2
S.C. Aquatim S.A., Gheorghe Lazar Str., no 11A, 300081Timisoara, Romania

Abstract

In this study, boron-doped diamond (BDD) electrode was tested in electrochemical oxidation and reduction processes using the
same vertical electrodes undivided cell in order to remove natural organic matter (NOM) and nitrogen compounds (NC) from
drinking water. Boron-doped diamond-based electrochemical oxidation process has proven to be an efficient and versatile
method suitable for NOM and NC in forms of nitrite and ammonium present in drinking water sources. However, the application
of BDD-based electrooxidation process is limited due to the nitrate formation as oxidation product for drinking water source
characterized by high content of nitrate. It has been found that BDD-based electroreduction process was not an efficient method
for nitrate removal, even if it allowed nitrite reduction but with high energy consumption.

Key words: drinking water treatment, electrochemical oxidation, natural organic matter, nitrogen compounds

Received: March, 2014; Revised final: August, 2014; Accepted: September, 2014

1. Introduction the main constituents of NOM, characterized by a

Natural organic matter (NOM) and nitrogen
compounds (NC) are considered to contribute to the
main groundwater treatment challenges in drinking
water treatment plants. As NOM and NC content can
significantly vary from a groundwater source to
another, an intensive research study is needed for the
best choice for the drinking water treatment process
in direct relation with groundwater source quality.
The electrochemical methods could be the
alternative to the conventional water treatment
processes, or could be included as new module in the
classical treatment methods, in order to improve the
drinking water quality.
Different NOM sources in groundwater led to
various groundwater characteristics in relation with
the organic loading. A vast domain of organic
compounds from largely aliphatic to aromatic
compounds, from small to large molecules
constitutes the NOM from waters, which can be low
or highly loaded. Humic and fulvic acids represent
heterogenic mixture of hydrophobic and hydrophilic
refractory compounds with high molecular weight.
Usually, the NOM content in waters is characterized
and quantified through total and dissolved organic
carbon (TOC and DOC) and ultraviolet absorbance at
254 nm (A254) (Joseph et al., 2012). In the drinking
water treatment plants, NOM is commonly removed
by coagulation, adsorption, ultra- and nano-filtration,
ion-exchange and advanced oxidation processes
(AOPs) (Militaru et al., 2013; Orha et al., 2013;
Segneanu et al., 2013). Matilainen and Sillanpää
made an exhaustive study on AOPs applied for NOM
removal, i.e., UV-light based application, ozone
based applications, heterogenous photocatalysis,
Fenton process, catalytic oxidation and
electrochemical oxidation (Matilainen and Sillanpää,
2010).
It is well-known that another significant
problem in groundwater treatment is the content of
nitrogenous compounds. Electro-coagulation,
advanced oxidation, electrolysis and bio-

 Author to whom all correspondence should be addressed: e-mail: florica.manea@upt.ro

 Manea et al./Environmental Engineering and Management Journal 13 (2014), 9, 2167-2172
electrochemical treatments are only few of the
electrochemical methods studied in the last years for
water denitrification (Lacasa et al., 2012; Masai et
al., 2009; Mousavi et al., 2011; Orescanin et al.,
2011; Pérez et al., 2012).
Taking into consideration the principle of
the electrooxidation and electroreduction processes,
these should be applied as separate and individual
stages of a drinking water technological flow or in
the same stage by simple reverse of potential. It is
clear that for the last possibility, it is imposed the use
of the same electrode. One of these types of the
electrodes is boron-doped diamond electrode, which
posses multiple application in water treatment
through electrooxidation, electroreduction,
electrodisinfection etc. (Fujishima et al., 2005; Kraft,
2007). An electrode material as boron doped
diamond, due to its outstanding features, e.g., large
potential window, generation of highly active
radicals, hardness, low environmental impact or
stable surface (Alfaro et al., 2006; Carter and Farrell,
2008; Vlaicu et al., 2011), could offer an efficient
solution in water treatment for both NOM and NC,
through controlled electrochemical oxidation-
reduction processes.
Based on the multiple applications of the
electrochemical treatment processes using boron
doped diamond electrodes in water and wastewater
treatment technology (Motheo and Pindeho, 2000;
Panizza and Cerisola, 2005; Vlaicu et al., 2011), and
the advantages of electrochemical oxidation
application in water treatment as simultaneous
removal of a wide range of pollutants, the aim of this
paper is to test the application of boron-doped
diamond (BDD) electrodes in the electrochemical
oxidation and reduction processes for the removal of
NOM and NC, as a possible solution for drinking
water treatment technology using real groundwater
sources.
2. Experimental
2.1. Groundwater characterization
All studies have been performed on real
groundwaters, from two different sources from Timis
County, names GW1 and GW2, one representative
for the waters characterized by high natural organic
load (GW1) and one contaminated with nitrogen
compounds (GW2), the last one belonging to nitrate
vulnerable area. Both groundwaters represent the
drinking water source for certain populated area. The
groundwater has been characterized, and the
following parameters have been determined: pH,
conductivity, total organic carbon (TOC), chemical
oxygen demand (COD), total nitrogen (TN),
ultraviolet absorbance at 254 nm (UV254) (Table 1).
Table 1. Groundwater characteristics
Water Conductivity SO42-
pH
sample µS/cm2 mgL-1
GW1 8.26 751 17.3 14.79
GW2 7.73 745 15.5 7.36
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For TOC measurements a Shimadzu TOC-L
Analyzer has been used, and the spectrometric
measurements were carried out using a UV-VIS
Spectrophotometer Varian Cary 100 Conc.
2.2. Electrochemical degradation of NOM and NC
Degradation of NOM and NC has been carried
out in a batch system using an undivided cell with a
volume capacity of 1 dm3, for the two groundwater
samples GW1 and GW2, in 100 mgL-1 Na2SO4
supporting electrolyte. The BDD/Nb planed-plate
electrodes (100 mm x 50 mm x 1 mm) with an active
geometric surface area of 280 cm2, provided by
CONDIAS, Germany, were used as vertical anodes
and stainless steel plates (100 mm x 50 mm x 1 mm).
Besides the common technical efficiency (ɳ),
the electrooxidation assessment has been performed
in terms of the electrochemical efficiency using Eqs.
(1, 2):
E A254 
A254 , 0  A254 , f   V (mg / C·cm ) 2
(1)
QS
ETOC 
TOC0  TOC  V (mg / C·cm2) (2)
QS
and also, in term of the mineralization efficiency by
Eq. (3):
nFVs ( TOC )exp
MCE   100 (%) (3)
4.32  107 mIt
where (A254,0-A254,f) is the change in absorption
determined at 254 nm wavelength; (TOC0-TOC) is
the change in total organic carbon concentration
determined during experiments for a charge
consumption, Q, corresponding to various
electrolysis time, V is the sample volume of 700 cm3,
and S is the area of the electrode surface, equal to
280 cm2. In the equation (3), n represent the number
of electrons consumed in the mineralization process
of NOM, F is the Faraday constant equal to 96487 C
mol-1, Vs is the solution volume (dm3), Δ(TOC)exp is
the experimental TOC decay (mg·dm-3), 4.32·107 is a
conversion factor for units homogenization, obtained
from 12000 mg C·mol-1 multiplied with 3600 s·h-1, m
is the number of carbon atoms in humic acid, I is the
applied current (A), and t is time (h) (Vlaicu et al.,
2011).
3. Results and discussion
Taking into account the real technological
issues, all BDD-based electrochemical processes
were tested without pH adjustment.
COD TOC NO3- NO2- NH4+
mgO2 L-1 mgL-1 mgL-1 mgL-1 mgL-1
6.61 - - -
5.015 1.49 0.52 1.782
 Boron-doped diamond electrode-based advanced treatment methods for drinking water

3.1. Application of BDD in the electrochemical
oxidation process for drinking water treatment
The first experiments for the optimization
working parameters were performed for the
groundwater characterized by high organic load
(GW1). The main operational parameter for applying
the electrochemical process is the current density.
Based on our previous published results (Vlaicu et
al., 2011) and taking into consideration the economic
aspects, various current densities were tested, i.e., 10,
25, 35 and 50 mA·cm-2. Figs. 1 a-d presents the
results obtained in terms of technical degradation
efficiency (ɳA254) and technical mineralization
efficiency (ɳTOC), electrochemical degradation
efficiency (EA254) and electrochemical mineralization
efficiency (ETOC).
Except the current density of 10 mA·cm-2, the
other all tested current density allowed reaching
similar technical degradation and mineralization
efficiency (Figs. 1 a, c). As we expected, the
significant differences are noticed for the assessment
in terms of the electrochemical degradation and
mineralization efficiencies (Figs. 1 b,d).
These results corroborated with mineralization
current efficiency (MCE) and specific electrical
energy consumption (Wsp) (Figs. 2 a,b) lead to select
25 mA·cm-2 as optimal current density from
technical-economical point of view.
For comparison, this current density was
applied for the electrooxidation of the second studied
groundwater source (GW2). The results are presented
in Fig. 3, and it can be noticed that better efficiency
was reached for GW1. Due to this water is
characterized by nitrogen content as nitrite and
ammonium, these parameters were followed after the
electrooxidation application under the working
operation of the current density of 25 mA·cm-2, also.
Fig. 4 presents the evolution of nitrogen
species (nitrate, nitrite and ammonium) during the
electrooxidation process, revealing a decrease of
ammonium and nitrite, and an increase of nitrate
species. These results are very promising for the
groundwater loaded with high concentrations of
nitrite and ammonium and without or low nitrate
concentration, which will not exceed the maximum
allowance concentration for nitrate.

a b

c d

Fig. 1. The influence of current density: 1-10 mA cm-2; 2-25 mA cm-2; 3-35 mA cm-2, 4-50 mA cm-2 on the removal efficiency of
humic acid and electrochemical efficiency using BDD electrodes in water electrooxidation process (GW1) in SO42- 100 mg·L-1,
characterized by (a, b) A245 nm and (c,d) TOC parameters

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 Manea et al./Environmental Engineering and Management Journal 13 (2014), 9, 2167-2172

a b
Fig. 2. Evolution of mineralization current efficiency (a ) energy consumption (b) at various current density values: 1-10
mA cm-2; 2-25 mA cm-2; 3-35 mA cm-2; 4-50 mA cm-2

a b
Fig. 3. Evolution of NOM removal and electrochemical efficiency (a ) and TOC removal and electrochemical efficiency (b) for
both types of groundwaters: 1,1’- GW1; 2,2’- GW2 at the optimum current density of 25 mA cm-2

based on nitrate and nitrite electrochemically

It must be underlined that the imposed reduced, which means that N2 probably is formed.
maximum allowance concentrations and the usual
content of ammonium and nitrite are very low in
comparison with nitrate concentration. For nitrate
removal from water, the application of
electroreduction process is further presented.

3.2. Application of BDD in the electrochemical

reduction process for drinking water treatment

To check the electroreduction process for

nitrate and nitrite removal from water, BDD
electrodes were tested on the electrolyzed water after
electrooxidation by reverse the potential value. The
electrolyzed water was spiked with 50 mg·dm-3 NO3-
and 1 mg·dm-3 NO2-, and the same current density of
25 mA·cm-2 was applied.
Under these conditions, no electroreduction of Fig. 4. Nitrogen compounds profile during the electrolysis
nitrate occurred, which led to apply a higher current time at the current density of 25 mA cm-2:1-nitrate; 2-
density of 50 mA·cm-2 and the results are gathered in nitrite and 3- ammonium
Table 2. It can be observed that an effective
3.3. Comparative assessment of BDD-based
reduction of nitrite occurred while only a low
electrochemical oxidation and reduction processes
efficiency for nitrate reduction (29%) was achieved,
for NC removal
probably due to occurring of a significant side
process of hydrogen evolution.
Based on the results reached for each applied
During the electroreduction process,
electrochemical process gathered in Table 3, a
ammonium was identified, but at the concentration
comparative assessment regarding the nitrogen
much lower in comparison with theoretical calculated

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 Boron-doped diamond electrode-based advanced treatment methods for drinking water

compounds removal from water was performed in 4. Conclusions

order to select or combine them within a certain
technological water treatment flow. In comparison
with the electrooxidation process, the performance of
electroreduction process is lower and characterized
by high energy consuming, which limits its real use
from economic point of view.
Based on these promising results regarding
BDD applying in the electrochemical oxidation
process, this should be integrated within the drinking
water treatment flow in direct relation with the water
source, groundwater and surface water.
Thus, the integration place of the
electrooxidation process within the drinking water
treatment flow is evidenced in Fig. 5.
Table 2. Evolution of electro-reduction process (i=50 mA·cm-2) of nitrate and nitrite
Boron-doped diamond electrode is a very
promising electrode suitable for electrooxidation and
electroreduction processes, regarded as alternative
processes in drinking water treatment flow
characterized by low capacity.
Boron-doped diamond-based electrochemical
oxidation process has proven to be an efficient and
versatile method suitable for various natural organic
matters (NOM) present in drinking water sources.
Also, nitrogen compounds in forms of nitrite and
ammonium can be oxidized simultaneously with
NOM by this technique, this process being efficient
for nitrite and ammonium removal from drinking
water.

Q/V t Wsp ConcNO2 ηNO2 ConcNO3 ηNO3 ConcNH4

Q [Ah] U [V]
[Ah/dm3] [min] [kWh/m3] [mg/L] [%] [mg/L] [%] [mg/L]
0 0 0 0 0 1.35 46.3 0.013
42 60 30 12.5 750 0.47 65 32.9 29 0.068
84 120 60 12.6 1512 0.18 87 32.9 29 0.068
126 180 90 12.7 2286 0.18 87 32.9 29 0.065
168 240 120 13.1 3144 0.18 87 32.9 29 0.062

Table 3. Process assessment parameters for NC electro-oxidation and electro-reduction on BDD electrodes

Electrochemical
Time [min] Wsp [kWh/m3] ηNO2 % ηNO3 % ηNH4 %
process
21.4 2 44 77
42.8 5 83 - 77
64.2 9 87 - 82
Electrooxidation
85.6 15 87 - 81
107 21 87 - 83
128.4 33 87 - 89
30 750 65 29 -
60 1512 87 29 -
Electroreduction
90 2286 87 29 -
120 3144 87 29 -

Fig. 5. The integration place of the electrooxidation process within the drinking water flow, in direct relation with the water
source, groundwater (a) and surface water (b).

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 Manea et al./Environmental Engineering and Management Journal 13 (2014), 9, 2167-2172
However, the application of BDD-based
electrooxidation process is limited due to the nitrate
formation as oxidation product for nitrate containing
drinking water source. BDD-based electroreduction
process is not an efficient method for nitrate removal,
even if it allowed nitrite reduction but with high
energy consumption.
Based on the above presented results, two
types of BDD-based electrooxidation step integrated
into the drinking water treatment flows in direct
relation to the drinking water sources were proposed
as alternative of the advanced treatment to the
conventional drinking water treatment flow.
Acknowledgements
The research presented in this paper was partially
supported by the IZERZO-142210/1(24RO-CH-
RSRP_01.01.2013) and PNII-60/2012 (WATUSER)
projects.
References
Alfaro M.A.Q., Ferro S., Martinez-Huitle C.A., Vong
Y.M., (2006), Boron doped diamond electrode for the
wastewater treatment, Journal of the Brazilian
Chemical Society, 17, 227–236.
Carter K.E., Farrell J., (2008), Oxidative Destruction of
Perfluorooctane Sulfonate Using Boron-Doped
Diamond Film Electrodes, Environmental Science &
Technology, 42, 6111–6115.
Fujishima A., Einaga Y., Rao T.N., Tryl D.A., (2005),
Diamond electrochemistry, Elsevier, Amsterdam.
Kraft A., (2007), Doped diamond: A compact review on a
new, versatile electrode material, International
Journal of Electrochemical Science, 2, 355-385.
Joseph L., Flora J.R.V., Park Y.-G., Badawy M., Saleh H.,
Yoon Y., (2012), Removal of natural organic matter
from potential drinking water sources by combined
coagulation and adsorption using carbon
nanomaterials, Separation and Purification
Technology, 95, 64–72.
Lacasa E., Llanos J., Canizares P., Rodrigo M.A., (2012),
Electrochemical denitrificacion with chlorides using
DSA and BDD anodes, Chemical Engineering
Journal, 184, 66–71.
2172
Massaï H., Loura B.B., Ketcha M.J., Chtaini A., (2009),
Study of Electrocatalytical Reduction of Nitrate on
Copper Electrode, Portugaliae Electrochimica Acta,
27, 691-698.
Matilainen A., Sillanpää M., (2010), Removal of natural
organic matter from drinking water by advanced
oxidation processes, Chemosphere, 80, 351–365.
Militaru C.M., Line A., Barna L., Todinca T., (2013),
Bentonite synthetic water behavior during
coagulation-flocculation process, Environmental
Engineering and Management Journal, 12, 943-950.
Motheo A.J., Pindeho L., (2000), Electrochemical
degradation of humic acid, Science of The Total
Environment, 256, 67-76.
Mousavi S.A.R., Ibrahim S., Aroua M.K., (2011), Ghafari
S., Bio-electrochemical denitrification -A review,
International Journal of Chemical and Environmental
Engineering, 2, 140-146.
Orescanin V., Kollar R., Nad K., (2011), The
electrocoagulation/advanced oxidation treatment of the
groundwater used for human consumption, Journal of
Environmental Science and Health, Part A:
Toxic/Hazardous Substances and Environmental
Engineering, 46, 1611–1618.
Orha C., Pop A., Tipomut V., Manea F., (2013), Composite
material based on silver-doped zeolite and multi-wall
carbon nanotubes for humic acid removal,
Environmental Engineering and Management Journal,
12, 917-921.
Panizza M., Cerisola G., (2005), Application of diamond
electrodes to electrochemical processes,
Electrochimica Acta, 51, 191-199.
Pérez G., Ibáñez R., Urtiaga A.M., Ortiz I., (2012), Kinetic
study of the simultaneous electrochemical removal of
aqueous nitrogen compounds using BDD electrodes,
Chemical Engineering Journal, 197, 475–482.
Segneanu A.E., Bandas C., Grozescu I., Cziple F., Slavici
T., Sfirloaga P., (2013), Hybrid materials for the
removal of organic compounds from water,
Environmental Engineering and Management Journal,
12(5), 1071-1077.
Vlaicu I., Pop A., Manea F., Radovan C., (2011),
Degradation of humic acid from water by advanced
electrochemical oxidation method, Water Science and
Technology: Water Supply, 11, 85-95.
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