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Manganese removal from groundwater: Characterization of filter media

coating

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DOI: 10.1080/19443994.2014.927802

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Manganese removal from groundwater:

characterization of filter media coating
abc b b bd
Jantinus H. Bruins , Branislav Petrusevski , Yness M. Slokar , Joop C. Kruithof & Maria D.
bc
Kennedy
a
WLN, Rijksstraatweg 85, 9756 AD, Glimmen, The Netherlands, Tel. +31 (0)50 4022121;
Fax: +31 (0)50 4094274
b
UNESCO-IHE Institute for Water Education, Westvest 7, 2611 AX, Delft, The Netherlands,
Tel. +31 (0)15 2151785, Tel. +31 (0)6 2151826, Tel. +31 (0)15 2151774; Fax: +31 (0)15
21222921
c
Technical University Delft, Stevinweg 1, 2628 CN, Delft, The Netherlands
d
Wetsus, Centre of Excellence for Sustainable Water Technology, P.O. Box 1113, 8900 CC,
Leeuwarden, The Netherlands
Published online: 18 Jun 2014.

To cite this article: Jantinus H. Bruins, Branislav Petrusevski, Yness M. Slokar, Joop C. Kruithof & Maria D. Kennedy (2014):
Manganese removal from groundwater: characterization of filter media coating, Desalination and Water Treatment, DOI:
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 Desalination and Water Treatment (2014) 1–13
www.deswater.com

doi: 10.1080/19443994.2014.927802

Manganese removal from groundwater: characterization of filter media

coating

Jantinus H. Bruinsa,b,c,*, Branislav Petrusevskib, Yness M. Slokarb, Joop C. Kruithofb,d,

Maria D. Kennedyb,c
a
WLN, Rijksstraatweg 85, 9756 AD, Glimmen, The Netherlands, Tel. +31 (0)50 4022121; Fax: +31 (0)50 4094274;
email: [email protected] (J.H. Bruins)
b
UNESCO-IHE Institute for Water Education, Westvest 7, 2611 AX, Delft, The Netherlands, Tel. +31 (0)15 2151785;
email: [email protected] (B. Petrusevski), Tel. +31 (0)6 2151826; email: [email protected] (Y.M. Slokar),
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

Tel. +31 (0)6 53165153; email: [email protected] (J.C. Kruithof), Tel. +31 (0)15 2151774; Fax: +31 (0)15 21222921;
email: [email protected] (M.D. Kennedy)
c
Technical University Delft, Stevinweg 1, 2628 CN, Delft, The Netherlands
d
Wetsus, Centre of Excellence for Sustainable Water Technology, P.O. Box 1113, 8900 CC, Leeuwarden, The Netherlands
Received 6 February 2014; Accepted 20 May 2014

ABSTRACT

Removal of manganese in conventional aeration-filtration groundwater treatment plants

(GWTPs) results in the formation of a manganese oxide coating on filter media. The forma-
tion of this coating is an essential prerequisite for efficient manganese removal. Different
manganese oxides have varying affinities for autocatalytic adsorption/oxidation of dis-
solved manganese. The aim of this study was to characterize manganese oxide(s) on filter
media from successfully operating manganese removal plants. Characterization of filter
media samples from full-scale groundwater treatment plants and identification of manga-
nese species was carried out by X-ray diffraction, scanning electron microscopy coupled
with energy dispersive X-radiation (SEM-EDX), Raman spectroscopy and electron paramag-
netic resonance (EPR). The results showed that the manganese oxide present in the aged
coating was poorly crystalline. Results from the Raman spectroscopy and the detailed EPR
analysis show that the manganese oxide in the ripened coating was of a Birnessite type,
and of physicochemical origin. The results transpiring from this research suggest that the
presence of Birnessite in the coating is essential for effective manganese removal in conven-
tional aeration-filtration treatment plants, since Birnessite has a considerable ability to
adsorb and oxidize dissolved manganese.

Keywords: Groundwater treatment; Manganese removal; MOCS; Filter media characterization;

Birnessite

*Corresponding author.

1944-3994/1944-3986 Ó 2014 Balaban Desalination Publications. All rights reserved.

 2 J.H. Bruins et al. / Desalination and Water Treatment

1. Introduction possibility of further oxidation. The valences of man-

ganese oxides shown in Fig. 1 are given in Table 1.
1.1. General
In nature, the most stable form of manganese oxide
Groundwater is the most abundant source for is Pyrolusite (βMnO2). Because the valence of manga-
drinking water production, representing over 90% of nese in this oxide is 4, no further oxidation can take
the world’s readily available freshwater. About 1.5 bil- place. Pyrolusite has a large adsorption capacity, but
lion people depend upon groundwater for their drink- no autocatalytic oxidative properties [6]. Conse-
ing water supply [1]. In addition to iron and quently, when the adsorption capacity is exhausted,
ammonium, groundwater frequently contains elevated the removal of manganese stops.
concentrations of dissolved manganese, which should Pyrolusite is formed when (powerful) oxidants
be lowered for both health and aesthetic reasons. In such as chlorine (Cl2), chlorine dioxide (ClO2), ozone
European countries, the removal of manganese from (O3) or potassium permanganate (KMnO4) are used.
groundwater is commonly achieved by aeration-rapid These oxidants are commonly applied in countries
sand filtration, eliminating the need for oxidant to such as the USA [19,20]. Pre-oxidation with powerful
enhance manganese oxidation. This type of manganese oxidants can achieve a very effective manganese
removal is effective and beneficial for both environ- removal. However, this type of process is associated
mental and economic reasons, but requires a long rip- with disadvantages such as continuous oxidant dosage
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ening period of virgin filter media. The ripening time to achieve manganese removal. This process is also
can last from several weeks to more than a year, associated with high costs and environmental risks,
before effective manganese removal is achieved [2–4]. and requires accurate oxidant dosage: under dosing
Although extensive research has been carried out causes incomplete manganese oxidation, and conse-
on manganese removal by aeration-rapid sand filtra- quently a poor manganese removal, while overdosing
tion, the mechanisms controlling the ripening period, with permanganate gives the water a pinkish colour.
including the formation of a manganese oxide coating Therefore in Western European countries, such as The
on virgin filter media, are still not well understood. Netherlands, manganese removal by conventional
Several researchers have suggested that the use of groundwater treatment with aeration-filtration is
(pre)coated or (“bio”) aged filter media can shorten preferred.
the ripening period [5–15]. Aged filter media in man- Based on thermodynamic considerations, the fol-
ganese removal filters typically consists of manganese lowing pathway for manganese oxidation in water is
oxide-coated sand (MOCS) and/or manganese oxide- proposed: (Pyrochroite)—Hausmannite—Manganite—
coated anthracite (MOCA). Autocatalytic properties Pyrolusite [21,22]. However, based on the pε/pH dia-
that are attributed to the coating of these filter media gram shown in Fig. 2 [16], chemical formation of Pyro-
enhance the adsorption of dissolved manganese and chroite (Mn(OH)2) under common groundwater
its subsequent oxidation. The ripening time of filter conditions (pH 6–8) is unlikely. Without a catalyst, the
media is controlled by the type and amount of manga- pH must be at least 8.6 to achieve Hausmannite
nese oxide(s) present in the coating. As proposed by (Mn3O4 formation), which is subsequently removed by
Stumm and Morgan [16], oxidation of manganese in filtration [21]. Formation of Pyrochroite requires an
homogeneous aqueous solution follows different path- even higher pH, of at least 11.
ways, as shown in a simplified scheme (Fig. 1). The exact pathway by which manganese oxidation
The propensity of manganese present in filter occurs under conditions commonly applied in ground-
media coating heavily depends on the valence of man- water treatment, is not known. Besides chemical oxi-
ganese in the oxide [17]. A higher valence restricts the dation, “biology” may play an important role.

Fig. 1. Simplified scheme of Mn2+ oxidation pathways according to Stumm and Morgan [16].
 J.H. Bruins et al. / Desalination and Water Treatment 3

Table 1 present in ripened media from manganese removal fil-

Types of manganese oxide and the average valence of ters may help to better understand the driving force
manganese in these oxides behind efficient manganese removal in conventional
Manganese oxide Valence of manganese
aeration-filtration groundwater treatment plants.

Pyrochroite 2 [16]
Hausmannite ~2.7 [17] 2. Materials and methods
Manganite/Feitknechtite 3 [17]
Buserite/Birnessite 3.5–3.9 [18] MOCS and MOCA characterized in this study
Nsutite ~4 [17] were collected from two GWTPs of two water compa-
Pyrolusite 4 [17] nies as follows.

MOCS from GWTP De Punt (Groningen, The

Netherlands).

The sample was taken from a depth of 140–150 cm,

from a filter bed that was removed after an operating
time of approximately 15 years.
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MOCA from GWTP Grobbendonk (Pidpa, Bel-

gium).

The sample was taken from the top of a filter bed,

in operation for more than 12 years.
Both GWTPs utilize conventional groundwater
treatment by aeration-filtration and achieve complete
manganese removal. Information on feed water qual-
ity, process design parameters and operational condi-
tions of full-scale plants De Punt and Grobbendonk
are shown in Table 2.
To characterize the filter media coatings and to
Fig. 2. Diagram of electron activity (pε) and redox poten-
tial (Eh in V) as a function of the pH showing the stability
identify the manganese oxide(s), the following supple-
zones of manganese-containing compounds in aqueous mentary techniques were used:
solution.
Source: adopted from Stumm and Morgan [16].
Raman spectroscopy;

X-ray diffraction (XRD);
Identification of the manganese oxide(s) present in fil-
Scanning electron microscopy coupled with
ter media coatings from manganese removal filters energy dispersive X-radiation analysis (SEM-
might give insight into the formation of manganese EDX); and
oxide coatings on virgin filter media. This may eluci-
Electron paramagnetic resonance (EPR).
date the mechanisms controlling the start-up of the
manganese removal process [23]. Based on these As these techniques are supplementary, for com-
results, recommendations for process modifications to plete identification and determination of the origin of
shorten the ripening period of manganese removal produced MnOx, application of all these methods is
filters may be made. required. Use of one single method is insufficient to
characterize and identify the manganese oxides.
For additional information with respect to Raman
1.2. Aim of this study spectroscopy (selection spectroscopy settings—Sec-
tion 3.1) and SEM-EDX (measuring trace (counter) ele-
The aim of this study was to characterize the coat- ments) Section 3.3), additional MOCS samples from
ing of MOCS and MOCA from (ripened) manganese post filters of two other plants were used, as follows.
removal filters in full-scale groundwater treatment
plants (GWTPs), by identification of the types of man-
MOCS from GWTP Onnen (Groningen, The
ganese oxide present in the coating. It was hypothe- Netherlands).
sized that identification of the manganese oxide
 4 J.H. Bruins et al. / Desalination and Water Treatment

Table 2
Feed water quality, process design parameters and operational conditions of full scale GWTP De Punt and GWTP Grob-
bendonk

Parameters feed water/technical information filter Unit De Punt Grobbendonk

Iron mg/L 4.5–6.9 0.03–0.14
Manganese mg/L 0.18–0.25 0.12–0.18
Ammonium mg/L 0.29–0.78 <0.05–0.23
pH [−] 7.3−7.5 7.5–7.6
Oxygen mg/L 8–10 >10
Redox potential mV −50 to +50 +200 to +300
Type of aeration – spray cascade
Position of filter – pre-filter post-filter
Type of filtration – down flow down flow
Type of filter media – quartz sand anthracite/quartz sand
Grain size fraction virgin media mm 1.8–2.4 0.8–1.8/0.4–0.8
Filter area m2 12.5 37.5
Filter bed height m 2 1.1 (0.6 + 0.5)
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

Flow per filter m3/h 60 190

Filtration rate m3/m2h 4.8 5.0
Empty bed contact time min 25 13.2
Backwash (BW) criterion - head loss head loss
Backwash frequency n/week 2 0.5
Filter bed expansion during BW – no yes (anthracite)
Filtered volume between BW m3 per filter run 5,000–7,000 10,000
Iron loading per filter run (FR) kg Fe/m2FR 2.5 <0.1

The sample is taken from the top of the filter, in

operation for more than 40 years. Table 3
Parameter settings for Raman spectroscopy analysis

MOCS from GWTP Wierden (Vitens, The Neth-
erlands). Parameter Setting
Exposure ≥30 s
The sample is taken from the top of the filter, in Current 0.05 mA
operation for more than 18 years. Confocal hole 1,000 μm
Slit 100 μm
Laser wave length 532.13 nm
2.1. Raman spectroscopy Grating 600
Objective x50
With Raman spectroscopy it is possible to distin-
Density filter D3
guish different (general) types of manganese oxides. Detector Synapse CCD
For the Raman spectroscopy analysis a Horiba Jobin Detector size 1,024 pixels
Yvon Labram instrument was used with the following
settings (Table 3).
Exposure of the samples to high power laser radia-
tion (5 mA) during Raman analysis for a long time
(>120 s) may change the structure of the manganese 2.2. XRD
oxides. However, under the applied conditions XRD can be used to determine whether manganese
(Table 3), no structural damage was detected during oxide is crystalline or amorphous. Furthermore, this
the tests. Detailed information on the effect of high technique can provide additional information to clarify
power radiation on structural changes of the manga- the sharpness of the peaks found with Raman spectros-
nese oxides is given in Section 3.1. Before analysis, the copy. Most XRD measurements were carried out with
samples (either the integral grain or powder coating) a Bruker-D8 Advance diffractometer in Bragg-Brentano
were dried at room temperature to avoid excessive focusing geometry. The instrument was equipped with
fluorescence caused by the presence of water in the a Vantec PSD detector. Measurements were carried out
samples. at room temperature with the use of monochromatic
 J.H. Bruins et al. / Desalination and Water Treatment 5

CoKα1 radiation (λ = 0.179026 nm). The 2θ scan was EPR analyses were carried out with a Bruker
made in the range 10–110˚2θ, using a step size of instrument operating at 9.46 GHz (W-waveband). The
0.038˚2θ. To check some of the analyses and to enhance analyses were carried out at two different tempera-
their performance, some XRD measurements were also tures, i.e. at 77 K (cooled with nitrogen) and 298 K
carried out with a Bruker-AXS D5005 diffractometer in (room temperature).
Bragg-Brentano focusing geometry, equipped with a
graphite monochromator in the diffracted beam. Before
analysis, the samples were dried at room temperature 3. Results and discussion
and then pulverized to a size of 10–50 μm. The sample 3.1. Raman spectroscopy
powder (for MOCS only the coating and for MOCA
the coating including the anthracite grain) was put in 3.1.1. Selection Raman spectroscopy settings
an aluminium sample holder. The 2θ scan was made in As explained in Section 2.1, the structure of
the range 10–110˚2θ, using a step size of 0.025˚2θ and a almost all manganese (oxide) compounds (except
counting time of 2 s per step. The radiation was CuKα1 Hausmannite) is subjected to Raman spectroscopic
(0.15406 nm). Results obtained by both the XRD instru- changes when exposed to a high current [24,25].
ments were evaluated with the internal Bruker EVA Laser irradiation in excess of 5 mA for longer than
software. 120 s causes structural changes of the exposed com-
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

pounds (polymorphism). To prevent these changes,

the current of the laser in this study was limited to
2.3. SEM-EDX
0.05 mA. The differences in spectra obtained with
SEM pictures show the structure of the coating high (5 mA, >120 s) and low (0.05 mA) radiation
and the manganese oxide inside. In addition, EDX intensities are shown in Fig. 3.
provides information about the trace (counter) ele- From the two spectra in Fig. 3 it can be seen that
ments present in these structures. Therefore, differ- high intensity laser irradiation changes the position of
ences in peak ratio found with Raman spectroscopy the peaks, as well as the pattern of the spectrum.
can be clarified. The SEM pictures were made with a According to [24,25], high current irradiation trans-
JEOL-6480LV. Samples (either the integral grain or forms all MnOx samples (and therefore also Birnessite)
powder coating) were placed on 15 mm diameter into Mn3O4 (Hausmannite). Hausmannite is very sta-
mounts with a double-sided carbon adhesive tab. The ble when exposed to a Raman laser, so its structure is
SEM was operated both under High Vacuum (HV) not changed by the high level of irradiation. Further-
and Low Vacuum (LV) conditions. more, due to its crystalline lattice structure it displays
Before observation under HV conditions, the sam- a sharp peak in the Raman spectrum. To ascertain this
ples were coated in a JEOL JFC-1200 fine coater with a transformation, Raman profiles of Birnessite from this
thin (10 nm) Au layer. The operation under HV condi- study and an MnO2 reference sample (Alfa Aesar)
tions was done at 6 kV at 10 mm Working Distance were exposed to high current radiation (5 mA, >120 s),
(WD) and Spot Size (SS) 20. Samples were also investi- and compared to a Hausmannite spectrum from the
gated without Au coating under LV conditions at 10 RRUFF database [26] (Fig. 4).
kV and SS 60. Composition of the adsorbed coating
layers was determined with an X-ray microanalysis
(EDX) System type Noran System SIX from the
Thermo Electron Corporation. Analyses were done at low radiation
10 kV and SS 70 for both the Au-coated samples at high radiation

HV conditions and non-coated samples at LV condi-

tions. In the latter, no Au peaks were observed in the
EDX spectrum.

2.4. EPR
Once the MnOx is characterized as “a type of 200 400 600 800 1000 1200
Raman shift (cm-1)
Birnessite”, EPR can be employed to identify the exact
type of Birnessite and additionally also to determine
the origin of the Birnessite. For EPR the whole grain Fig. 3. Raman spectra at 532 nm of MOCS (Onnen),
was always used. exposed to low (grey line) and high laser radiation (black
line).
 6 J.H. Bruins et al. / Desalination and Water Treatment

MOCS De Punt
MOCA Grobbendonk
MOCS Wierden
MOCS Onnen

200 400 600 800 1000 1200

200 400 600 800 1000 1200 Raman shift (cm-1)

Raman shift (cm-1)

Fig. 5. Raman spectra (at 532 nm) of the four MOCS/
Fig. 4. Raman spectra (at 532 nm) of Birnessite from a sam- MOCA samples.
ple of this study (light grey line) and MnO2 reference
(black line) after exposure to 5 mA for >120 s, compared to Hasserode, the Harz Mountains, Sachsen-Anhalt,
a Hausmannite spectrum (dark grey line) from the RRUFF Germany [29].
database [26]. Fig. 6(B) shows that the main peaks from the Bir-
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

nessite reference as well as the MOCA and MOCS

From Fig. 4, it can be seen that the spectra of samples were on the same Raman shift. Only the ratio
Birnessite in a sample from this study as well as and height of the peaks varied between the different
the MnO2 reference, exposed to high laser radiation, samples and the reference, probably due to a different
show a close resemblance to the spectrum of concentration of counter ions in the materials [24,25],
Hausmannite. This indicates that both manganese as shown by SEM-EDX (Section 3.3, Table 4).
oxides (Birnessite and MnO2) underwent structural The Raman spectra strongly suggested that the
changes when exposed to high laser power, as sta- manganese oxides in the MOCA and MOCS samples
ted by [25]. were of a Birnessite type.
In order to exclude the presence of other manga-
nese oxides in the coatings, the Raman spectra of sam-
3.1.2. Characterization of MOCA and MOCS by ples from this study were compared with the
Raman spectroscopy reference spectra of four other manganese oxides
The Raman spectra of manganese-coated samples Pyrochroite (A), Hausmannite (B), Manganite (C) and
from four GWTPs are presented in Fig. 5. From Fig. 5, Pyrolusite (D) (Fig. 7). Spectra A-C were taken from
it can be seen that the spectral patterns of all samples the RRUFF database [26] and spectrum D from the
were similar, indicating a similar type of manganese measured reference sample (Alfa Aesar).
oxide. The three most pronounced absorbance peaks The four manganese oxides displayed one peak in
were found at Raman shifts of 495–505, 570–575 and the same region as the MOCS/MOCA samples
635–655 cm−1, typical for the Birnessite group of man- between 630 and 650 cm−1. This wavelength is charac-
ganese oxides [24]. All spectra exhibited a less pro- teristic for all manganese oxides and not indicative of
nounced peak at a Raman shift at 400–420 cm−1. The a particular one. Therefore, it was concluded that
undulating peaks were typical for oxides with a apart from Birnessite no other manganese oxides were
poorly crystalline structure, such as Birnessite [27]. present in the coating of the filter media.
To confirm the presence of Birnessite, the spectra
of the MOCS/MOCA samples were compared with 3.2. XRD
the spectra of synthetically produced Birnessite [28],
shown in Fig. 6(A). Comparison of the spectra pro- Fig. 8 shows an XRD spectrum of MOCS coating
duced in this study with previously reported results from GWTP De Punt (black line) and a MOCA coating
strongly suggested that the manganese oxide in the from GWTP Grobbendonk (grey line). The analysed
coating of the MOCS and MOCA samples was of a MOCA sample contained some crushed anthracite
Birnessite type. (carbon) since it was impossible to separate the coat-
The spectra of MOCS and MOCA samples were ing completely from the anthracite.
also compared with a Raman profile of a reference From Fig. 8 it can be seen, as already shown by
sample of naturally formed Birnessite (Fig. 6(B)), the Raman spectroscopy that the MOCS coating was
obtained from the Aufgeklärt Glück mine in poorly crystalline. The only peak (31˚, 2θ) belonged to
 J.H. Bruins et al. / Desalination and Water Treatment 7

(A)

(B)

200 300 400 500 600 700 800 900

Raman shift (cm-1)

Fig. 6. (A) Raman spectra of synthetically produced Birnessite at 514 nm [28]. (B) Raman spectra of samples from this
study (grey lines) compared to the spectrum of the Birnessite reference (bold black line).
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

Table 4
SEM-EDX analysis of counter (trace) elements in weight (%)

MOCA Grobbendonk MOCS De Punt MOCS Onnen MOCS Wierden

Aluminium (Al) 0.5 <0.1 0.6 <0.1
Calcium (Ca) 6.8 2.3 7.2 7.7
Magnesium (Mg) 0.3 <0.1 0.4 0.3
Potassium (K) 0.2 <0.1 <0.1 <0.1
Silica (Si) 1.0 5.9 2.6 0.9
Sodium (Na) <0.1 <0.1 0.2 <0.1

MOCS
(A) MOCA (B) MOCS
MOCA
Pyrochroite (RUFF)
Hausmannite (RUFF)

200 400 600 800 1000 1200 200 400 600 800 1000 1200
Raman shift (cm-1) Raman shift (cm-1)

(C) (D)
MOCS MOCS
MOCA MOCA
Manganite (RUFF) Pyrolusite (Alfa Aeser)

200 400 600 800 1000 1200 200 400 600 800 1000 1200
Raman shift (cm-1) Raman shift (cm-1)

Fig. 7. Raman spectra at low power and 532 nm of MOCS De Punt and MOCA Grobbendonk, compared to (A) Pyrochro-
ite, (B) Hausmannite, (C) Manganite and (D) Pyrolusite.
 8 J.H. Bruins et al. / Desalination and Water Treatment

coating of MOCS (De Punt) manganese oxide(s) in the MOCS and MOCA samples
MOCA (Grobbendonk)
were not crystalline manganese oxides (i.e. MnO2,
Mn2O3 or MnO).

3.3. SEM-EDX
In Fig. 10a SEM image of virgin quartz (sand) filter
media is shown. Fig. 10 shows that the surface of
20 30 40 50 60 70 80 virgin sand was not completely smooth, indicating a
2-theta high porosity and specific surface area, and therefore
probably contained many sites for attachment of bac-
Fig. 8. XRD spectra (conducted with a Bruker D8), of pul- teria and/or manganese, which could shorten the rip-
verized MOCS coating and MOCA (the latter including ening time.
crushed anthracite core). In Fig. 11 SEM images of MOCS and MOCA sam-
ples are shown.
silica originating from the filter media. Additional Images A and B in Fig. 11 confirm the Raman
spectroscopy results and the XRD analysis that the
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

(sharp) peaks were not present in the spectra from the

MOCS sample, so no crystalline MnOx was present on manganese coating was poorly crystalline.
the MOCS. Also, no crystalline MnOx was found on Results of the SEM-EDX analyses show that apart
the MOCA. The few small peaks and the broad peak from manganese and iron, the coating of the filter
in the MOCA sample (25˚, 2θ) originate from carbon media contained (trace) elements such as aluminium,
or graphite (C) from crushed anthracite, that could not calcium, magnesium, potassium, sodium and/or silica
be removed completely from the coating (as men- (Table 4).
tioned above). The counter (trace) elements in Table 4 are of
For comparison, the XRD spectra of three Alfa Ae- importance with respect to the ratio and height of the
sar reference manganese oxides i.e. MnO2, Mn2O3 and Raman peaks, as discussed in Section 3.1 and shown
MnO with crystalline structure are presented in Fig. 9. in Fig. 6(B). Counter ions present in filter media coat-
Contrary to the MOCA and MOCS coating, the ings may also impact the adsorptive properties of the
XRD spectra of the three reference manganese oxides coating.
showed sharp peaks and the 2θ positions of the peaks
were confirmed by the reference XRD spectra of oxi-
des from the internal Bruker EVA database. If the 3.4. EPR
manganese oxide in the samples from this study had In Fig. 12 the EPR spectra of MOCS De Punt mea-
been crystalline, sharp peaks should have been sured at two temperatures (298 K—room temperature
observed similar to the spectra of the three reference
manganese oxides. The absence of sharp peaks con-
firmed the amorphous character of the sample coating.
Thus, the XRD results also confirmed that the

MnO Mn2O3 MnO2

20 30 40 50 60 70 80 90 100
2-theta

Fig. 9. XRD spectra of reference manganese oxides: MnO, Fig. 10. SEM image of virgin quartz media (sand); 500×
Mn2O3 and MnO2 (Alfa Aesar). magnification.
 J.H. Bruins et al. / Desalination and Water Treatment 9

Fig. 11. SEM images of filter media coating. (A) MOCS De Punt; 10,000×. (B) MOCA Grobbendonk; 5,000×.
Downloaded by [Jantinus H. Bruins] at 06:05 21 June 2014

Fig. 12. EPR spectra of MOCS De Punt.

Notes: Top half: spectra measured at 298 K (grey line) and 77 K (black line). Bottom half: expanded spectrum measured
at 77 K.

and 77 K) are shown. Due to the analytical interfer- possible to obtain a complete EPR spectrum for
ence of carbon (originating from anthracite), it was not MOCA Grobbendonk.
 10 J.H. Bruins et al. / Desalination and Water Treatment

The detailed EPR pattern (Fig. 12, the bottom half) 3.5. The importance of Birnessite formation on MOCA/
shows the “6 line hyperfine structure of manganese”. MOCS for manganese removal
This pattern is typical for oxides containing manganese
The mineral Birnessite was found in 1956 in a
ions with a different valence, including Mn2+ [30].
small hamlet called Birness, Scotland, UK [32]. At that
Birnessite has a valence between 3.5 and 3.9 [18,27,31],
time it was a new mineral to which the name Birnes-
due to the presence of Mn3+ and Mn4+ in the lattice.
site, after the locality, was given. Its molecular struc-
This pattern is an additional indication that the pre-
ture was given as (Na0.7Ca0.3)Mn7O14.2.8H2O. In time,
dominant manganese component of the MOCS coating
different formulas were proposed for Birnessite, indi-
is a manganese oxide, containing manganese ions with
cating there is no single structure, but different com-
different oxidation numbers, such as Birnessite.
positions exist (“minerals of the Birnessite type”).
Generally, EPR spectra are characterized by two
From this study, it can be observed that Birnessite was
parameters: (i) the line width: ΔH in gauss and (ii) the
the manganese compound formed during filter ripen-
spectroscopic splitting factor: g (g-factor). EPR was
ing, and predominantly present in all manganese
used to investigate the origin of different types of
oxide coatings extracted from the four GWTPs that
Birnessite [31]. These values of ΔH measured at 77
showed complete manganese removal. Consequently,
and 298 K and the g-factor calculated at 298 K are
Birnessite appears to be of particular importance for
characteristic of Birnessite.
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manganese removal in conventional aeration-filtration

ΔH is measured as the distance between the high-
groundwater treatment plants. The presence of Birnes-
est and lowest point of the signal wave, and the g fac-
site may provide an explanation for the very effective
tor is calculated from the spectrometer microwave
manganese removal in these filters in practice. Birnes-
frequency (y) and the magnetic field (H0) applied dur-
site is extremely suitable to remove manganese,
ing the analysis when the signal is zero (Eq. 1):
because of its structure as described by Post [27]: “the
Birnessite group of minerals has layered structures,
h y which may readily undergo oxidation-reduction and
g¼  (1)
lB H0 cation-exchange reactions and play a major role in
controlling groundwater chemistry”. The high cation
where exchange and adsorption capacity of Birnessite is also
h = Planck constant (6.62 × 10−34 Js); described by several other researchers [10,33–39].
μB = Bohr magneton (9.27 × 10−28 J/G); Thus, Birnessite is very suitable to adsorb Mn2+.
y = spectrometer microwave frequency (GHz); The Birnessite group of minerals (including Buse-
H0 = applied magnetic field where signal is zero rite) is also important, because of its high reactivity
(gauss). [27,40]. In Buserite and Birnessite the average valence
ΔH values measured at 298 and at 77 K were number of manganese ranges from +3.5 to +3.9 [18].
2,642 gauss and 3,950 gauss, respectively (Fig. 12—top Although restricted compared to other manganese oxi-
half). Taking into account the applied magnetic field des, further oxidation of Buserite and Birnessite is still
(H0) of 3,455 gauss at 298 K, the calculated g factor possible. The combination of properties makes Birnes-
was 1.956. Comparing the EPR results from this study site a highly reactive manganese oxide, with very
with the data reported by [31], a few conclusions can good adsorptive properties for dissolved manganese,
be drawn. Firstly, the EPR analysis confirmed the and its subsequent autocatalytic oxidation. The knowl-
results obtained by Raman spectroscopy that the man- edge that Birnessite is the manganese oxide responsi-
ganese oxide on MOCS is Birnessite. Next, comparing ble for efficient manganese removal can help
the two ΔH values and the g factor with the results substantially accelerate the ripening process of virgin
from [31] shows that the Birnessite in the coating of filter media, by creating conditions favouring the
MOCS De Punt was of physicochemical origin. How- formation of Birnessite. Knowing that the oxidation
ever, this does not mean that the growth of manga- from Mn2+ into Pyrolusite [16], via Birnessite (Pyro-
nese oxide on the virgin filter media (ripening chroite → Buserite/Birnessite → Nsutite → Pyrolusite,
process) starts exclusively chemically. The MOCS sam- Fig. 2), is only possible under (very) alkaline condi-
ple from GWTP De Punt was taken after more than tions [41], it is not likely that a fast filter ripening of
15 years of operation, and consequently the EPR anal- virgin filter media starts in a chemical way, without
ysis only confirmed the physicochemical nature of Bir- oxidant dosage. Therefore, the formation of the man-
nessite after this elapsed time. ganese coating may be initiated by bacterial activity.
 J.H. Bruins et al. / Desalination and Water Treatment 11

Several researchers have suggested that manganese Science and Engineering from the Technical University
removal is influenced by bacteria (e.g. Pseudomons sp., of Delft for their help with the analyses of samples
Leptothrix sp.), which are able to oxidize Mn2+ [31,42–52]. and interpretation of the results. The authors would
Therefore, the ripening of the filter media probably also like to thank the Belgian water company Pidpa
starts with the biological formation of Birnessite. In and the Dutch water company Vitens for providing fil-
time very fast physicochemical auto-catalytic adsorp- ter media for this study and their willingness to dis-
tion/oxidation reactions may become more important close their groundwater treatment plant data. Finally,
and result in production of Birnessite of physicochem- we would like to thank Dr Thomas Witzke
ical origin, whose presence is shown in this study. (mineralogist) for donating a naturally formed
However, further research is required to support this Birnessite reference sample.
hypothesis.

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