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pubs.acs.org/est

Application of XPS and Solution Chemistry Analyses to Investigate

Soluble Manganese Removal by MnOx(s)-Coated Media
Jose M. Cerrato,†,|| William R. Knocke,*,† Michael F. Hochella, Jr.,‡ Andrea M. Dietrich,† Andrew Jones,† and
Thomas F. Cromer§
†
The Charles E. Via Jr. Department of Civil and Environmental Engineering, Virginia Polytechnic Institute and State University,
Blacksburg, Virginia 24061-0246, United States
‡
Center for NanoBioEarth, Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg,
Virginia 24061-0420, United States
§
Surface Analysis Laboratory, Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg,
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Virginia 24061-0001, United States

bS Supporting Information
ABSTRACT: X-ray photoelectron spectroscopy (XPS) was applied to investigate
Mn(II) removal by MnOx(s)-coated media under experimental conditions similar
to the engineered environment of drinking water treatment plants in the absence
and presence of chlorine. Macroscopic and spectroscopic results suggest that
Mn(II) removal at pH 6.3 and pH 7.2 in the absence of chlorine was mainly due to
adsorption onto the MnOx(s) surface coating, while removal in the presence of
chlorine was due to a combination of initial surface adsorption followed by
subsequent surface-catalyzed oxidation. However, Mn(III) was identified by XPS
analyses of the Mn 3p photoline for experiments performed in the absence of
chlorine at pH 6.3 and pH 7.2, suggesting that surface-catalyzed Mn oxidation also
occurred at these conditions. Results obtained at pH 8.2 at 8 and 0.5 mg 3 L
1
dissolved oxygen in the absence of chlorine suggest that Mn(II) removal was
mainly due to initial adsorption followed by surface-catalyzed oxidation. XPS
analyses suggest that Mn(IV) was the predominant species in experiments operated in the presence of chlorine. This study confirms
that the use of chlorine combined with the catalytic action of MnOx(s) oxides is effective for Mn(II) removal from drinking water
filtration systems.

’ INTRODUCTION
Soluble manganese (Mn) removal through the catalytic action
of MnOx(s)-coated media surfaces combined with the applica-
tion of free chlorine (e.g., HOCl, OCl
) is a very effective water
treatment technique.1
4 Several decades of research have re-
vealed critical aspects of this technique: (a) efficient soluble Mn
removal occurred after Mn-oxide coatings naturally developed in
filter media through a process referred to as “filter aging”4 resulting
in an apparent “natural greensand effect” with the presence of
various oxidants;1,5 (b) effective soluble Mn(II) removal was
accomplished on MnOx(s)-coated media in the absence of an
oxidant because sorption capacity increases with increasing pH or
surface MnOx(s) concentration or both;1,2 (c) the application of
free chlorine together with MnOx(s)-coated media resulted in
effective Mn removal at pH 6 or above, resulting in continuous
“regeneration” of media surface Mn adsorption sites over time;1,2
(d) filter backwashing may have altered the physical and chemical
properties of MnOx(s)-coated media.3,6
Although the research cited above has provided invaluable
information about key factors influencing soluble Mn removal by
MnOx(s)-coated media, the specific mechanisms that affect this
treatment technique are still unknown. Most studies to date have
obtained kinetic information from solution chemistry experi-
mental data; there is limited microscopic and spectroscopic
evidence that can provide a more specific perspective about
possible reaction mechanisms applicable to the context of
drinking water treatment. Extensive biogeochemistry research
performed in natural environmental systems has focused on
biotic and abiotic heterogeneous oxidation reactions on MnOx-
(s) surfaces, reporting the presence of Mn(III), but its role is still
unclear.7
13 More recently, researchers have attempted to link
macroscopic and microscopic analyses to better understand the
role of MnOx(s)-coated media in drinking water treatment.6,14
17
Few investigators have characterized the mineral phase and
oxidation state of MnOx(s)-coated media surfaces. X-ray diffrac-
tion (XRD), a surface analysis technique appropriate for cry-
stalline phases, has also been used to study the mineral phases in
Received: September 16, 2011
Accepted: October 31, 2011
Revised: October 27, 2011
Published: October 31, 2011

r 2011 American Chemical Society 10068 dx.doi.org/10.1021/es203262n | Environ. Sci. Technol. 2011, 45, 10068–10074
Environmental Science & Technology
MnOx(s)-coated media.6,16 However, the applicability of the
results obtained by XRD is limited due to the amorphous and
heterogeneous nature of MnOx(s)-coated media typically used in
drinking water treatment.6,15,16
X-ray photoelectron spectroscopy (XPS) is a well established
surface analysis technique that has been used to determine Mn
oxidation states in minerals.6,7,18
20 Mn(IV) and Mn(III, IV)
oxidation states have been identified in MnOx(s)-coated media
using XPS through the determination of the Mn 3s multiplet
splitting and the shape and position of the Mn 3p photopeak.6,20
Other investigators used the XPS Mn 2p3/2 peak and detected a
mixed Mn(III) and Mn(IV) oxidation state in the surface of Mn-
oxide coated sand21 and in the biological products resulting from
biofiltration.22 However, literature shows that determination of
Mn oxidation states using the XPS Mn 2p3/2 peak is not a
practical approach as the resulting photopeak shifts from differ-
ent oxidation states are so small that it is difficult to detect their
separation.7,23
The objective of this investigation was to better understand
the mechanisms by which soluble Mn-removal by MnOx(s)-
coated anthracite media is accomplished in the absence and
presence of free chlorine. The novel aspect of this study was
to couple carefully controlled mass balance measurements
(obtained during Mn adsorption and subsequent elution studies)
with independent measurements of Mn oxidation states on the
media coating using XPS Mn 3p analyses. Integration of XPS and
solution chemistry analyses allow for more definitive assessments
of the relative role of surface adsorption versus surface-catalyzed
Mn oxidation in the overall removal of soluble Mn observed in
drinking water treatment plants that employ MnOx(s)-coated
filter media.
’ EXPERIMENTAL SECTION
Sample Site. MnOx(s)-coated anthracite media were col-
lected in 500 mL autoclaved polyethylene bottles from the filter
of a drinking water treatment facility in North Carolina. This
conventional water treatment facility utilizes a ferric chloride
coagulant and its filtration system consists of dual-media filter
beds of anthracite and silica sand. Chlorine is applied just prior to
the filtration step for water disinfection and MnOx(s)-coated
media regeneration; the chlorine residual in the filter effluent
typically ranged from 3 to 6 mg 3 L
1.
Laboratory Column Experiments. Column tests were per-
formed to evaluate soluble Mn(II) uptake under experimental
conditions representative of drinking water treatment plants in
the absence and presence of chlorine. A previous investigation
showed that Mn-oxidizing and -reducing microorganisms are
present in filtration media and could potentially affect the fate of
Mn in drinking water treatment plants.24 Particles of MnOx(s)-
coated anthracite media obtained from the North Carolina
facility were soaked in a 100 mg 3 L
1 chlorine solution for
48 h prior to being placed in the experimental setup. This was
done in order to achieve MnOx(s) coating regeneration on the
media and inactivate microorganisms present on the media to
reduce the possible effect of microbiologically influenced Mn-
redox processes during the course of the experiments. Glass
columns of 0.95 cm internal diameter were packed with regener-
ated MnOx(s)-coated anthracite media. Filter column media depths
were only 7.62 cm due to the high Mn(II) removal capacity of the
MnOx(s) coatings obtained from North Carolina.2,15 Using a
manganous chloride stock, an influent soluble Mn(II) concentration
10069
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of 0.3 mg 3 L
1 was dosed to columns operated at pH 6.3 and pH
7.2 in the absence and presence of free chlorine under oxic
conditions (8 mg 3 L
1 dissolved oxygen (DO)). The pH range of
6.3
7.2 was chosen for this study because it is characteristic of
surface water coagulation treatment plants. Another set of experi-
ments was performed using influent Mn(II) concentrations of 0.3
mg 3 L
1 (also added as manganous chloride) to feed columns
operated at pH 8.2 in the absence of chlorine with DO concentra-
tions of 8 mg 3 L
1 and 0.5 mg 3 L
1. Nitrogen gas was bubbled
through feed solution to maintain 0.5 mg 3 L
1 DO levels through
the system for this specific condition. A “control” column was
operated with no influent Mn and no chlorine addition at pH 6.3 to
assess soluble Mn(II) release from the MnOx(s)-coated anthracite
media columns due to chemically or microbiologically catalyzed
reduction. Solutions consisting of 1 M NaOH and 1 M HCl were
used to adjust the feedwater in the column experiments to achieve
the desired pH values. The feedwater used for these experiments
consisted of deionized water with 0.5 meq 3 L
1 as CaCO3 hardness
and 1 meq 3 L
1 as CaCO3 alkalinity as a source for background
ions. Stocks of CaCl2 and NaHCO3 were used as the source of
calcium and bicarbonate. Chlorine concentrations for the experi-
ments were targeted at 3 mg 3 L
1 dosed as sodium hypochlorite at
an application point located close enough to the columns so that the
target reaction time with Mn(II) before reaching the columns was
approximately 5 s. This reaction time would have been insufficient
to promote homogeneous oxidation of Mn(II) with chlorine prior
to reaching the MnOx(s)-coated anthracite media.5 Hydraulic
loading rates targeted at 2500 L 3 day
1 3 m
2 were applied to the
columns using peristaltic pumps to control the flow.
Effluent Mn was monitored for 48 h for the columns operated
with chlorine and 72 h for the columns operated with no
chlorine. These monitoring times were selected based on the
results obtained from previous studies which indicated that (a)
48 h is more than adequate time to evaluate soluble Mn uptake
on an MnOx(s) surface in the presence of chlorine due to the
rapid regeneration of the MnOx(s) media surface Mn adsorption
sites, and (b) 72 h is a reasonable time for the MnOx(s) media to
reach sufficient exhaustion due to adsorptive capacity saturation
when free chlorine is not present.2,25 After this column-loading
period, all columns were eluted with a mild acid solution
(pH 5.0) consisting of deionized water (H2SO4 or NaOH were
added for pH adjustment) to assess the fraction of Mn(II) that
was adsorbed (unoxidized) during column operation. As stated
in a previous study,2 it was assumed that operation at pH 5 would
promote the release of adsorbed unoxidized Mn(II) due to
competition with H+ for adsorption sites26 without promoting
reduction of MnOx(s) to Mn(II). Effluent Mn concentrations
were measured using a Perkin-Elmer 5100 flame atomic absorp-
tion spectrophotometer (Waltham, MA, USA) and a Hach
DR/2400 spectrophotometer (preprogrammed method for
low range concentrations: 0.006
0.700 mg 3 L
1 Mn). Chlorine
was measured using a Hach pocket colorimeter II test kit
(DPD
total chlorine method).
A check was performed using the leucoberbelin method27,28 to
assess whether any oxidized Mn was present in the elution from
the columns using a procedure described by Cerrato et al.24 The
leucoberbelin method can distinguish between Mn(II) and
oxidation states Mn(III) or higher.28,29
Elemental Extractions. A previously developed method2 was
used to determine the extractable elemental content on the
filtration media samples as described in another article.20 Solu-
tion samples were filtered through a 0.45-μm membrane and
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Environmental Science & Technology
Table 1. Peak Position and Fit Parameters for the Gaussian

Lorentzian Asymmetric Algorithm Curve-Fit of the XPS Mn
3p Photo-Peaks Obtained for the Mn(II), Mn(III), and
Mn(IV) Reference Standards
peak
standard position (eV) fwhma % Gaussb T.L.c T.S.c
Mn (II) 47.99 1.91 88 73.3 0.49
Mn(III) 48.43 2.07 96 64.1 0.64
Mn(IV) 49.07 2.35 85 76.1 0.36
a
fwhm = Full width at half-maximum. b % Gauss = Percent of the pure
Gaussian line shape. c T.L. and T.S. = Parameters describing the tail of
the asymmetric Gaussian
Lorentzian XPS peak. d χ2 = Chi-squared
goodness of fit parameter.
metal concentrations were analyzed using an inductively coupled
plasma mass spectrophotometer ICP-MS according to Standard
Method 3125-B.30
XPS Analysis. The oxidation state of Mn was identified using
XPS by analysis of the position and shape of the Mn 3p photo-
line as described by Cerrato et al.20 XPS analyses were also
performed in the Mn 3s core-level region. However, there was no
clear evidence for the detection of Mn(III) by XPS through the
determination of the Mn 3s multiplet splitting under the experi-
mental conditions used for his study.31 Thus, XPS Mn 3p
analyses were pursued instead as it was expected that the chances
of detecting Mn(III) in the presence of Mn(IV) and Mn(II)
could be greater in the Mn3p region (located ∼45
54 eV)
because it is closer to the valence band than the Mn 3s region
(located ∼80
94 eV) and, thus, more sensitive to photopeak
shifts. A Perkin-Elmer 5400 X-ray photoelectron spectrometer
(Physical Electronic Industries, Inc.) consisting of an aluminum
X-ray source and two-channel collector was used. The X-ray
anode was operated at 12 keV and 250 W and the vacuum was
maintained at or below 5  10
7 Torr. The pass energy for
survey wide scans was 89.45 eV. The pass energy for narrow scans
was 17.9 eV. Data were analyzed using AugerScan 3.12 (RBD
Enterprises Inc.). The binding energy of the samples analyzed in
the Mn 3p region was charge referenced to the gold Au 4f7/2 peak
position at 84.0 eV; gold was vacuum deposited on all samples.
Narrow scans of the Mn 3p photoline were first analyzed using
Shirley background subtraction;18,32 the data were normalized
for comparison with Mn(II), Mn(III), and Mn(IV) reference
standards as shown by Cerrato et al.20 An asymmetrical
Gaussian
Lorentzian algorithm was then employed for curve-
fitting of MnOx(s) media column samples based on the careful
determination of the shape and position of the Mn(II), Mn(III),
and Mn(IV) reference standards. The peak position and fit
parameters obtained for the Gaussian
Lorentzian asymmetric
algorithm curve-fit of the Mn 3p photopeaks obtained for the
Mn(II), Mn(III), and Mn(IV) reference standards are presented
in Table 1. A similar approach for the analysis of narrow scans was
used in a previous study that treated the Fe 3p spectra as a single
peak.33 Theoretical and experimental justification for the single
broad asymmetric line of the Mn 3p photoelectron spectra is
provided elsewhere.34
’ RESULTS AND DISCUSSION
Mn Content of MnOx(s)-Coated Anthracite Media. The
total Mn content of the MnOx(s)-coated anthracite media
collected for this study was 30.7 mg extractable Mn (g dry weight
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χ2d
1.07
0.44
0.98
Figure 1. (a) Mn(II) uptake of columns used to conduct the experi-
ments performed with an influent Mn(II) concentration of 0.3 mg 3 L
1
at pH 6.3 in the absence and presence of chlorine (target = 3 mg 3 L
1
HOCl). (b) Release of Mn(II) from columns originally operated at pH
6.3 with an influent Mn(II) concentration of 0.3 mg 3 L
1 in the absence
and presence of chlorine (target = 3 mg 3 L
1 HOCl) after elution with a
mildly acid solution (pH 5.0).
of sample)
1, showing that there is considerable total Mn
content in the surface of this sample. This value is comparable
to those reported in other studies.15,20
Control Column Experiments. Observed levels of effluent Mn
varied from very mild (<0.01 mg 3 L
1 Mn) to levels below the
instrumental detection limit (0.006 mg 3 L
1) during the operation
of the “control” (unreacted) column with no influent Mn in the
absence of chlorine. Thus, there was no evidence of soluble Mn
released from the MnOx(s)-coated media used in these control
columns that could possibly be attributed to chemical or micro-
bially catalyzed reduction.
Mn-Removal in the Absence and Presence of Chlorine at
pH 6.3 and pH 7.2. The results obtained for Mn-removal in the
absence and presence of chlorine at pH 6.3 and at pH 7.2 are
presented in Figure 1 and Figure S1 (Supporting Information, SI),
respectively. The data presented in Figures 1 and S1 represent
Mn(II) sorption/uptake (1a and S1a) and Mn(II) desorption/
release after elution with a mildly acidic solution (1b and S1b).
These results are consistent with the observations reported in a
previous study.2
The Mn uptake calculated for the columns operated with no
chlorine at pH 6.3 was 1.8 mg Mn 3 g
1 of MnOx(s)-coated
media and the uptake at pH 7.2 was 2.6 mg Mn 3 g
1 of MnOx(s)-
coated media. These results indicate that more Mn was removed
at pH 7.2 when compared to pH 6.3, suggesting that Mn(II)
adsorption capacity in MnOx(s)-coated media increases in direct
proportion to pH increase as reported in other studies.1,2,15
Progressive exhaustion of MnOx(s)-coated media sites available
10070 dx.doi.org/10.1021/es203262n |Environ. Sci. Technol. 2011, 45, 10068–10074
Environmental Science & Technology
Table 2. Summary of Mn 3p XPS and Mn(II) Elution Results Obtained for Each of the Treatments Applied to the Laboratory
Column Experiments (Mn Influent to All Columns Was 0.3 mg 3 L
1)
sample (experimental condition) Mn(IV)
1 (control media; no treatment)a a 100%
b 100%
2 (pH 6.3, No chlorine) a 70
85%b
b 46
60%
3 (pH 7.2, No chlorine) a 78
82%
b 64
72%
4 (pH 6.3, 3 mg 3 L
1 as HOCl) a 87
94%
b 85
89%
5 (pH 7.2, 3 mg 3 L
1 as HOCl) a 100%
b 100%
6 (pH 8.2, no chlorine) a 51
65%
b 72
82%
a
Letters a and b for each row reflect two different particles obtained from the same column/experimental condition. b An estimated range of the percent
of Mn(IV), Mn(III), and Mn(II) is provided. When Mn(II) and Mn(IV) are present in a sample (i.e., 1a, 1b, 2a, 2b, 3a, 3b, etc.), it is challenging to
quantify the amount of Mn(III) in the Mn 3p region. c BDL = Below detection limit. d NA = Not applicable.
for sorption of Mn(II) was observed under both pH 6.3 and pH
7.2 over time in the absence of chlorine. Results obtained from
elution experiments after exposure to a mild acid (pH 5.0) solution
of these columns suggest that Mn uptake in these columns was
mostly due to adsorption. These results are shown in Figure 1b
and Figure S1b, respectively. No evidence of oxidized Mn in
solution was detected with spectrophotometric measurements of
the effluent samples using the leucoberbelin blue method; only
Mn(II) was detected in the effluent elution samples. The calcu-
lated % Mn(II) recovered from elution experiments, as shown in
Table 2, indicates that approximately 70% and 76% of the
absorbed Mn(II) was released during elution for columns oper-
ated in the absence of chlorine at pH 6.3 and 7.2, respectively.
As reported in other studies,1,2,15 individual comparisons of
columns operated with and without chlorine at pH 6.3 and pH
7.2 clearly indicate that efficient long-term Mn(II) removal is
enhanced by the presence of chlorine due to continuous “re-
generation” of the Mn-oxide coated media surface caused by
oxidation. Less than 5% of the Mn(II) uptake was released during
elution for the experiments operated in the presence of chlorine,
suggesting that more than 95% of the Mn(II) removed in these
columns was oxidized on the media surface and not available for
elution by mild acid desorption.
A previous investigation25 performed under experimental
conditions similar to those presented in this study yielded an
average of 88% Mn release under pH 5.0 desorption conditions
for columns containing MnOx(s)-coated filter media operated in
the absence of free chlorine during filter loading. When free
chlorine was present in the filter loading the pH 5.0 desorption
studies yielded an average of only 7% Mn being released from the
media. The authors hypothesized that the presence of free
chlorine promoted surface-catalyzed Mn oxidation that subse-
quently inhibited desorptive release under mild acid conditions.
Mn-Removal at pH 8.2 at 8 mg 3 L
1 DO and 0.5 mg 3 L
1
DO in the Absence of Chlorine. Results obtained for these
conditions are presented in Figure S2 (SI). The calculated Mn
uptake at pH 8.2 for the column operated under 8 mg 3 L
1 DO was
4.2 mg Mn 3 g
1 of MnOx(s)-coated media and the uptake under
0.5 mg 3 L
1 DO was 0.9 mg Mn 3 g
1 of MnOx(s)-coated media.
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XPS results
Mn(III) Mn(II) % Mn(II) recovery after acid elution
BDLc BDL NAd
BDL BDL
BDL
17% 12
15% 70%
BDL
21% 30
40%
BDL
6% 16
22% 76%
BDL
20% 16
28%
BDL
13% BDL
6% <5%
BDL
12% BDL
11%
BDL BDL <5%
BDL BDL
BDL
36% 5
35% 30%
BDL
18% 5
18%
These results indicate that uptake is greater for columns operated in
the presence of higher DO, which acts as an oxidant. Interestingly,
results obtained from elution experiments for both of these columns
suggest that Mn uptake was mostly due to initial adsorption and
subsequent surface-catalyzed Mn oxidation even at low DO condi-
tions; these results are shown in Figure 2bS. The calculated %
Mn(II) recovered for each laboratory column experiment is sum-
marized in Table 2. Only 30% and 44% of Mn(II) adsorbed to the
columns operated under 8 mg 3 L
1 and 0.5 mg 3 L
1 DO, respec-
tively, was released during the elution experiments. These results
suggested that at least 50% of the soluble Mn uptaken by the
columns was oxidized and not available for elution by desorption.
Metal oxidation catalyzed by MnOx(s) and other metal-oxides under
suboxic or anoxic conditions has been reported in other studies.35,36
XPS Analyses. Curve fitting results from XPS analyses at the
Mn 3p photopeak reporting the percentage of Mn(IV), Mn(III),
and Mn(II) in each of the MnOx(s) coated media samples are
shown in Table 2. Curve fits for representative XPS spectra are
illustrated in Figure S3 (SI). An example of the curve fitting
sequence for a sample containing Mn(IV), Mn(III), and Mn(II)
is shown in Figure S4 (SI). Mn(IV) was included as the first
option in the fitting sequence since it was determined that the
control MnOx(s) coated media sample (no treatment) consisted
of 100% Mn(IV) (see Table 2). Because 70% Mn was eluted
from the desorption experiments performed for this specific
sample, then Mn(II) was added to the fit. Finally, Mn(III) was
included to evaluate if the quality of the fit improved. Note that
the typical depth of analysis for XPS, for these types of materials
and at the energies of these Mn photoelectrons, is roughly 5 nm
(86% of the signal), with the signal contribution dropping off
exponentially through that depth.18 The sorption/desorption
and heterogeneous oxidation reactions studied occur in the
“surface” region; that is, at the solid
aqueous interface. The
reader should keep in mind that the XPS signals corresponding to
the results presented in this article were generated from the
“near-surface” region which includes the first few nanometers of
the MnOx(s) coated media samples.
Mn(IV) was identified in the “control” sample obtained from
the column operated with no manganese and no chlorine;
10071 dx.doi.org/10.1021/es203262n |Environ. Sci. Technol. 2011, 45, 10068–10074
Environmental Science & Technology
Figure 2. XPS Mn 3p (7P) photopeak spectrum for (a) sample 1B
(S1B): media not exposed to laboratory column experiments;
(b) sample 2B (S2B): pH 6.3, no chlorine, Mn influent = 0.3 mg 3 L
1;
(c) sample 3B (S3B): pH 7.2, no chlorine, Mn influent = 0.3 mg 3 L
1.
no evidence of Mn(II) or Mn(III) was observed in the control.
The XPS narrow scan spectra obtained in the Mn 3p region for
the two control samples (unreacted) are illustrated in Figure 2a
and Figure S5a (SI). This result was expected because the
MnOx(s) coated media used for this study were pretreated with
100 mg 3 L
1 to achieve surface oxidation.
Mn(IV) was identified as the predominant oxidation state in
all cases. However, as confirmed by the elution experiments,
analyses of the XPS narrow scan spectra also reveal the presence
10072
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Figure 3. XPS Mn 3p (7P) photopeak spectrum for (a) sample 4A
(S4A): pH 6.3, 3 mg 3 L
1 chlorine; (b) sample 5A (S5A): pH 7.2, 3
mg 3 L
1 chlorine; and (c) sample 6A (S6A): pH 8.2, no chlorine. Mn
influent to all columns = 0.3 mg 3 L
1.
of Mn(II) in the surface of the two MnOx(s)-coated media
particle samples obtained from the column operated at pH 6.3
and pH 7.2 in the absence of chlorine (Figure 2b and c, and
Figure S5b and c, SI). Consideration of Mn(IV) and Mn(II)
oxidation states in the curve fitting analyses (Figure S4b, SI)
significantly improved the quality of the fit when compared to
that obtained by considering only Mn(IV) (Figure S4a, SI). The
quality of the fit did not improve or degrade by inclusion of
Mn(III) (Figure S4c, SI) in addition to the previously considered
dx.doi.org/10.1021/es203262n |Environ. Sci. Technol. 2011, 45, 10068–10074
Environmental Science & Technology
Mn(IV) and Mn(II) oxidation states. A similar result was observed
when using the Mn 3s core-level region; it was not possible to
conclusively identify the presence of Mn(III) through the deter-
mination of the Mn 3s multiplet splitting when Mn(II) and
Mn(IV) were also present.31 Nevertheless, close observation of
the shape and position of the Mn 3p photoline show that adding a
Mn(III) contribution is definitely consistent with the observed
spectra taken from the MnOx-coated media used in the column
experiments in the absence of chlorine. The possible presence of
Mn(III) in these samples is also consistent with the fact that only
70
76% (not 100%) of Mn(II) was recovered in the elution
experiments; this suggests that, although adsorption is the main
Mn uptake mechanism at pH 6.3 and 7.2 in the absence of
chlorine, some heterogeneous Mn (II) oxidation was catalyzed by
MnOx-coated media. In addition, other studies have reported
the possible presence of Mn(III) when heterogeneous oxidation of
Mn(II) is catalyzed by oxide-coated media.7
9
Although XPS results suggest the possible presence of Mn-
(III), Mn(IV) was identified as the predominant oxidation state
for media samples obtained from the column operated in the
presence of chlorine at pH 6.3 (Figure 3a and Figure S6a, SI).
Mn(IV) was identified as the predominant oxidation state in the
XPS analyses performed for media samples obtained from the
column operated in the presence of chlorine at pH 7.2 (Figure 3b
and Figure S6b, SI). These XPS results are consistent with the
elution experiment results, which show that <5% of Mn was
released from column experiments, suggesting a minor presence
of Mn(II) in the surface. Mn(II) was below the detection limit of
XPS for the samples reacted in the presence of chlorine.
XPS analyses suggest that Mn(IV), Mn(III), and Mn(II) are
present in the samples recovered from the column operated at
8 mg 3 L
1 DO at pH 8.2. The XPS narrow scans for this
experimental condition are illustrated in Figures 3c and S6c
(SI). As observed for the MnOx-coated media samples obtained
from the column experiments in the absence of chlorine at pH 6.3
and 7.2, the quality of the fit did not improve by inclusion of
Mn(III) (Figure S4c, SI) in addition to the previously considered
Mn(IV) and Mn(II) oxidation states (data not shown). However,
as explained above, the presence of Mn(III) together with Mn-
(IV) and Mn(II) is consistent with the shape and position of the
Mn 3p spectra illustrated in Figures 3c and S6c (SI), normalized
versus Mn(IV), Mn(III), and Mn(II) reference standards. The
presence of Mn(III) and Mn(IV) is again also consistent with the
fact that only 30% of the Mn uptaken by the column was released
during the elution experiment. Thus, it is very likely that most of
the Mn (II) removed consists of oxidized species not available for
desorption by mild acid elution. No XPS analyses were performed
for the experiments executed at 0.5 mg 3 L
1 DO at pH 8.2.
Implications for Water Treatment. The incorporation of
XPS surface analysis techniques into these experimental studies
on Mn adsorption
desorption behavior allows for a much better
understanding of the means by which soluble Mn interacts with
MnOx(s)-coated filter media. For example, XPS results clearly
showed that when sufficient free chlorine is applied across the
filter media the soluble Mn removed is rapidly adsorbed and
subsequently oxidized to an insoluble Mn(IV) valence state,
most likely corresponding to the formation of MnO2(s). Once
adsorbed and then oxidized by the free chlorine, this Mn is not
available for dissolution back into the water.
In the absence of filter-applied free chlorine, the majority of
the adsorbed Mn was not oxidized as evidenced by both the
significant presence of Mn(II) detected by XPS analysis and the
10073
ARTICLE
high degree of Mn recovery during desorption tests at pH 5.0.
For the portion of the adsorbed Mn that was subsequently
oxidized, the results indicated that dissolved oxygen present in
solution may have played a role in that observed oxidation,
especially when considering that increases in solution pH and
higher levels of dissolved oxygen (oxygen effects studied speci-
fically at pH 8.2) promoted substantial evidence of Mn oxidation
on the media surface. However, most conventional surface water
treatment plants employing aluminum or ferric salts for chemical
coagulation would operate under slightly acidic to neutral pH
conditions, a range wherein much less evidence of Mn oxidation
on the MnOx(s) surface was observed. Under those treatment
conditions, adsorbed Mn would appear not to be readily oxidized
and, hence, available for release from the filter media. Finally, this
discussion has focused on chemical oxidation methods for Mn
adsorbed to the media. In the absence of free chlorine microbial
populations would develop on the MnOx(s)-coated filter media
that could result in microbially mediated oxidation of any sorbed
Mn.22,24,37,38
’ ASSOCIATED CONTENT
bS Supporting Information. Six additional figures (S1
S6).
This material is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: knocke@vt.edu; phone: (001) (540) 231-9050; fax:
(001) (540) 231-4384.
Present Addresses
)
Department of Energy, Environmental, and Chemical Engineer-
ing, One Brookings Drive, Washington University, Saint Louis,
Missouri 63130, United States.
’ ACKNOWLEDGMENT
Dr. Jeffrey Parks provided the ICP-MS analysis. Funding for
this research was provided by the National Science Foundation
(NSF IGERT grant DGE-0504196) and the Via Department of
Civil and Environmental Engineering at the Virginia Polytechnic
Institute and State University. Any opinions, findings, conclu-
sions or recommendations expressed in this material are those of
the authors and do not necessarily reflect the views of the
National Science Foundation.
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