ARTICLE

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

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

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 χ2d

Mn (II) 47.99 1.91 88 73.3 0.49 1.07

Mn(III) 48.43 2.07 96 64.1 0.64 0.44
Mn(IV) 49.07 2.35 85 76.1 0.36 0.98
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)
Figure 1. (a) Mn(II) uptake of columns used to conduct the experi-
could be greater in the Mn3p region (located ∼45
54 eV) ments performed with an influent Mn(II) concentration of 0.3 mg 3 L
1
because it is closer to the valence band than the Mn 3s region at pH 6.3 in the absence and presence of chlorine (target = 3 mg 3 L
1
(located ∼80
94 eV) and, thus, more sensitive to photopeak HOCl). (b) Release of Mn(II) from columns originally operated at pH
shifts. A Perkin-Elmer 5400 X-ray photoelectron spectrometer 6.3 with an influent Mn(II) concentration of 0.3 mg 3 L
1 in the absence
(Physical Electronic Industries, Inc.) consisting of an aluminum and presence of chlorine (target = 3 mg 3 L
1 HOCl) after elution with a
X-ray source and two-channel collector was used. The X-ray mildly acid solution (pH 5.0).
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 of sample)
1, showing that there is considerable total Mn
survey wide scans was 89.45 eV. The pass energy for narrow scans content in the surface of this sample. This value is comparable
was 17.9 eV. Data were analyzed using AugerScan 3.12 (RBD to those reported in other studies.15,20
Enterprises Inc.). The binding energy of the samples analyzed in Control Column Experiments. Observed levels of effluent Mn
the Mn 3p region was charge referenced to the gold Au 4f7/2 peak varied from very mild (<0.01 mg 3 L
1 Mn) to levels below the
position at 84.0 eV; gold was vacuum deposited on all samples. instrumental detection limit (0.006 mg 3 L
1) during the operation
Narrow scans of the Mn 3p photoline were first analyzed using of the “control” (unreacted) column with no influent Mn in the
Shirley background subtraction;18,32 the data were normalized absence of chlorine. Thus, there was no evidence of soluble Mn
for comparison with Mn(II), Mn(III), and Mn(IV) reference released from the MnOx(s)-coated media used in these control
standards as shown by Cerrato et al.20 An asymmetrical columns that could possibly be attributed to chemical or micro-
Gaussian
Lorentzian algorithm was then employed for curve- bially catalyzed reduction.
fitting of MnOx(s) media column samples based on the careful Mn-Removal in the Absence and Presence of Chlorine at
determination of the shape and position of the Mn(II), Mn(III), pH 6.3 and pH 7.2. The results obtained for Mn-removal in the
and Mn(IV) reference standards. The peak position and fit absence and presence of chlorine at pH 6.3 and at pH 7.2 are
parameters obtained for the Gaussian
Lorentzian asymmetric presented in Figure 1 and Figure S1 (Supporting Information, SI),
algorithm curve-fit of the Mn 3p photopeaks obtained for the respectively. The data presented in Figures 1 and S1 represent
Mn(II), Mn(III), and Mn(IV) reference standards are presented Mn(II) sorption/uptake (1a and S1a) and Mn(II) desorption/
in Table 1. A similar approach for the analysis of narrow scans was release after elution with a mildly acidic solution (1b and S1b).
used in a previous study that treated the Fe 3p spectra as a single These results are consistent with the observations reported in a
peak.33 Theoretical and experimental justification for the single previous study.2
broad asymmetric line of the Mn 3p photoelectron spectra is The Mn uptake calculated for the columns operated with no
provided elsewhere.34 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)-
’ RESULTS AND DISCUSSION coated media. These results indicate that more Mn was removed
at pH 7.2 when compared to pH 6.3, suggesting that Mn(II)
Mn Content of MnOx(s)-Coated Anthracite Media. The adsorption capacity in MnOx(s)-coated media increases in direct
total Mn content of the MnOx(s)-coated anthracite media proportion to pH increase as reported in other studies.1,2,15
collected for this study was 30.7 mg extractable Mn (g dry weight 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 ARTICLE

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)

XPS results

sample (experimental condition) Mn(IV) Mn(III) Mn(II) % Mn(II) recovery after acid elution

1 (control media; no treatment)a a 100% BDLc BDL NAd

b 100% BDL BDL
2 (pH 6.3, No chlorine) a 70
85%b BDL
17% 12
15% 70%
b 46
60% BDL
21% 30
40%
3 (pH 7.2, No chlorine) a 78
82% BDL
6% 16
22% 76%
b 64
72% BDL
20% 16
28%
4 (pH 6.3, 3 mg 3 L
1 as HOCl) a 87
94% BDL
13% BDL
6% <5%
b 85
89% BDL
12% BDL
11%
5 (pH 7.2, 3 mg 3 L
1 as HOCl) a 100% BDL BDL <5%
b 100% BDL BDL
6 (pH 8.2, no chlorine) a 51
65% BDL
36% 5
35% 30%
b 72
82% BDL
18% 5
18%
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 These results indicate that uptake is greater for columns operated in
7.2 over time in the absence of chlorine. Results obtained from the presence of higher DO, which acts as an oxidant. Interestingly,
elution experiments after exposure to a mild acid (pH 5.0) solution results obtained from elution experiments for both of these columns
of these columns suggest that Mn uptake in these columns was suggest that Mn uptake was mostly due to initial adsorption and
mostly due to adsorption. These results are shown in Figure 1b subsequent surface-catalyzed Mn oxidation even at low DO condi-
and Figure S1b, respectively. No evidence of oxidized Mn in tions; these results are shown in Figure 2bS. The calculated %
solution was detected with spectrophotometric measurements of Mn(II) recovered for each laboratory column experiment is sum-
the effluent samples using the leucoberbelin blue method; only marized in Table 2. Only 30% and 44% of Mn(II) adsorbed to the
Mn(II) was detected in the effluent elution samples. The calcu- columns operated under 8 mg 3 L
1 and 0.5 mg 3 L
1 DO, respec-
lated % Mn(II) recovered from elution experiments, as shown in tively, was released during the elution experiments. These results
Table 2, indicates that approximately 70% and 76% of the suggested that at least 50% of the soluble Mn uptaken by the
absorbed Mn(II) was released during elution for columns oper- columns was oxidized and not available for elution by desorption.
ated in the absence of chlorine at pH 6.3 and 7.2, respectively. Metal oxidation catalyzed by MnOx(s) and other metal-oxides under
As reported in other studies,1,2,15 individual comparisons of suboxic or anoxic conditions has been reported in other studies.35,36
columns operated with and without chlorine at pH 6.3 and pH XPS Analyses. Curve fitting results from XPS analyses at the
7.2 clearly indicate that efficient long-term Mn(II) removal is Mn 3p photopeak reporting the percentage of Mn(IV), Mn(III),
enhanced by the presence of chlorine due to continuous “re- and Mn(II) in each of the MnOx(s) coated media samples are
generation” of the Mn-oxide coated media surface caused by shown in Table 2. Curve fits for representative XPS spectra are
oxidation. Less than 5% of the Mn(II) uptake was released during illustrated in Figure S3 (SI). An example of the curve fitting
elution for the experiments operated in the presence of chlorine, sequence for a sample containing Mn(IV), Mn(III), and Mn(II)
suggesting that more than 95% of the Mn(II) removed in these is shown in Figure S4 (SI). Mn(IV) was included as the first
columns was oxidized on the media surface and not available for option in the fitting sequence since it was determined that the
elution by mild acid desorption. control MnOx(s) coated media sample (no treatment) consisted
A previous investigation25 performed under experimental of 100% Mn(IV) (see Table 2). Because 70% Mn was eluted
conditions similar to those presented in this study yielded an from the desorption experiments performed for this specific
average of 88% Mn release under pH 5.0 desorption conditions sample, then Mn(II) was added to the fit. Finally, Mn(III) was
for columns containing MnOx(s)-coated filter media operated in included to evaluate if the quality of the fit improved. Note that
the absence of free chlorine during filter loading. When free the typical depth of analysis for XPS, for these types of materials
chlorine was present in the filter loading the pH 5.0 desorption and at the energies of these Mn photoelectrons, is roughly 5 nm
studies yielded an average of only 7% Mn being released from the (86% of the signal), with the signal contribution dropping off
media. The authors hypothesized that the presence of free exponentially through that depth.18 The sorption/desorption
chlorine promoted surface-catalyzed Mn oxidation that subse- and heterogeneous oxidation reactions studied occur in the
quently inhibited desorptive release under mild acid conditions. “surface” region; that is, at the solid
aqueous interface. The
Mn-Removal at pH 8.2 at 8 mg 3 L
1 DO and 0.5 mg 3 L
1 reader should keep in mind that the XPS signals corresponding to
DO in the Absence of Chlorine. Results obtained for these the results presented in this article were generated from the
conditions are presented in Figure S2 (SI). The calculated Mn “near-surface” region which includes the first few nanometers of
uptake at pH 8.2 for the column operated under 8 mg 3 L
1 DO was the MnOx(s) coated media samples.
4.2 mg Mn 3 g
1 of MnOx(s)-coated media and the uptake under Mn(IV) was identified in the “control” sample obtained from
0.5 mg 3 L
1 DO was 0.9 mg Mn 3 g
1 of MnOx(s)-coated media. 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 ARTICLE

Figure 3. XPS Mn 3p (7P) photopeak spectrum for (a) sample 4A

Figure 2. XPS Mn 3p (7P) photopeak spectrum for (a) sample 1B (S4A): pH 6.3, 3 mg 3 L
1 chlorine; (b) sample 5A (S5A): pH 7.2, 3
(S1B): media not exposed to laboratory column experiments; mg 3 L
1 chlorine; and (c) sample 6A (S6A): pH 8.2, no chlorine. Mn
(b) sample 2B (S2B): pH 6.3, no chlorine, Mn influent = 0.3 mg 3 L
1; influent to all columns = 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. of Mn(II) in the surface of the two MnOx(s)-coated media
The XPS narrow scan spectra obtained in the Mn 3p region for particle samples obtained from the column operated at pH 6.3
the two control samples (unreacted) are illustrated in Figure 2a and pH 7.2 in the absence of chlorine (Figure 2b and c, and
and Figure S5a (SI). This result was expected because the Figure S5b and c, SI). Consideration of Mn(IV) and Mn(II)
MnOx(s) coated media used for this study were pretreated with oxidation states in the curve fitting analyses (Figure S4b, SI)
100 mg 3 L
1 to achieve surface oxidation. significantly improved the quality of the fit when compared to
Mn(IV) was identified as the predominant oxidation state in that obtained by considering only Mn(IV) (Figure S4a, SI). The
all cases. However, as confirmed by the elution experiments, quality of the fit did not improve or degrade by inclusion of
analyses of the XPS narrow scan spectra also reveal the presence Mn(III) (Figure S4c, SI) in addition to the previously considered
10072 dx.doi.org/10.1021/es203262n |Environ. Sci. Technol. 2011, 45, 10068–10074
Environmental Science & Technology ARTICLE

Mn(IV) and Mn(II) oxidation states. A similar result was observed high degree of Mn recovery during desorption tests at pH 5.0.
when using the Mn 3s core-level region; it was not possible to For the portion of the adsorbed Mn that was subsequently
conclusively identify the presence of Mn(III) through the deter- oxidized, the results indicated that dissolved oxygen present in
mination of the Mn 3s multiplet splitting when Mn(II) and solution may have played a role in that observed oxidation,
Mn(IV) were also present.31 Nevertheless, close observation of especially when considering that increases in solution pH and
the shape and position of the Mn 3p photoline show that adding a higher levels of dissolved oxygen (oxygen effects studied speci-
Mn(III) contribution is definitely consistent with the observed fically at pH 8.2) promoted substantial evidence of Mn oxidation
spectra taken from the MnOx-coated media used in the column on the media surface. However, most conventional surface water
experiments in the absence of chlorine. The possible presence of treatment plants employing aluminum or ferric salts for chemical
Mn(III) in these samples is also consistent with the fact that only coagulation would operate under slightly acidic to neutral pH
70
76% (not 100%) of Mn(II) was recovered in the elution conditions, a range wherein much less evidence of Mn oxidation
experiments; this suggests that, although adsorption is the main on the MnOx(s) surface was observed. Under those treatment
Mn uptake mechanism at pH 6.3 and 7.2 in the absence of conditions, adsorbed Mn would appear not to be readily oxidized
chlorine, some heterogeneous Mn (II) oxidation was catalyzed by and, hence, available for release from the filter media. Finally, this
MnOx-coated media. In addition, other studies have reported discussion has focused on chemical oxidation methods for Mn
the possible presence of Mn(III) when heterogeneous oxidation of adsorbed to the media. In the absence of free chlorine microbial
Mn(II) is catalyzed by oxide-coated media.7
9 populations would develop on the MnOx(s)-coated filter media
Although XPS results suggest the possible presence of Mn- that could result in microbially mediated oxidation of any sorbed
(III), Mn(IV) was identified as the predominant oxidation state Mn.22,24,37,38
for media samples obtained from the column operated in the
presence of chlorine at pH 6.3 (Figure 3a and Figure S6a, SI). ’ ASSOCIATED CONTENT
Mn(IV) was identified as the predominant oxidation state in the
XPS analyses performed for media samples obtained from the bS Supporting Information. Six additional figures (S1
S6).
column operated in the presence of chlorine at pH 7.2 (Figure 3b This material is available free of charge via the Internet at http://
and Figure S6b, SI). These XPS results are consistent with the pubs.acs.org.
elution experiment results, which show that <5% of Mn was
released from column experiments, suggesting a minor presence ’ AUTHOR INFORMATION
of Mn(II) in the surface. Mn(II) was below the detection limit of
XPS for the samples reacted in the presence of chlorine. Corresponding Author
XPS analyses suggest that Mn(IV), Mn(III), and Mn(II) are *E-mail: [email protected]; phone: (001) (540) 231-9050; fax:
present in the samples recovered from the column operated at (001) (540) 231-4384.
8 mg 3 L
1 DO at pH 8.2. The XPS narrow scans for this Present Addresses
experimental condition are illustrated in Figures 3c and S6c
)

Department of Energy, Environmental, and Chemical Engineer-

(SI). As observed for the MnOx-coated media samples obtained ing, One Brookings Drive, Washington University, Saint Louis,
from the column experiments in the absence of chlorine at pH 6.3 Missouri 63130, United States.
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, ’ ACKNOWLEDGMENT
as explained above, the presence of Mn(III) together with Mn-
(IV) and Mn(II) is consistent with the shape and position of the Dr. Jeffrey Parks provided the ICP-MS analysis. Funding for
Mn 3p spectra illustrated in Figures 3c and S6c (SI), normalized this research was provided by the National Science Foundation
versus Mn(IV), Mn(III), and Mn(II) reference standards. The (NSF IGERT grant DGE-0504196) and the Via Department of
presence of Mn(III) and Mn(IV) is again also consistent with the Civil and Environmental Engineering at the Virginia Polytechnic
fact that only 30% of the Mn uptaken by the column was released Institute and State University. Any opinions, findings, conclu-
during the elution experiment. Thus, it is very likely that most of sions or recommendations expressed in this material are those of
the Mn (II) removed consists of oxidized species not available for the authors and do not necessarily reflect the views of the
desorption by mild acid elution. No XPS analyses were performed National Science Foundation.
for the experiments executed at 0.5 mg 3 L
1 DO at pH 8.2.
Implications for Water Treatment. The incorporation of ’ REFERENCES
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