Rapid Determination of Manganese in Wastewaters and Seawater by

Stripping Potentiometry
Geoffrey R . Scollary,*' Guo Nan Chen," Terence J . Cardwell,fi a n d Victoria A . Vincente-Beckett"'
+

School of Chemistry, University of Melbourne, Parkville, 3052, Australia

++
Centre for Scientific Instrumentation, La Trobe University, Melbourne, 3083, Australia
+++ Department of Applied Chemistry, Royal Melbourne Institute of Technology, GPO Box 2476V, Melbourne, 3001, Australia

Received: October 4, 1993

Final version: March 7, 1994
Abstract
A rapid stripping potentiometric method for the determination of trace levels of manganese in seawater and industrial waste waters has
been developed. The analysis is performed in the presence of oxygen with an analysis time of less than 2.5 min per sample at manganese
concentratioris lower than 5pg/L. The precision of the method is satisfactory and the results for 5 seawater and waste water samples
compare favorably with graphite furnace atomic absorption spectrophotometry.
Keywords: Stripping potentiometry, Manganese, Seawater, Industrial waste waters, Trace analysis

1. Introduction and Ecoff [9] also investigated the determination of manganese by

The analysis of manganese in waters is of interest as, together
with iron, it can significantly influence the redox behavior of the
water body [I]. Further, there are prob1em:j with manganese in
water treatment plants and reticulation systems. These include
taste and odor problems at concentrations above 100 pg/L and
dirty (or black) water production at much lower manganese
concentrations [2, 31.
Various electrochemical methods have: been used in the
determination of manganese. Some studies have used polaro-
graphy [4-71, but the detection limit is too high for routine
monitoring of waters containing manganese. O'Halloran [S]
demonstrated that anodic stripping voltammetry (ASV) at a
mercury film electrode (MFE) could be applied to the
determination of manganese with a detection limit of 0.2nM
(1 1 ng/L). However, a more recent study by Coetzee and Ecoff [9]
of the ASV determination of manganese at a M F E coated onto a
cylindrical carbon fiber showed that the background current was
high and not reproducible. Problems with the background current
were still encountered in the presence of lo-' M potassium
chloride as supporting electrolyte [9]. A further difficulty
associated with the ASV determination (of manganese is the
requirement for a high negative potential for preconcentration as
this can lead to hydrogen evolution. To address some of the
problems associated with the direct ASV method, Wang and
Mahmoud [101 have developed a stripping voltammetric proce-
dure based on the prior accumulation 'of manganese as its
Eriochrome Black T chelate at a hanging mercury drop
electrode. A detection limit of 32 ng/L was reported [lo].
Stripping potentiometry is now recognized as a viable
alternative to stripping voltammetry. Eskilsson and Turner
[I 1 1 have compared batch and flow stripping potentiometric
methods for manganese using a mercury coated glassy carbon
electrode. While both methods worked well, preconcentration
times up to 8min were required for sarnples containing low
concentrations of manganese. Further, it was also necessary to
reduce the stripping rate as it was observed that fast reoxidation
of manganese during the stripping step resulted in broad and
indistinct peaks. A slow stripping step was achieved by oxygen
removal in the batch method (ie: lowering the total oxidant
concentration) or by using aqueous Ca.Br2 as the stripping
solution to effect oxygen exclusion in the flow method. Coetzee
stripping potentiometry on the same electrode system used in their
ASV study. They concluded that stripping potentiometry gave
better results than ASV, the major advantage of stripping
potentiometry being the small and reproducible background.
They cite a detection limit (2g) of 2 x M (0.1 pg/L), similar to
that quoted by Eskilsson and Turner [ 1I]. To achieve this detection
limit, preconcentration times of 4min were required [9].
This article describes the rapid determination of manganese
by batch stripping potentiometry in industrial waste waters and
seawater. The particular advantages of this new procedure over
those described previously [9, 111 include a short preconcen-
tration time ( 1 min), the ability to determine low concentration
of manganese without the requirement for deoxygenation and
the use of instrumentation with fast data sampling rates. The
consequence of these advantages is a shorter overall analysis
time, which is significant for the routine monitoring of
manganese.
2. Experimental
2.1. Reagents
A 1000mg/L manganese(][) solution (BDH atomic absorp-
tion spectroscopy reagent) and mercury(i1) nitrate (BDH Aristar
grade) were used. A p H 9.0 buffer solution was prepared from
2 M aqueous ammonia (BDH Analar grade) and 2 M hydro-
chloric acid (BDH Aristar grade). MilliQ water was used for
solution preparation and for dilution.
2.2. Certified Sea Water
Nearshore seawater reference material (CASS-2) was
obtained from Marine Analytical Chemistry Standards Pro-
gram, Division of Chemistry, National Research Council,
Canada.
2.3. Samples
Industrial samples were collected from waste management
drains from various industrial sites and stored in polyethylene

Electroanulysis 1995, 7, No. 4 0 VCH Verlugsgesellschuft mbH. 0-69469 Weinheim, 1995 104O-O39719Sj0404-386$ S.OO+ ,2510
Determination of Manganese in Wastewaters and Seawater 387

bottles until used. A seawater sample was collected from Port 8o 1

Phillip Bay (Black Rock Point), Melbourne. Generally the
samples were used as received.

2.4. Apparatus
A Radiometer (Copenhagen) TraceLab system consisting of a
PSU20 potentiometric stripping unit and a SAM20 sample
station with a F3600 glassy carbon working electrode, a PI36
platinum auxiliary electrode and a K436 calomel reference
electrode was used. Data were collected (sampling rate of
30 kHz) and processed using Radiometer (Copenhagen) 'Tap2'
0
40 -
software on an IBM compatible PC. Check analyses were
9
3
carried out on an Hitachi 27000 graphite furnace atomic PI
absorption spectrophotometer and a Perkin-Elmer 5100
graphite furnace atomic absorption spectrophotometer.
20 -
2.5. Mercury Film Preparation
The glassy carbon electrode was first polished with Buehler
(Lake Buff, Illinois) Micropolish alumina powder (0.3 pm) on a
Buehler (Lake Buff, Illinois) Microcloth polishing cloth. Excess
alumina was removed by sonication in ethanol and the fresh O
7 8 9 10
l
11
electrode surface rinsed with MilliQ water. The electrode was
placed in a Radiometer (Copenhagen) mercury plating solution PH
(S2201: 800 mg/L mercury in 1.3 M HCI) and a plating potential
of -800 mV was applied for 5 min with stirring (approximately Fig. 1. Effect of pH on the stripping peak for manganese (5pg/L Mn;
preconcentration potential = - 1800mV; preconcentration time = 1 min;
1500rpm). The film was generally used for 4 to 5 h before rest time = 1 min).
renewal.
speed of stirring during preconcentration. A preconcentration
2.6. Analytical Procedure potential of - 1800mV (vs. SCE) was used as in previous work
[9, 1 I]. Of the variables considered, the pH of the solution was
The supporting electrolyte (2 mL of NH4CI-NH3 buffer found to be critical as shown in Figure 1 . The stripping signal
solution) and the stripping agent (20 pL of 1000mg/L
5
mercury(i1) solution in 1 M HCI to give a final mercury
concentration of 1 mg/L) were added to the electrochemical
cell. An appropriate volume of the sample (such that the
manganese concentration in the test solution did not exceed &.s
5pg/L) and sufficient MilliQ water to give a final volume of
20mL were also added. Oxygen removal was not employed. A 0
preconcentration potential of - 1800mV (vs. SCE) was applied
5-
for 1 min. Stirring (approximately 1000-1200 rpm) was used
during the preconcentration step. At the end of the preconcen-
1. 2. 3
tration period, the stirrer was stopped and the potential
maintained at -1800mV for the rest period (equal to the
preconcentration period). The potential was then switched off
and the stripping curve recorded in the potential range - 1800 to 0
- 1200 mV. On completion of the stripping process, the
potential of the working electrode was set at 0 mV for 10 s to 5
clean the electrode prior to the next analysis. Quantitation was 1. 2. 3.::
achieved by standard additions. Generally three additions were
made, the volume change being corrected for by the software.
Blank values were recorded using MilliQ water in place of the
sample.
0

3. Results and Discussion Potential I V

Fig. 2. Typical stripping curve for manganese at pH 9. a) preconcen-

Initial experiments were directed towards optimizing the tration time = 1 min; 1.: blank; 2.: 2 pg/L; 3.: 5 bg/L; b) preconcentration
conditions for the determination of manganese. Variables time = 20 s; Repeat stripping curves for 40 pg/L; c) preconcentration
examined included the preconcentration time, rest time, time = 10 s; 1.: 100pg/L; 2.: 150 pg/L; 3.: 2OOpglL (other conditions as in
solution pH, mercury(n) (k.,oxidant) concentration and Figure 1).

Electroanalysis 1995, 7, No. 4

388 G.R. Scollary et a!.

(peak area) reaches a maximum at pH 9 and consequently a Table I . Interference studies (manganese = 5pg/L; preconcentration
pH 9 ammonium chloride-ammonia buffer was used routinely potential = -1800mV; preconcentration time = 1 min; rest time =
1 min).
in subsequent work.
Figure 2a shows typical stripping curves for 2 and 5pg/L Interfering metal Added interferunt Mungunese recovery
manganese standards (preconcentration time of 1 min). A rest concentrution [ p g / L ] [%]
period equal to the preconcentration period was found to give
the optimum signal. A long rest period ensures that the solution cu" 10 88
50 [a1 98
is quiescent, such that the oxidizing agent (I-Ig2+)is transported
strictly by diffusion. The effect of a long rest time may also be Ni" 10 54
equivalent to the use of a lower stirring rate for the last part of 10 [bl 98
the preconcentration period reported by Eskilsson and Turner
[ll]. The stripping peaks shown in Figure 2a are well-defined Fe"' 500 [c] 102
and clearly demonstrate that there is no need to remove oxygen 1000 [c] 95
2000 [c] 70
prior to stripping.
[a] In presence of tOOpg/L Zn". [b] In presence of 50pg/L Zn". [c] After
allowing Mn"/Fe"' solution to stand in pH 9.0 buffer overnight.
3.1. Linear Working Range
on the manganese stripping signal was observed up to a Fe/Mn
A linear working range up to 5 pg/L ( I = 0.9989) was mass ratio of 200. This result is particularly relevant for
achieved with a preconcentration time of Imin. Figure 2b seawater samples and many industrial waste water samples as
shows the reproducible stripping curves that can be obtained for the natural pH of the sample should ensure that the iron
40 pg/L manganese using a preconcentrat~ontime of 20 s and concentration is sufficiently low to minimize any possibility of
the stripping curves in Figure 2c (100, 150, 2OOpglL) were interference.
obtained with only 10 s preconcentration time. While well-
defined stripping curves and a linear calibration plot could be
obtained in the 5-200 kg/L concentratioin range (preconcen- 3.5. Analysis of Water Samples
tration time = lOs), the plot had a negative intercept on the
y-axis, which of course does not permit calibration by standard Table 2 presents results for two seawater samples and three
additions. Consequently, all samples required dilution prior to industrial waste water samples. The agreement between the
analysis so that the manganese concentration of the test solution stripping potentiometry result and the certified value for the
in the electrochemical cell was less than 5 iug/L. The reason for CASS-2 seawater is excellent. Agreement between the two
the difference in calibration behavior between the narrow and methods is acceptable for the other samples. The samples used
wide calibration ranges is not clear, but it may be a consequence in this study were not prefiltered nor treated in any other way
of some catalytic enhancement of the stripping signal at high (except for dilution) prior to analysis. The absence of any
manganese concentrations. requirement for pretreatment again demonstrates the simplicity
of the method.
Analyses on the five samples were carried out without the
3.2. Precision addition of zinc and without the need for prior precipitation of
the iron. Table 3 gives some analytical data for the potentially
For a 5 pg/L solution, the r.s.d. was 5.4% for 10 determina- interfering metals in the water samples. It is obvious from these
tions of the same solution using the same mercury film. The data that the ubiquitous character of zinc ensures that it is
r.s.d. increased to 7.0% for 10 determinations of the same present at a sufficiently high concentration to eliminate any
solution, but using a new film for each determination. This interference from copper and nickel. Similarly, the iron
procedure therefore shows good precision for trace levels of concentration is generally of the same order of magnitude as
manganese. the manganese concentration and consequently does not cause
any interference. Therefore, for samples of the type examined
here, it is reasonable to expect that interference from copper,
3.3. Detection Limits nickel and iron will not present a major problem in the
determination of manganese by stripping potentiometry. One of
The limit of detection ( 3 4 was found to be 0.025 pg/L while the industrial waste samples (waste 3) was known to be
the limit of quantitation (IOU) was calculated to be 0.08 pg/L. saturated with oil and grease. These organic components of
The 3c7 limit of detection is significantly better than the detection the sample did not cause any interference with the determin-
limits quoted for other stripping potentiometric methods [9, 111 ation. This demonstrates the applicability of the method to a
and approximates the values for the ASV determination [8] and wide variety of sample types.
the adsorptive stripping voltammetric me:thod [lo].
Table 2. Results for manganese determinations (pg/L) for seawater and
wastewater samples.
3.4. Interferences
Sample Stripping Check Method
Both copper and nickel were found to interfere in the potentiometry value
determination of manganese, as described previously [9, 1 I].
The addition of zinc eliminated this interference (Table 1). Seawater (CASS-2) 2.0 1.99 3= 0.15 Certified value
Significant interference from both iron(u) and iron(m) at a Seawater (Port Phillip Bay) 4.9 5.4 GFASS
mass ratio greater than 10 was also observed. However, if the Industrial waste 1 10.5 8.7 GFAAS
mixed Mn/Fe solutions were allowed to stand overnight in the Industrial waste 2 6.0 6.8 GFAAS
Industrial waste 3 1.3 9.1 GFAAS
pH 9.0 buffer, most of the iron precipitated and no interference

Elertroanalysis, 1995, 7 , No. 4

Determination of Manganese in Wastewaters and Seawater 389

Table 3. General analytical data (units of pg/L) for seawater and - no requirement to remove oxygen at any stage of the
wastewater samples [a]. procedure;
- the capacity to record short stripping times with high
Ni cu Zn Fe [el precision;
Seawater 0.298 0.675 1.97 1.20 2.0 - no need for sample pretreatment before the analysis;
(CASS-2) [b] - the use of a simple pH buffer as supporting electrolyte,
Seawater 1.9 N D [d] 7.4 ND 4.9 thereby minimizing any chance of sample contamination.
(Port Phillip Bay)
Industrial waste 1 950 240 3200 (10 10.5 While specifically being developed in the batch mode, this
Industrial waste 2 104 60 300 (10 6.0 method has the possibility of being adapted to on-line
Industrial waste 3 0.25 10 40 ND 7.3 monitoring. The suitability of stripping potentiometry for
[a] Analyses performed by CRA-Advanced Technical Development
on-line and/or on-site monitoring is under consideration in our
unless otherwise specified. [b] Certified values except for Mn. [c] Values laboratory.
determined by stripping potentiometry (see Table 2). [d] N D = not
determined.

All stripping potentiometric analyses were carried out with a 5. Acknowledgements

preconcentration time of 1min or less. Concentrations as low as
0.5 pg/L could be reliably determined with a preconcentration
time of 1 min. The TraceLabTM system used in this work
features a data acquisition rate of 30kHz, equivalent to a
sampling rate of 33 ps. This fast sampling rate allowed stripping
times between 10 and 20ms to be recorded with precisions of
about 5% r.s.d.
With a rest time equal to the preconcentration time and a
stripping time in the order of milliseconds and as oxygen
removal is not employed, the analysis time is about 2min. This
demonstrates the speed with which determinations of manga-
nese at the trace level can be performed by stripping
potentiometry. Furthermore, the limit of detection is compar-
able to that achievable by voltammetric methods. This
potentiometric stripping procedure has the advantage of a
simple test solution composition and does not require the
addition of a chelate as is needed in adsorptive voltammetnc
procedures.
4. Conclusion
A rapid method for the determination of low concentrations
of manganese has been developed. The significant features of
this new approach include:
This work was sponsored by funding provided by BHP
Research and CRA-Advanced Technical Development. The
provision of a TraceLab system by Radiometer (Copenhagen) is
acknowledged. The Director of the Center for Scientific
Instrumentation at La Trobe University is thanked for
facilitating this study as is Mr S. Roden of CRA-Advanced
Technical Development for assistance with manganese analyses
by graphite furnace atomic absorption spectrophotometry.
6. References
[l] E.R. Sholkovitz,in: Chemical Process in Lakes (Ed: W. Stumm), Wiley,
New York 1985, Ch. 6.
[2] B. Chiswell, D.R. Dixon, G. Hamilton, L.I. Sly, T.D. White, Chem. Aust.
1992, 59, 400.
[3] B. Chiswell, M.B. Mokhtar, in: Surface and Colloid Chemistry in Natural
Waters and Water Treatment (Ed: R. Beckett), Plenum, 1987, p. 143.
[4] W. Davison, J . Elecrroanal. Chem. 1976, 72, 229.
[5] W. Davison, Limnol. Oceanogr. 1977,22, 746.
[6] S. Knox, D.R. Turner, Estuarine Coastal Mar. Sci. 1980, 10, 317.
[7] S . Knox, D.R. Turner, A.G. Dickson, M.I. Liddicoat, M. Whitfield, E.I.
Butler, Estuarine Coastal Mar. Sci. 1981, 13, 357.
[8] R.J. OHalloran, Anal. Chim. Acta 1982, 140, 51.
[9] J.F. Coetzee, M.J. Ecoff, Anal. Chem. 1991,63,957.
[lo] J. Wang, J.S. Mahmoud, Anal. Chim. Acta 1986, 182, 147.
[Ill H. Eskilsson, D.R. Turner, Anal. Chim. Acta 1984, 161, 293.

- short (1 min) preconcentration time and consequent short

overall analysis time;

Electroanalysis 1995, 7, No. 4