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Environ Monit Assess (2014) 186:8865–8874

DOI 10.1007/s10661-014-4051-8

The simultaneous stripping of arsenic and selenium


from wastewaters using hollow-fibre supported liquid
membranes
Lihle D. Mafu & Titus A. M. Msagati &
Bhekie B. Mamba

Received: 30 May 2013 / Accepted: 11 September 2014 / Published online: 25 September 2014
# Springer International Publishing Switzerland 2014

Abstract The extraction of total arsenic and selenium Introduction


using hollow-fibre supported liquid membranes
(HFSLMs), with specific interest in the optimal condi- Arsenic and selenium are amongst metallic pollutants
tions for the extraction in wastewater, is reported. The found in many aquatic environments, and they both
extraction time, type of liquid membrane, sample and exist in two dominant oxidation states, namely, As(III)
donor pH and stirring rate were optimised, and thereaf- and As(V), and Se(IV) and Se(VI), respectively (Jain
ter, the developed method was tested in real wastewater and Ali 2000; Kumar and Riyazuddin 2011; Sharif et al.
samples. The optimal HFSLMs adopted, after optimisa- 2005). Arsenic and selenium compounds and/or com-
tion tests, comprised of Aliquat 336, 0.8 M NaOH, plexes have been used for over a decade in pesticides,
200 rpm and 80 min as the extractant, stripping phase, wood preservatives and electronic industries, but their
stirring rate and reaction time, respectively. The devel- main sources in the environment are fossil fuel and
oped method had reasonable-to-high extraction efficien- biomass combustion, natural disasters such as volcanic
cies in real wastewater samples with the final effluent eruptions, as well as in food additives and cosmetics
recording as high as 73 and 78 % removal efficiencies (Kobya et al. 2011; Miekeley et al. 2005; Najafi et al.
for Se and As, respectively. Considering the initial con- 2010; Salleh et al. 2000). Both these metalloids and their
centrations found in the samples, use of this developed complexes have been reported to have carcinogenic
method could bring down the concentrations to levels effects which may lead to the disruption of ATP produc-
admissible by the United States Environmental tion, lung cancer, cancer of the kidneys, etc. (Dogan
Protection Agency (US-EPA) and World Health et al. 2010). It is thus very important to remove these
Organisation (WHO). pollutants, existing in any form, because they tend to
undergo redox reactions which may lead to the forma-
Keywords Aliquat 336 . Arsenic . Selenium . tion of one or more of the toxic speciation forms. For
Hollow-fibre supported liquid membranes . Wastewater example, As(V) can easily be reduced to As(III) in
acidic conditions just like Se(VI) can easily be reduced
to Se(IV) in acidic conditions.
L. D. Mafu : T. A. M. Msagati (*) : B. B. Mamba Sample preparation and remediation methods that
College of Science, Engineering and Technology, have previously been used for the removal of heavy
Nanotechnology for Water Sustainability Research Unit, metals such as As and Se include solvent extraction,
University of South Africa (Florida),
UNISA Science Campus, Corner of Christiaan de Wet Road co-precipitation, solid-phase extraction, coagulation,
& Pioneer Avenue, Florida, 1709 Johannesburg, South Africa flocculation, ion exchange and ultrafiltration (Najafi
e-mail: msagatam@unisa.ac.za et al. 2010; Miekeley et al. 2005; Kobya et al. 2011;
8866 Environ Monit Assess (2014) 186:8865–8874

Manajlovic et al. 2009). Not only were these methods Organic solvents have been reported in the literature
used for the remediation of As and Se, other metals as for the enrichment of metals and include octanol
well have been pre-concentrated and extracted. All these (Es’haghi and Azmoodeh 2010), n-dodecane (Liu and
methods have been applied with various degrees of Shi 2009) undecane, CYANEX® 301 (Pancharoen et al.
success, but shortcomings such as the usage of large 2009) and AliquatTM 336 (Fontàs et al. 2000). These
volumes of organic solvents, complex operations, diffi- solvents have been used very effectively to extract
culties in automation, longer extraction times and also metals such as copper (Es’haghi and Azmoodeh 2010;
high capital and maintenance costs overshadowed their Yang and Kocherginsky 2006), lead (Zeng et al. 2010),
successes (Vassileva et al. 2001; Zeng et al. 2010). cadmium (Peng et al. 2007) and mercury (Pancharoen
The use of hollow-fibre supported liquid membranes et al. 2009). Aliquat 336 is a basic extractant; it is highly
(HFSLMs) is not new but has been used to remove other recommended for utilisation in HFSLM procedures for
pollutants (both organic and inorganic) mostly individ- separation of metals due to its ease of forming temporal
ually. Reports on simultaneous extraction of pollutants complexes with most metals, hence facilitating the
using HFSLMs are not too common (Liu et al. 2007; movement of pollutants from the sample phase to the
Poliwoda et al. 2010; Zhang et al. 2010). It has many donor phase. It is also categorised as one of the green
advantages which far outweigh its disadvantages, and solvents (Guell et al. 2008). The structure of Aliquat 336
among the striking features of the HFSLM technique is consists of long hydrocarbon chains attached to a central
their high removal efficiencies, less usage of organic and positive nitrogen atom which makes it a more
solvents and ease in automation (Zeng et al. 2010). suitable extractant for a wide range of anionic metal
Figure 1 shows a drawing of a polypropylene hollow compounds. It can form salts with anions over a wide
fibre. It is a porous tube with a hollow lumen which pH range; hence, it finds most applications in acidic
holds the stripping phase, pores which are immobilised media to slightly alkaline pH levels (Fontàs et al.
with a few microlitres of organic solvent which facili- 2000). It has also been used to remove heavy metals
tates the stripping/extraction. from wastewater in the textile industries (Asai et al.
The outside of the hollow fibre generally contains the 2006), as an anti-static agent, in the cosmetic industry,
unwanted pollutants where the extraction mechanism is and as a colorant or a de-colorant (Guell et al. 2008;
highly dependent on the ability of the organic phase to Nayl 2010).
extract analytes and also the stripping solution’s affinity Considering that Aliquat 336 is generally used in
to the analytes. Another instrumental factor in the strip- metal extraction and has the ability to strip most toxic
ping is the difference in pH values between the sample metals, the need to carry out a study on more than one
and the stripping phase because it facilitates the move- metal extraction is significant. To the best of our knowl-
ment of ions between the two phases and hence the edge, the simultaneous stripping of these two metals
movement of the cationic species as well (Chimuka using Aliquat 336 has not been performed successfully
et al. 2010; Lozano et al. 2011). to date, and no findings have yet been reported in

Fig. 1 Hollow-fibre supported


liquid membrane
Environ Monit Assess (2014) 186:8865–8874 8867

literature. This work reports on the development of a Table 1 Parameters and their values measured in situ
method using a hollow-fibre supported liquid mem- Sampling stage pH Temperature Conductivity
brane for the effective pre-concentration of arsenic and (°C) (18.4 MΩ)
selenium from wastewater for detection and analysis by
various analytical techniques. Anaerobic 1.9 20.1 3,999
Anoxic 2.1 19.8 3,999
Aeration 3.0 20.0 3,999
Materials and methods Final effluent 6 21.7 2,137

Chemicals and reagents


bulk stock standard solutions. Subsequent dilution stan-
Undecane, octanol, Aliquat 336, acetone, nitric acid, dards were prepared from the stock standard solutions
hydrochloric acid and sodium hydroxide (AR grade), by dilutions using deionised water.
supplied by Merck (Darmstadt, Germany), were all of
analytical grade and were used without any further HFSLM procedure
purification. Deionised water (18.4-MΩ conductivity)
was obtained from an in-house reverse osmosis system A polypropylene hollow fibre was cut into equal
and was used for most dilutions and the preparation of lengths, 6 cm each, and cleaned with acetone, and one
standards. Q3/2 Accurel polypropylene hollow-fibre end of the polypropylene hollow fibre was sealed. The
membrane (200-μm wall thickness, 600-μm inner di- pores of the hollow fibre were then immobilised with the
ameter and 0.2-μm pore size) was obtained from organic solvent (Aliquat 336, Aliquat 336+octanol and
Membrana GmbH (Wuppertal, Germany). Aliquat 336+undecane) of choice, thus allowing the
solution to fill the pores. The hollow fibre was then
Instrumentation rinsed lightly, and an aqueous solution acting as the
acceptor phase was introduced into the lumen of the
For the analysis and quantification of the stripped and hollow fibre by syringe. The other end was also sealed
pre-concentrated arsenic and selenium, inductively and then the polypropylene hollow fibre was immersed
coupled plasma-optical emission spectroscopy (ICP- in a sample solution while stirring for an optimal period
OES) was used (Wirsam Scientific, GBC Quantima of time. In order to ensure optimal extraction perfor-
Series ICP connected to a GBC SDS 720 auto sampler). mance, selectivity and reproducibility of the method,
different conditions such as the temperature, pH of both
Sampling the sample (donor) and organic phases, and the extrac-
tion time were optimised in a sequence where one
The treatment plan of interest is categorised into differ- parameter is varied while keeping the other variables
ent stages from which each plays a different role in the constant. The enrichment factor, per cent extraction and
treatment process. The chosen stages are anaerobic, the amount extracted were then calculated using
anoxic, aeration and the final effluent. On sampling, Eqs. (1), (2) and (3), respectively:
samples were kept in sampling bottles that had been
C fst
rinsed with 10 % HNO3 and these samples were kept EF ¼ ð1Þ
C is
below 5 °C until use. Sample pH, temperature and
conductivity were recorded in situ and are presented in C i −C f
Table 1. %E ¼  100 ð2Þ
Ci

Preparation of standards E ¼ C i −C f ð3Þ

Arsenic and selenium metals were dissolved in a small where


amount of 15 M aqua regia and 0.5 M HNO3, respec-
tively, and then diluted to the mark with deionised water EF is the enrichment factor
(in a 1,000-ml volumetric flask), and this formed the Cfst is the initial concentration in the stripping phase
8868 Environ Monit Assess (2014) 186:8865–8874

Cis is the initial analyte concentration in the sample stripping phase is aqua regia 0.1 M, Aliquat+undecane
phase (1:1) as the organic phase and 100 μg l−1 in 0.1 M aqua
%E is the percentage removal of analytes from the regia. The results for experiments carried out for arsenic
sample are presented in Fig. 2.
Ci is the initial concentration in the sample before From Fig. 2, it is evident that all the organic solvents
extraction tested were able to remove more than 20 % of the total
Cf is the final concentration in the sample after As in all the solutions. Also to be noted is that the
extraction alteration of each parameter affected the percentage
E is the extracted amount removal either positively or negatively. As outlined in
many other studies (Chimuka et al. 2010; Pancharoen
et al. 2009; Peng et al. 2007), the performance of the
HFSLM technique is governed by parameters such as
Results and discussions pH, temperature and extraction duration; therefore, it is
essential to optimise these factors in order to develop an
Optimisation of various parameters effective technique operating optimally to remove pol-
lutants in samples, be it organic or inorganic.
Organic phase and pH From the first optimisation step, it was evident that
sodium hydroxide was the best stripping reagent in
The organic phase or extractant is a fundamental tool in terms of efficiency in the stripping phase (area marked
the operations of a hollow-fibre supported liquid mem- 3 in Fig. 2). By using sodium hydroxide, it was possible
brane as metal ions are transferred into the stripping to achieve recoveries of more than 69 % independent of
solution while the extractant recedes and diffuses to the acidity of the sample or the organic phase used. This
the opposite side of the liquid membrane by the concen- implies that sodium hydroxide was a better stripping
tration gradient to react again with metal ions in the feed phase reagent compared to the acidic aqua regia. Also,
solution(Chimuka et al. 2010). Different organic sol- in Fig. 2, it can be observed that the samples with a
vents extract different pollutants differently, but the higher acidity seem to enhance the stripping of arsenic
amount of stripped pollutant is almost the same for as evidenced from the rise of the slope in the graph
inorganic species with similar properties (Jönsson and (removal percentage) in the sample compartments (i.e.
Mathiasson 2000). In this study, undiluted Aliquat 336, 3.3.3>3.3.2, 3.2.3>3.2.2 and 3.1.3>3.1.2).
Aliquat/octan-1-ol (1:1) and Aliquat/undecane (1:1) The circled areas marked (i), (ii) and (iii) in Fig. 2
were tested to evaluate their performance in the removal represent the highest points of extraction in each stage.
of both arsenic and selenium in synthetic samples con- Another observation from Fig. 2 is that Aliquat 336 was
taining 500 μg l−1 of each metal element. The influence found to be the best extractant in all stages as it was able
of pH and temperature on the performance of the differ- to strip more than 50 % of the target metallic species.
ent extractant proportions/mixtures was investigated. The observation can be summarised in that phase sys-
Table 2 shows the parameters investigated in the three tems 3.1.2 and 3.1.3 were the most efficient in terms of
organic phases. the amount of total arsenic removed even though phase
The primary optimisation model incorporates codes systems 3.2.2, 3.2.3, 3.3.2 and 3.3.3 also achieved more
which represent specific groups, e.g. 132 means that the than 70 % of arsenic removals. Therefore, phase system
3.1.3 was used for all subsequent stripping experiments.
Figure 3 shows the trend in the optimisation of phase
Table 2 Optimisation setup
systems in the stripping of selenium.
Stripping solutions Organic phase Samples One significant observation from Fig. 3 is that all the
HFSLM phase combinations and the net extraction per-
Aqua regia 0.1 M Aliquat only Aqua regia only centages of selenium were found to be lower than those
Aqua regia ≥0.1 M Aliquat+octanol (1:1) 100 μg l−1 in 0.1 of arsenic although high enough (~77 %) to conclude
M aqua regia
that there was substantial stripping. It is thus worth
NaOH (0.2 M) Aliquat+undecane (1:1) 100 μg l−1 in 0.2
noting that the removal trends shown in Figs. 2 and 3
M aqua regia
are similar, in that the highest stripping for both metals
Environ Monit Assess (2014) 186:8865–8874 8869

Fig. 2 Primary optimisation


results for arsenic (NB: phase
combinations as in Table 3)

was obtained when phase systems 3.1.2 and 3.1.3 were Mathiasson 2000). Appropriate optimisation of the ex-
employed. These phase systems are combinations of traction time in order to enhance the enrichment of the
NaOH (stripping phase), Aliquat 336 (extractant), ana- analyte is required. On the other hand, it is essential that
lyte in 0.1 M aqua regia and NaOH (stripping phase), the sample have sufficient contact time with the
and Aliquat 336 (extractant) for analytes present in HFSLMs for the effective mass transfer to occur. The
2.0 M aqua regia. time optimisation experiments for stripping time rang-
For the subsequent series of optimisation steps, un- ing from 10 to 110 min using 0.5 M NaOH as the
diluted Aliquat 336 was used as the extractant of choice stripping solution, Aliquat 336 as the extractant and
and NaOH as the stripping reagent for acidified samples. 100 μg l−1 As and Se dissolved in 0.1 M aqua regia
were carried out separately for the two different toxi-
Stripping time dependence cants (arsenic and selenium), and the results are present-
ed in Fig. 4.
Stripping of analytes from environmental matrices using From Fig. 4, it can be seen that the amount of both
liquid membranes is time dependent (Jönsson and arsenic and selenium extracted increased with

Fig. 3 Optimisation of phase


system in the stripping
experiments for selenium
(NB: phase combinations
as in Table 3)
8870 Environ Monit Assess (2014) 186:8865–8874

Fig. 4 The amount of inorganics


removed as a function of time

increasing extraction time up until 70 min after which a extracted after 70 min, whilst extraction of selenium
decrease was observed. A significant decline started was highest at a time of 90 min. Taking this factor into
after 80 min of extraction time for both arsenic and consideration, the optimal extraction time for the simul-
selenium. This can be attributed to the possible back- taneous stripping of arsenic and selenium was set at
diffusion of the inorganic species (arsenic and selenium) 80 min.
into the sample phase that may be caused by the changes
in the pH of the receiving phase and also the new Effect of stirring rate
concentration gradient established after extraction
(Lozano et al. 2011). According to Guell et al. (2008), stirring enhances mass
Another factor that may be playing an important role transfer during the enrichment processes; it promotes
in the effective stripping of the two metalloids is the size the equilibrium of solutes in the stirred sample and
of the two species because the bigger the size of the improves the continued active interaction between the
metalloid, the lower the efficiency in the extraction sample and the extraction material. The effect of stirring
(Lozano et al. 2011). The two metalloids differ in terms rate was therefore investigated by varying the stirring
of their molecular sizes and thus their stripping trends rate from 20 up to 1,000 r min−1, while monitoring the
differ, such that for arsenic, the highest amount was stripping capacity, as shown in Fig. 5.

Fig. 5 Effect of stirring rate on


extraction
Environ Monit Assess (2014) 186:8865–8874 8871

Fig. 6 Effect of the concentration


variation of NaOH in mol/L

Figure 5 shows that there was a slight increase in the The results given in Fig. 6 show that the concentra-
percentage removal as the stirring rate was increased tion of NaOH in the stripping phase does affect the
from 20 to 300 r min−1 with a maximum and a signifi- stripping of the two target pollutants, because the per-
cant decline with a further increase in the stirring rate centage stripped increased with increasing concentra-
(Fig. 5). This may be attributed to the fact that at high tion of NaOH almost throughout the concentration
stirring rate, there is minimal contact between the sam- range studied. The optimum concentration for subse-
ple molecule and the liquid membrane, thus slowing quent experiments was then fixed at 0.8 M. This implies
down the diffusion of analyte molecules across the that the stripping of these elements depends solely on
hydrophobic liquid membrane supported in the pores the amount of ions freely moving in the stripping solu-
of the hollow fibre. tion. Since the pollutants are also ions in solution, their
removal is therefore improved as the amounts of ions
Effect of the reagent concentration in the stripping freely roaming in the stripping solution are increased.
phase
Method validation and the simultaneous removal of As
Since the stripping phase plays an essential role in the and Se
membrane extraction processes (Chimuka et al. 2010), it
is essential to find the ideal reagent concentration suit- After having optimised the various operational parame-
able for optimal removal of analytes. The effect of the ters, the technique was then tested on the simultaneous
concentration of the NaOH as the stripping phase re- stripping or removal of both target pollutants in samples
agent for the two metals was investigated by varying the from a wastewater treatment plant. The conditions under
concentration from 0.1 up to 1.0 M while monitoring the which this test was performed are listed in Table 3.
percentage stripped (Fig. 6).
Table 4 Selectivity of HFSLM for the stripping of arsenic and
selenium
Table 3 Optimal parameters for developed HFSLM
Element Removal (%) Enrichment factors
Parameter Optimal response
As 78 99
Stripping reagent 0.8 M NaOH Se 74 93
Extractant Aliquat 336 (undiluted) Pb 39 20
Extraction time 80 min Cd 48 29
Stirring rate 200 r min−1 Hg 41 34
8872 Environ Monit Assess (2014) 186:8865–8874

Table 5 Performance of the HFSLM on samples from wastewater selectivity of HFSLMs for the target species arsenic and
treatment plants
selenium during simultaneous extraction and stripping
Sampling stage Removal (%) (As) Removal (%) (Se) in one single stage in the presence of lead, mercury and
cadmium.
Anaerobic 65 60
Anoxic 64 60 Analysis of wastewater treatment plant samples
Aeration 73 69
Final effluent 78 73 After the optimisation procedure, this method was then
implemented in environmental wastewater effluent sam-
ples to pre-concentrate As and Se. Wastewater treatment
For validation of the developed method, the metal plant samples (samples collected as described in the
recovery experiments were performed using a simulated “Sampling” section) were filtered through a Whatman
solution containing metal concentrations of 0.1 mg l−1, filter paper without any adjustment to the sample pH.
and the extraction using HFSLMs was carried out using All the treatment stages of the wastewater treatment
optimal conditions as given in Table 3. It was found that plant, i.e. pre-anoxic, anaerobic, anoxic, aeration, elutri-
the method could successfully remove 81 and 76 % of ation and final effluent stages, were sampled and
arsenic and selenium, respectively, with pre- analysed. The results obtained are given in Table 5.
concentration factors of 101 and 93, respectively. The results show that the developed method is capable
of removing arsenic and selenium from wastewater
Selectivity studies for the developed method sources. Further observations suggest that most of the
toxicants are removed in the final effluent stage (78 and
In as much as the two toxicants were removed from the 73 % of arsenic and selenium, respectively) even though
wastewater matrix, it was essential to carry out selectiv- during the aeration stage the removals were also high
ity studies to determine the specificity of the developed (73 and 69 % of arsenic and selenium, respectively).
method for the targeted analytes. To accomplish this The proposed possible mechanism for the simulta-
task, a synthetic solution was prepared and spiked with neous stripping of arsenic and selenium whereby all the
arsenic, selenium and also lead, mercury, and cadmium, forms of arsenic and selenium present in the solution
and the HFSLM extraction was performed under the interact with the Aliquat 336 to form arsenic and sele-
optimal conditions as identified (Table 3). The results nium complexes in the hydrophobic membrane phase is
are depicted in Table 4 and clearly show a fairly good shown in Fig. 7. The anionic part of the complex formed

Fig. 7 Proposed extraction mechanism for the simultaneous extraction of both arsenic and selenium
Environ Monit Assess (2014) 186:8865–8874 8873

in the membrane phase is then extracted by the NaOH degrees of freedom and conclude that there is no differ-
during the stripping phase forming a sodium-arsenic/ ence in the removal efficiencies of As and Se simulta-
selenium complex, hence removing the arsenic/ neously using the developed method.
selenium from the sample in the sample phase. The
mechanism may be represented by the following general
Eqs. (4) and (5) Zhang et al. 2010: Conclusions
A þ N R4 Cl→N R4 A þ Cl − ð4Þ
A hollow-fibre supported liquid membrane method was
N R4 A þ NaOH→N R4 OH þ NaA ð5Þ successfully developed by optimising experimental pa-
rameters such as sample pH, acceptor phase pH, type
Equations (4) and (5) show the interactions that take
and concentration of acceptor phase solution, stirring
place at the sample phase-membrane interface and at the
rate and extraction time. The summary of the optimised
stripping phase-membrane interface, respectively,
results is presented in Table 3. On application in actual
whereby A represents each of the two As and Se
wastewater samples, the developed method was able to
oxyanions. It can be noted from Fig. 7 that as the
pre-concentrate and remove 78 and 73 % of arsenic and
extraction progresses, OH− takes the place of Cl−.
selenium, respectively, from the final effluent stage
sample. This developed method also showed a selectiv-
Statistical evaluation of As and Se removal
ity coefficient of >1 towards both target analytes. From
analysis of the method performance on real water sam-
The simultaneous removal efficiency of the developed
ples, it was concluded that the removal of As and Se is
method is satisfactory and it opens up new possibilities
the same which may also imply that the remediation of
in remediation science. However, the quantities of the
these analytes in water happens via the same
removals of As against Se seem to be in the same region.
mechanism.
As such, the test statistic t was analysed for pooled data
to establish if there is any statistical difference in the
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