Arsenic Removal with Ferric Sulphate by Precipitation and Flotation

U. Yenial, M.K. Aydoan, G. Bulut, A.A. Sirkeci

Department of Mineral Processing Engineering, Istanbul Technical University, Istanbul, Turkey
*Corresponding Author (yenial@itu.edu.tr)

ABSTRACT: Arsenic contamination is one of the environmental problems which become popular
because of global warming and geothermal and tectonic activities. Arsenic contamination has occurred in
groundwater and surface water almost every country. Generally, in Turkey this water contamination is in
west locations and several methods were developed for arsenic removal. In this study, adsorbing colloid
flotation and precipitation methods were applied for removing arsenic from waters. Ferric sulphate
(Fe2(SO4)3xH2O) and ferric chloride was used for generation arsenic-iron compounds. In flotation
experiments arsenic removal investigated with pH, collector type and dosage, ferric concentration and
acid type. In precipitation experiments, pH and time were examined with ferric sulphate. According to
adsorbing colloid flotation experiments arsenic content lowered from 10 ppm to 0.01 ppm with using
SDS and K-Oleate. In addition 0.01 ppm arsenic content was obtained at 48 hours at precipitation
experiments. As a result it is found that both methods are effective and flotation was found to be an
alternate to precipitation for arsenic removal.

INTRODUCTION

Arsenic is a semi-metallic element that causes some symptoms, in the human body until it reaches a
concentration at which it induces chronic toxicity. As and its compounds are highly toxic. The minimum
lethal dose for adult humans for various compounds has been reported to be 100 to 200 mg (Schweitzer
and Pesterfield, 2010). Short-term exposure to arsenic can lead to dermal, respiratory, gastrointestinal,
cardiovascular, mutagenic and carcinogenic effects, and it may interfere with the immune system. Long-
term exposure to arsenic can cause cancer of the bladder, lungs, skin, kidney, liver, nasal passages and
prostate (NRC, 1999). Thus, The World Health Organization (WHO, 2006) the United States
Environmental Protection Agency (USEPA, 2009) and also Turkish Standards Institute (TSE-266, 2005)
have applied the maximum allowable level of arsenic in drinking water as 10 g/L (10 ppb).
Arsenic in natural waters is a worldwide problem. Arsenic pollution has been reported recently in
USA, China, Chile, Bangladesh, Taiwan, Mexico, Romania, United Kingdom, Argentina, Poland,
Canada, Hungary, New Zealand, Vietnam, Japan and India (Smedley and Kinniburgh, 2002). It is stated
that Turkey is one of the countries under the threat of arsenic pollution. Arsenic concentrations are
ranging from 10 g/L to 7754 g/L in the west region of Turkey (Alta et al., 2011).
Arsenic in water systems is mostly introduced from natural and anthropogenic sources. Natural sources
include the washout and erosion of arsenic-containing mineral ores and soil, which probably occurs
because of long-term geochemical changes. Anthropogenic sources include forestry, agricultural
application of pesticides, herbicides and fertilizers, and industrial effluents from metallurgy, electronics,
mining, glass processing, ceramic, pharmaceuticals, dye and pesticides manufacturing, wood
preservatives, petroleum refining and landfill leaching (Kim et al., 2002; Budinova et al., 2009;
Altundogan et al., 2000; Smedley and Kinniburgh, 2002). Industrial wastewater is a prominent
contamination source. Arsenic in aqueous systems includes inorganic arsenic and organic arsenic.
Inorganic arsenic is more poisonous to biological systems than organic arsenic (Schaeffer et al., 2005).
Since As occurs in Cu and Pb minerals, flue dusts from smelters treating these minerals contain As2O3.
These dust are the principal industrial source of As. The sulfide ores realgar and orpiment are roasted in
air to give oxide As2O3As forms two oxides arsenic (III) and arsenic (V) oxide As2O5. The dissolution of
As2O3 in H2O gives the arsenious acid H3AsO3. H3AsO3 is very weak monoprotic acid, with the anion
H2AsO3- having a log Kp value of 9.2. Arsenic acid H3AsO4 is formed by the oxidation of As or As2O3
with HNO3 or by adding As2O5 to water. The tribasic acid completely soluble in water and its anions
show the following log Kp values:

AsO43-/ HAsO42- pK=11.6 (1)

HAsO42-/ H2AsO4- pK=6.8 (2)
H2AsO4-/ H3AsO4 pK=2.3 (3)

To remove arsenic from water, various methods have been employed. Techniques have included
chemical coagulation precipitation (Pal et al., 2007), electrolysis (Emamjomeh and Sivakumar, 2009),
liquid-liquid extraction (Guell et al., 2010), ion exchange (Anirudhan and Jalajamony, 2010; Greenleof et
al., 2006), reverse osmosis (Walker et al., 2008; George et al., 2006), membrane separation (Fagarassy et
al., 2009; Manna et al., 2010) adsorption (Yenial, 2012) and flotation (Aydoan, 2011, Peng and Di,
1994; Kordmostafapour et al., 2006; Stoica et al., 2008). Flotation technique is widely used for mineral
separation based on their surface character, such as hydrophobic and hydrophilic. The use of flotation in
the wastewater treatment is showing a great potential due to the high throughput of modern equipment,
low sludge generation and the high efficiency of the separation schemes already available (Rubio, et al.,
2002).
Adsorbing colloid flotation (ACF) is based on the adsorption of material, in this case the waste to be
treated, onto colloidal sized particles which then collect at the gas liquid interface. It typically involves
the formation of a hydrous metal oxide (e.g. hydrous oxides of Fe (III) and Al (III)) and the adsorption or
coprecipitation of waste species onto this hydrous metal oxide. If not hydrophobic, the colloid is made so
by the addition of a surfactant. Flotation of the hydrophobic colloid is then affected by passing it through
a stream of gas (usually compressed air) where the surfactant coated colloid is collected into foam. The
foam, when separated from the mother liquid, contains the waste in a concentrated form suitable for land
disposal. The foam produced here gives rise the possibility of a stabilized land disposal form. Much of the
significance and control of these steps can be traced through the history and origin of ACF, and
particularly its similarity to microflotation and precipitate flotation (Lemlich, 1972).
The objective of present work was to investigate various parameters affecting the removal of arsenic
by adsorbing colloid flotation and precipitation by using ferric sulfates. pH, ferric sulfate and arsenic
concentration effect and two types of collectors were investigated to remove arsenic.

MATERIAL AND METHOD

All chemicals used in this study were analytical grade. Anionic sodium dodecyl sulfate (SDS;
(C12H25SO4Na) and anionic potassium Oleatee (K-Oleatee, (C18H33KO2) were used as collectors. Fe+3
solution was prepared dissolving Fe2(SO4)3xH2O salt in a double distilled water. The pH was adjusted
using NaOH, H2SO4 when necessary. Arsenic (Merck) was provided as 1000 ppm standard solution and
diluted to desired concentrations for experiments. All experiments were carried out with deionized
distilled water.
In precipitation experiments, pH and time were examined with ferric sulphate. 10 ppm arsenic and 20
pmm ferric was added to 100 mL solution, after 5 minutes mixing time, the solution was left for
precipitation. After essential precipitation time upper part of the solution was taken for arsenic analyzing.
In the adsorbing colloid flotation tests, a laboratory flotation column with 125 mL volume was used. The
flotation column was constructed by a 3 cm diameter and 24 cm high glass tubing with a fritted glass
disk. The feed solution containing as for the flotation column was prepared in a beaker adding required
amount of Fe+3 and pH of the solution was adjusted. The mixed solution was stirred for 5 minutes, then
SDS or K-Oleatee was added, and the solution was stirred again for 5 minutes using a magnetic stirrer.
The solution was transferred in to the flotation cell. Flotation test was performed for 5 minutes at 400
mL/min of air rate. At the top the flotation cell, a thin layer of foam was formed. The foam containing
the precipitates overflowed continuously through a foam discharge port and was collected in a beaker.
The foam product was generally a small portion of the original solution volume. After 5 minutes flotation
time the gas was turned off and remaining solution was taken from the lower part of the flotation cell to
determine the arsenic concentration remaining in the solution.
Arsenic analysis made by molybdate method procedure (Funing and Daren 1982). The results were
evaluated as arsenic removal and the residual arsenic concentration was expressed as the removal
efficiency of arsenic (As removal, %) as follows:

Arsenic Removal, %= (1- Cf/Ci)*100 (4)

Where Ci and Cf are the initial and final (residual) concentrations of arsenic solutions, respectively.

RESULTS AND DISCUSSION

Precipitation experiments were performed with constant arsenate concentration (10 ppm) ferric
concentration (40 ppm) to investigate the effect of pH.
Adsorbing colloid flotation experiments were carried out with constant arsenate concentration (10
ppm) ferric concentration (40 ppm) to search effect of pH, collector type and concentration of ferric
where the dosages of SDS and K-Oleatee were 20 ppm. The pH of the solution was adjusted using NaOH
and H2SO4.

Precipitation Experiments

The arsenic removal against to pH varied by time was presented in Figure 1. As it seems from figure,
increasing time increased the arsenic removal. After 48 hours, 0.07, 0.01, 0.28, 0.30 arsenic
concentrations were measured at pH 4, 5, 5.5, 6 respectively. Thus the maximum arsenic removal
obtained at pH 5.

Figure 1 Precipitation experiments related with the pH and time.

When an iron salt, for instance FeCl3 or Fe2(SO4)3, is added to water, it hydrolyzes to form ferric
hydroxide [Fe(OH)3(s)], which has a net positive charge on the surface of the particles formed. The net
positive charge of Fe(OH)3(s) particles changes depending on the water pH, and as the pH of feed water
decreases, the number of positively charged sites on the Fe(OH)3(s) particles increases. A pH around 7.3
is required for Fe(OH)3(s) particles to have a net positive charge. Since arsenate is an anion and will
adsorb onto positively charged Fe(OH)3(s) particles by surface complexation, arsenic removal should be
optimized at a pH of 7.3 or less. Arsenic removal may also occur at higher pH levels, but not as
effectively as at lower pH values (Chwirka et al., 2004). It was also reported that better arsenic removal at
low pH values is due to decreased concentration of hydroxide anion, which is an excellent ligand that
strongly competes with arsenic for adsorption sites (Ghurye et al., 2004).

Adsorbing Colloid Flotation Experiments

Effect of Collector type and pH

The removal arsenic as a function of pH is shown in Figure 2 with using SDS as a collector. As it seems
from figure, at pH 4 arsenic removal was found to be 99.4% and arsenic concentration in the remaining
water found as 0.6 ppm. Same experiment performed with K-Oleatee and the results are shown in Figure
3.As it seems from figure, at pH 5.5 arsenic removal was found as 87.2% and arsenic concentration in the
remaining water found to be 1.28 ppm. Both collectors were effective below pH 6 due to arsenic behavior
in aquatic system. SDS found as more effective than K-Oleatee, thus SDS was used in continued
experiments.
100 10
Removal

Arsenic Concentration, ppm

80 8
Arsenic Removal, %

60 6

40 4

20 2

0 0
3 4 5 6 7 8 9 10
pH
Figure 2. Arsenic removal by using SDS as a collector.
100 10
Removal
Arsenic Concentration, ppm

80 8
Arsenic Removal, %

60 6

40 4

20 2

0 0
3 4 5 6 7 8 9 10
pH
Figure 3. Arsenic removal by using K-Oleatee as a collector.
Effect of Collector Dosage

Figure 4 shows the effect of the SDS concentration on arsenic removal. A concentration of 40 ppm was
found to produce stable and efficient foam for arsenic removal. If concentration of SDS was very low, a
thin and unstable foam layer was generated and readily broke apart. On the other hand, if concentration of
SDS was too high, the formation of hydrophilic micelles around the particles made the flocs unfloatable
(Peng and Di, 1994). Thus increasing SDs concentration increased arsenic removal, as a result the
remaining water consisted 0.02 ppm As.

Figure 4. Collector dosage effect on arsenic removal.

Effect of Arsenic Ferric Ratio

In order to investigate the effect of the ferric concentration on the arsenic removal 10, 20 and 40 ppm
ferric added to solution at pH 4. The efficiency of arsenic removal improved with increasing ferric
concentration as shown in Table 1. Higher ferric concentrations produce higher surface area for arsenic
adsorption. At 40 ppm ferric concentration arsenic removal found to be 99.9%. Thus there was no need
to use more ferric arsenic removal.

Table 1. Effect of arsenic : ferric ratio on arsenic

removal
As:Fe Arsenic Removal, As Concentration,
(ppm) (%) ppm
10 : 10 96.3 0.4
10 : 20 98.8 0.2
10 : 40 99.9 0.01

The arsenic removal efficiency is thought to be strongly dependent on the initial iron and arsenic
concentrations (U.S. EPA, 2005). The U.S. EPA (2005) suggests that a ratio of iron to arsenic of at least
20:1 (mass Fe:As) is required for removal efficiency greater than 80%. The Fe:As ratio is referred to by
many researchers who have examined iron-based methods and it is commonly noted that an increase of
the As/Fe ratio increases the As removal (Mamtaz and Bache, 2000; Donahue and Hendry, 2003). In
many cases the ratio required for adequate removal may be well in excess of 20:1. Meng et al. (2001)
noted that the applicable Fe:As ratio is a function of more complex water quality parameters including the
presence of competing ions.
CONCLUSIONS

As a conclusion of this study, the effect of pH with both collectors, collector dosage, arsenic ferric ratios
determined. The results of absorbing colloid flotation were also matched up with precipitation
experiments. Regarding comparison of SDS and K-Oleate, results showed that SDS is more effective than
K-Oleate. The flotation which is made by using SDS at pH 4, the arsenic removal efficiency was 99.4%
however the flotation which was made by using K-Oleate at pH 5.5, the arsenic removal efficiency found
as 87.2%. Since SDS used flotation experiments had better efficiency, SDS concentration was changed 5,
10, 20 ,40 ppm and the result of this experiments was 40 ppm SDS provided 99.8% arsenic removal. The
best condition was chosen as 40 ppm SDS at pH 4 and coagulant concentration was changed, however the
best result was fixed 40 ppm Fe+3.The precipitation experiments results show that precipitation method
can reach absorbing flotation efficiency after 30 minutes which is twice longer than absorbing colloid
flotation method.

REFERENCES

Alta L., Ik M., Kavurmac M., 2011. Determination of arsenic levels in the water resources of Aksaray
Province, Turkey. Journal of Environment Management, 92, 2182-2192.
Altundogan, H.S., et al., 2000. Arsenic removal from aqueous by adsorption on red mud. Waste Manage.
20 (8), 761-767.
Anirudhan, T.S., Jalajamony, S., 2010. Cellulose-based anion exchanger with tertiary amine functionality
for the extraction of arsenic (V) from aqueous media. J. Environ. Manage. 91 (11), 2201-2207.
Aydoan, M.K, 2011. Investigation of adsorbing colloid flotation method for remediation of arsenic
bearing waters. Bachelor Thesis, Istanbul Technical University, Istanbul. (In Turkish).
Budinova, T., et al., 2009. Biomass waste-derived activated carbon for the removal of arsenic and
manganese ions from aqueous solutions. Appl. Surf. Sci. 255 (8), 4650-4657.
Chwirka J. D., Colvin C., Gomez J. D., Mueller P. A., 2004. Arsenic removal from drinking water using
the coagulation/microfiltration process, Jour. AWWA, 96:3, 106-114.
Donahue, R. and J. Hendry. 2003. Geochemistry of arsenic in uranium mine mill tailings, Saskatchewan,
Canada. Applied Geochemistry. Vol.18. pp. 1733-1750.
Emamjomeh, M.M., Sivakumar, M., 2009. Review of pollutants removed by electrocoagulation and
electrocoagulation/flotation processes. J. Environ. Manage.90 (5), 1663-1679.
Fagarassy, E., et al., 2009. Treatment of high arsenic content wastewater bymembrane filtration.
Desalination 240 (1e3), 270-273.
Funing L., Daren C. 1982. Rapid spectrophotometric determination of arsenic and phosphorus after
development of molybdenum blue complex at room temperature. Analytical Abstracts, 42, 130.
Ghurye G., Clifford D., Tripp A., 2004. Iron coagulation and direct microfiltration to remove arsenic
from groundwater, Jour. AWWA, 96:4, 143-152
Greenleof, J.E., Lin, J., Sengupta, A.K., 2006. Two novel applications of ion Exchange fibres: arsenic
removal and chemical-free softening of hard water. Environ.Prog. 25, 300-311.
Guell, R., et al., 2010. Modelling of liquid-liquid extraction and liquid membrane separation of arsenic
species in environmental matrices. Sep. Purif. Technol. 72 (3), 319-325.
Kim, M.J., Nriagu, J., Haack, S., 2002. Arsenic species and chemistry in groundwater of southeast
Michigan. Environ. Pollut. 120 (2), 379-390.
Kordmostafapour, F., Pourmoghades, H., Shahmansouri M.R., Parvaresh, A., 2006. Arsenic removal by
dissolved air flotation, Journal of Applied Science, 6 (5), 1153-1158.
Lemlich, R. 1972, Adsorptive Bubble Separation Techniques, Academic Press, New York.
Mamtaz, R. and D. Bache. (2000). Low-cost technique of arsenic removal from water. Journal of the
Chartered Institution of Water and Environmental Management. Vol.14. No.4, pp.260-269.
Meng, X., G. Korfiatis, C. Christodoulatos and S. Bang. (2001). Treatment of arsenic in Bangladesh well
water using a household co-precipitation and filtration system. Water Research. Vol.35. No.12,
pp.2805-2810.
National Research Council (NRC), 1999. Arsenic in Drinking Water. National Academy of Sciences,
Washington, DC.
Pal, P., et al., 2007. Removal of arsenic from drinking water by chemical precipitation-a modelling and
simulation study of the physicalechemical processes. Water Environ. Res. 79, 357-366.
Peng, F. F., Di, P, 1994. Removal of arsenic from aqueous solution by adsorbing colloid flotation, Ind.
Eng. Chem., Res., 33, 922-928.
Rubio, J., Souza, M.L., Smith, R.W., 2002, Overview of flotation as a wastewater treatment technique,
Minerals Engineering, 15, 139-155.
Schaeffer, R., et al., 2005. Determination of arsenic species in seafood samples from the Aegean Sea by
liquid chromatography-(photo-oxidation)-hydride generationatomic fluorescence spectrometry. Anal.
Chim. Acta 547 (1), 109-118.
Schweitzer G.K., Pesterfield L.L., 2010. The Aqueous Chemistry of Elements. Oxford University Press.
Smedley, P.L., Kinniburgh, D.G., 2002. A review of the source, behaviour and distribution of arsenic in
natural waters. Appl. Geochem. 17 (5), 517-568.
Stoica L.,I Irimia A., Oproiu G.C., Ordeanu V., 2008. Kinetic Modelling of as(V) by Dissolved Air
Flotation. Rev. Chim. 59(4), 379-384.
TSE (Turkish Standards Institution), 2005. Quality of water intended for human consumption, TS 266, p.
10, Ankara, Turkey.
USEPA, 2005. Treatment Technologies for Arsenic Removal. National Risk Management Research
Laboratory, Cincinnati, OH.
USEPA, 2009. Integrated Risk Information System (IRIS). US Environmental Protection Agency.
Yenial U, 2012. Arsenic removal from waters. Master Thesis, Istanbul Technical University, Istanbul. (In
Turkish).
Walker, M., Seiler, R.L., Meinert, M., 2008. Effectiveness of household reverseosmosis systems in a
Western US region with high arsenic in groundwater. Sci. Total Environ. 389 (2e3), 245-252.
World Health Organization (WHO), 2006. Guidelines for Drinking-Water Quality, First Addendum to
Third Edition, vol. 1. Recommendations, Geneva.