Bioresource Technology 101 (2010) 6594–6600

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Oil removal from water using biomaterials

Asha Srinivasan, Thiruvenkatachari Viraraghavan *
Faculty of Engineering and Applied Science, University of Regina, Regina, SK, Canada S4S0A2

a r t i c l e i n f o a b s t r a c t

Article history: A batch study was conducted to evaluate efficiencies of four types of biomaterials to remove oil from
Received 29 April 2009 water. The oils used in the study were standard mineral oil, vegetable oil and cutting oil. Two fungal
Received in revised form 16 March 2010 biomasses of Mucor rouxii and Absidia coerulea along with chitosan and walnut shell media were the
Accepted 16 March 2010
biomaterials used. The study was carried out with an initial oil concentration of 200 mg/L for 6 h. Non-
Available online 7 April 2010
viable M. rouxii biomass was found to be more effective than A. coerulea biomass in removing oil from
water. The study demonstrated that the removal efficiencies by M. rouxii for these oils were in the
Keywords:
77–93% range at a pH of 5.0. The adsorption capacities for standard mineral oil, vegetable oil and cutting
Oil removal
Oil-in-water emulsions
oil were 77.2, 92.5, and 84 mg/g of biomass, respectively. The adsorption capacities for various oils
Fungi exhibited by M. rouxii biomass were less than those of chitosan and walnut shell media.
Chitosan Ó 2010 Elsevier Ltd. All rights reserved.
Walnut shell media

1. Introduction
The discharge of oil-containing wastewater to the environment
increases every year due to urbanization and industrial develop-
ment. Oils that are found in contaminated waters can be fats, lubri-
cants, cutting liquids, heavy hydrocarbons (tars, grease, crude oils
and diesel oil), and light hydrocarbons (kerosene, jet fuel and gas-
oline). Major industrial sources of oily wastewater include petro-
leum refineries, metal manufacturing and machining, and food
processors. Unlike free or floating oil spilled in sea, most of the
industrial wastewaters contain oil-in-water emulsions among
their basic contaminants. The presence of emulsified oil in waste-
waters is of real concern as it often results in fouling of process
equipment and creates problems during biological treatment of
such wastewaters.
The best available technologies for oil removal include chemical
treatment, gravity separation, parallel plate coalescers, gas flota-
tion, cyclone separation, granular media filtration and catridge fil-
tration (Yang et al., 2002). Emulsified oils can be effectively
removed from water by adsorption. Various adsorption materials
such as crushed and/or processed plant materials have been exam-
ined for their oil adsorption capacities (Johnson et al., 1973; Sun
et al., 2002; Silva-Tilak, 2002). Deschamps et al. (2003) used cotton
as a bed material to recover oil from oily water. Mathavan and Vir-
araghavan (1992) used horticultural peat as a bed material to
examine the capability of the filter bed in oily water clean-up.
Materials such as bentonite organoclay and vermiculite have been
* Corresponding author. Tel.: +1 306 585 4094; fax: +1 306 585 4855.
E-mail address: t.viraraghavan@uregina.ca (T. Viraraghavan).
examined for their oil adsorption capacities (Moazed and Viraragh-
avan, 2005; Mysore et al., 2005).
Fungi Mucor rouxii and Absidia coerulea, chitosan and walnut
shell are biomaterials which have been used for many applications
in separation technology. M. rouxii is a filamentous fungus in which
chitosan is the most abundant component (33%) of the cell wall.
M. rouxii contains large quantities of chitosan, chitin, phosphate
and absence of glucose polymers on its cell wall (Muzzarelli,
1977; Bartnicki-Garcia and Nickerson, 1962). During the life cycle
of M. rouxii, the chemical differentiation of cell walls take place,
where it is evident that the highest proportion of chitosan is pres-
ent in the hyphae stage (Bartnicki-Garcia and Nickerson, 1962).
Large quantities of positively charged chitosan and negatively
charged phosphate and glucouronic acid on the cell wall of M. rou-
xii have been found to offer extensive possibilities for binding hea-
vy metals (Volesky, 1993). A. coerulea is a fungus belonging to
Absidia strains of zygomycetes in which chitosan accounts for
10.4% of the vegetative cells and the degree of deacetylation has
been found to have reached 95% (Miyoshi et al., 1992). Extensive
research had been conducted for the production of chitosan by fer-
mentation using A. coerulea (Rane and Hoover, 1993; Muzzarelli
et al., 1994) and M. rouxii (White et al., 1979; Knorr and Klein,
1986).
Chitosan is a cationic amino polysaccharide, essentially com-
posed of b-1,4-D-glucosamine linked to N-acetyl-D-glucosamine
residues. It is a partially deacetylated derivative obtained by alka-
line treatment of chitin. Chitosan has properties such as biodegrad-
ability, adsorption potential, flocculation ability and regeneration.
Ahmad et al. (2005a,b) conducted studies to evaluate the use of
chitosan as an adsorbent for residue oil removal from palm oil mill
effluent (POME) and these studies showed significant uptake of

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.03.079
 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600
residue oil by chitosan. Walnut shell is a chemically inert biode-
gradable material, which is used to treat oil field produced water,
refinery wastewater, steel mill direct spray and caster water (Blu-
menschein et al., 2001). Walnut shell has been found to be an effec-
tive filtration media when separating crude oil from water (Owens
and Lee, 2007). Walnut shells possess excellent surface character-
istics for coalescing and filtration and superior resilience to attri-
tion. USFilter Zimpro products, USA have developed an auto-shell
walnut shell filter to remove oily contaminants from water (USFil-
ter Corporation, 2005). The walnut shell media was found to have a
good oil sorption capacity and it showed promising results for
sorption of pure oil and oil on an aqueous medium (Srinivasan
and Viraraghavan, 2008).
The objective of the present study was to examine the
removal of various oils from water using non-viable fungal bio-
masses M. rouxii and A. coerulea and compare their adsorption
capacities with those of chitosan and walnut shell media. No work
has been conducted so far on the removal of oil from water by non-
viable fungal adsorbents, although, a few studies have been con-
ducted on uptake of oil by live fungi (Srinivasan and Viraraghavan,
2007).
2. Methods
2.1. Experimental materials
Fungal strains of M. rouxii and A. coerulea were purchased from
American Type Culture Collection (ATCC), Rockville, Maryland, USA
(ATCC #24905, ATCC #10738a). Chitosan from crab shells (Aldrich
417963) was purchased from Sigma–Aldrich Corporation, Ontario,
Canada. Walnut shell media was supplied by USFilter, part of the
Water Technology Division of Siemen’s Industrial Solutions and
Services (I&S) Group, USA.
The following oils were used in the study:
(1) Standard (light) mineral oil (SMO) marketed by Fisher Scien-
tific Company, USA, emulsified with oleic acid and trietha-
nolamine using Regina tap water according to the
procedure used by Biswas (1973).
(2) Canola oil (CO), a vegetable oil marketed in Canada, emulsi-
fied similar to SMO.
(3) DoALL Bright-Edge 80, a cutting oil manufactured by DoALL
Company, IL, USA, emulsified similar to SMO.
2.2. Preparation of non-viable fungal biomass
M. rouxii and A. coerulea strains were routinely maintained on
potato dextrose agar plates. They were grown aerobically using
the shake flask method. They were cultivated using the same
growth medium comprising of yeast extract (3 g/L), peptone
(10 g/L) and glucose (replaced by dextrose) (20 g/L) (Bartnicki-
Garcia and Nickerson, 1962; Muzzarelli et al., 1994). The pH of
the growth medium for M. rouxii was maintained at 4.5 and for
A. coerulea at 5.0 by 1.0 N HCl. The cultures were grown at room
temperature (22 ± 2 °C) with 100 mL of the liquid medium in
250 mL conical flasks on a rotary shaker agitated at 125 rpm.
M. rouxii was harvested after three days of growth and A. coerulea
after four days by filtering the growth media through a 150 lm
sieve. The harvested fungal biomass was washed with generous
amounts of deionized water and autoclaved for 30 min at
121 °C and 103 kPa. The autoclaved biomass was allowed to cool
down and then it was dried in an oven at 60 °C for 24 h. The
dried biomass was powdered into a fine size using a grinder.
The biomass passing through a 400 mm sieve was used for the
study.
6595
2.3. Surface area analysis and surface charge measurement
The surface area and pore size measurements of the autoclaved
biomass were carried out using MicromeriticsÒ ASAP 2020 acceler-
ated surface area and porosimetry analyzer. Data on surface
charges of SMO and CO were obtained from a study conducted
by Mysore et al. (2005). Surface charge of Bright-Edge 80 cutting
oil was measured using Zetasizer, model HSA 3000 (Malvern,
Worcestershire, England). Methods used for characterizing the
adsorbents and oils are described elsewhere (Srinivasan and Virar-
aghavan, 2008).
2.4. Biosorption studies
The oil-in-water emulsion of 100 mL volume was contacted for
six hours with 0.2 g of the fungal biomass at a speed of 175 rpm in
a platform shaker (Model: Classic C2), manufactured by New
Brunswick Scientific, New Jersey, USA. The study was carried out
with an initial oil concentration of 200 mg/L at two pH conditions
of 5.0 and 7.6. pH was adjusted using 0.1 M HCl or 0.1 M NaOH
solution. The experiments were conducted under controlled pH
conditions using buffer solutions (Lange, 1973). 0.2 M of sodium
phosphate and 0.1 M of citric acid were used in different ratios
(Lange, 1973) to adjust the pH. The oil-in-water emulsion was vac-
uum-filtered through a 1.5 mm glass micro-filter after biosorption
experiments. A control with no biomass was also set up for each
run. The filtrate was analyzed for oil concentration using Horiba
OCMA-350 oil content analyzer (Horiba Instruments Inc., CA). Hor-
iba OCMA-350 has an inbuilt NDIR spectrophotometer and dis-
plays oil concentration directly in mg/L on a digital panel. Oil
was extracted with tetrachloroethylene (ultra-resi analyzed) be-
fore analysis. All experiments were conducted in triplicate and
the mean values were used in the analysis of data. Statistical anal-
ysis of data which included mean and standard deviation were
conducted using MINITAB™ release 15 statistical software (Mini-
tab, 2007).
3. Results and discussion
3.1. Characterization of adsorbents and oil
The fungal biomasses were passed through a 400 mm sieve.
The mean size of walnut shell media used in the study was
56.28 mm. The characteristics of all the four materials are
presented in Table 1. The characteristics of oils used in the study
are provided in Table 2. Surface charges of the three oil-in-water
emulsions at different pH conditions are presented in Fig. 1.
3.2. Oil removal by biomaterials
The pH of all three oil-in-water emulsions was in the range of
7.5–7.6 and the study examined the effect of slightly acidic (pH
5.0) and slightly basic pH (7.6). The adsorption capacities of M. rou-
xii, A. coerulea, chitosan and walnut shell media at pH 7.6 and 5.0
are shown in Figs. 2–4. The residual oil concentrations (ranges
and means) obtained by using the four different biomaterials are
presented in Table 3. Every batch test was conducted in triplicate
and the mean is represented by one data point in the figures. The
deviations of the three points from the mean were found to be
within ±1%; the standard deviation for each set of data was found
to be relatively small compared to the mean. Among the three oils
studied, maximum oil removals were observed in the case of cano-
la oil for all the four adsorbents (see Table 4). The adsorption
capacities for canola oil at pH 5.0 were 92.5, 90.5, 99.9, and
96 mg/g by M. rouxii, A. coerulea, chitosan and walnut shell media,
6596 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600

Table 1
Characteristics of the biomaterials.

Characteristics values M. rouxiia A. coeruleab Chitosanc Walnut shelld

Physical characteristics
pH 6.4 4.5 6.8 7.5
Moisture content (%) 4.6 4.7 2.8 2.0
Density – – – 0.64 kg/L
Specific gravity – – – 1.2–1.4
Porosity (%) 85 60 62 52
Surface area (m2/g) 20.55 0.68 0.65 for Sigma C3646 0.17
Color Light brown Light brown Faintly beige Light brown
Chemical analysis (% by weight) Chitosan – 32.7 Chitosan – 10.4 >85% Deacetylation Nitrogen – 0.10
Chitin – 9.4 Sp. Cellulose – 40.60
Lipids – 7.8 Lignin – 20.30
Fucose – 3.8 Toluene solubility – 0.5–1.0
Mannose – 1.6 Methoxyl – 6.5
Galactose – 1.6 Chlorine – 0.10
Protein – 6.3 Ash – 1.5
Phosphate 23.3 Cutin – 1.0
Magnesium – 1.0
Calcium – 1.0
Glucuronic acid – 11.8
a
Note: composition of M. rouxii cell wall was obtained from Bartnicki-Garcia and Nickerson (1962).
b
Percentage of chitosan on A. coerulea cell wall was obtained from Miyoshi et al. (1992).
c
The degree of deacetylation is >85%; surface area of chitosan was obtained from Uzun (2006).
d
Density, specific gravity, and chemical analysis of walnut shell media were provided by USFilter, USA.

Table 2 It enhances the formation of smaller emulsion droplets with great-

Characteristics of oils used for the study at 20 °C.
er kinetic stability (Aserin, 2007).
Type of oil Density (kg/ Viscosity Interfacial tension (dynes/ Better oil removals for all three oils were obtained at pH 5.0
m3) (Pa S) cm) than at pH 7.6 for all four adsorbents. From Fig. 1 it can be seen that
SMO 841.9 0.143 5.3 for all the three oils, the zeta-potential value was less electroneg-
Canola oil 913.2 0.070 3.1 ative at pH 5.0 when compared to that at pH 7.0. Zeta-potential
Bright-Edge 821.5 0.023 2.7
indicates the stability of oil-in-water emulsions. A higher magni-
80
tude of zeta-potential would refer to greater forces of repulsion be-
tween particles in the emulsion which would lead to better
stability of emulsions (Reynolds and Richards, 1995). With a de-
crease in the magnitude of zeta-potential, the possibility of coagu-
40
lation of dispersed particles increases and the emulsion becomes
20
less stable (Pushkarev et al., 1983; Riddick, 1968). Hence a value
lower in electro-negativity observed at pH 5.0 for the three oils
0
studied resulted in a higher removal efficiency. Similar behavior
Zeta potential (mV)

0 2 4 6 8 10
-20
-40
-60
-80
-100
pH
Fig. 1. Zeta-potential of oil-in-water emulsions.
respectively. This could be due to the fact that in comparison with
the other two emulsions, vegetable oil emulsions are known for
their limited stability (Vesala et al., 1985). Vegetable oils predom-
inantly consist of triglycerides (Pushkarev et al., 1983) and emul-
sions based on oils from the triglyceride group showed poor
stability in comparison with emulsions based on hydrocarbon oils
(Ozgen et al., 2006). Bright-Edge 80 cutting oil was found to exhibit
minimum removal by all the four adsorbents studied. Bright-Edge
80 cutting oil is the one with the least interfacial tension among
the three oils studied. Low interfacial tension would result in re-
duced free surface energy associated with formation of droplets.
was found by Ahmad et al. (2005a) with chitosan, which was used
SMO
to remove residue oil from POME effluents. They observed that
Canola oil
when pH was lower than 5.0, the percentage of residue oil adsorp-
Cutting oil tion could be increased to 99%. Also, at pH more than 5.0 the per-
centage of adsorption was found to decrease and when the pH was
7.0 the percentage of residue oil adsorption was the lowest. Similar
trends were observed with bentonite and activated carbon which
showed a higher oil removal at a pH less than 5.0 (Ahmad et al.,
2005b). It was suggested that the acidic conditions acted in cata-
lyzing the reaction between the residue oil molecules and adsorp-
tion site of chitosan (–NH2 group) (Ahmad et al., 2005a). Fungal
biomass surfaces have been generally observed to be negatively
charged because of the ionization of functional groups present in
them (Yan and Viraraghavan, 2003). At acidic pH, some of the func-
tional groups present in the fungal cell wall will be positively
charged and negative charge intensity on the sites will be reduced,
which might have an effect on the sorption characteristics of the
biomass (Yan and Viraraghavan, 2003). Uptake by dead fungal cell
takes place as a result of the functional groups of the cell and, in
particular, the cell wall. The mechanism of uptake by the cell wall
has been broadly categorized as: (1) uptake directed by functional
groups like phosphate, carboxyl, amine and phosphate diester spe-
cies of these compounds; (2) physio-chemical interactions directed
by adsorption phenomena (Kapoor and Virarghavan, 1995). Bio-
sorption mechanisms have been found to include ion-exchange,
co-ordination, complexation, chelation, adsorption and micropre-
 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600 6597

120

100

Adsorption capacity (mg/g)

M. rouxii pH 7.6
80 A. Coerulea pH 7.6
Chitosan pH 7.6
Walnut shell media pH 7.6
60
M. rouxii pH 5.0
A. coerulea pH 5.0
40 Chitosan pH 5.0
Walnut shell media pH 5.0

20

0
0 2 4 6 8
Time (h)

Fig. 2. Adsorption capacity versus time for SMO.

120

100
Adsorption capacity (mg/g)

80 M. rouxii pH 7.6
A. coerulea pH 7.6
Chitosan pH 7.6
Walnut shell media pH 7.6
60
M. rouxii pH 5.0
A. coerulea pH 5.0
Chitosan pH 5.0
40 Walnut shell media pH 5.0

20

0
0 2 4 6 8
Time (h)

Fig. 3. Adsorption capacity versus time for canola oil.

cipitation (Yan and Viraraghavan, 2000). It is necessary to carry out
more detailed studies to understand the specific mechanism in-
volved in biosorption of oil by the fungal adsorbents. The mecha-
nism of oil removal in the case of walnut shell media has been
observed to be sorption (Rahman, 1992). Oil is found at the inter-
stices of the finely divided granules of the walnut shell media
which is observed to be an excellent coalescing material.
Among the two fungal biomasses studied, M. rouxii was found
to be better for oil sorption than A. coerulea. The adsorption capac-
ity of M. rouxii at pH 5.0 for SMO, canola oil and Bright-Edge 80
were 77.2, 92.5, and 84 mg/g, respectively. The higher adsorption
capacity for oil by M. rouxii could be due to its higher BET surface
area. An adsorbent with higher surface area has been found to
facilitate the adsorption of residue oil (Ahmad et al., 2005a). Myce-
lium of M. rouxii grows in the form of suspended growth leading to
a larger surface area of the biomass for adsorption (Yan and Virar-
aghavan, 2000). In the case of A. coerulea, it grows in the form of
pellets with a lower surface area. Most Absidia species are found
to have a strong inclination to form pellets during their growth
in a fermentor (Davoust and Persson, 1992). A higher adsorption
capacity for oil by M. rouxii compared to A. coerulea could also be
due to a higher amount of chitosan present in the cell wall of M.
rouxii. Yan and Viraraghavan (2000) have observed that biosorp-
tion capacity for heavy metals were higher for M. rouxii than A. ni-
ger and the difference was ascribed to the larger surface area of M.
rouxii.
M. rouxii has been more effective in removing all three oils than
A. coerulea and walnut shell media. The effectiveness of M. rouxii in
6598 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600

120

100

Adsorption capacity (mg/g)

M. rouxii pH 7.6
80 A. coerulea pH 7.6
Chitosan pH 7.6
Walnut shell media pH 7.6
60
M. rouxii pH 5.0
A. Coerulea pH 5.0
40 Chitosan pH 5.0
Walnut shell media pH 5.0

20

0
0 2 4 6 8
Time (h)

Fig. 4. Adsorption capacity versus time for Bright-Edge 80.

Table 3
Residual oil concentration obtained using different biomaterials.

Oil Time M. rouxii A. coerulea Chitosan Walnut shell

(h)
pH 7.6 pH 5.0 pH 7.6 pH 5.0 pH 7.6 pH 5.0 pH 7.6 pH 5.0
Range Mean Range Mean Range Mean Range Mean Range Mean Range Mean Range Mean Range Mean
SMO
1 75.4– 75.6 65.6– 65.7 87.8– 88.0 72.4– 72.6 26.3– 26.6 17.1– 17.3 150–151 150.7 67.0– 67.7
75.8 65.8 88.1 72.7 26.7 17.4 68.0
2 71.0– 72 57.2– 57.3 81.9– 82.0 64.3– 64.5 23.4– 23.7 12.1– 12.2 141.7– 142.0 49.2– 49.3
73.0 57.5 82 64.7 23.8 12.3 142.5 49.5
3 69.0– 69.1 46.6– 46.8 78.9– 79.1 55.5– 55.8 13.0– 13.3 4.9–5.0 5.0 134.8– 135.1 35.5– 35.6
69.2 46.9 79.2 55.9 13.4 135.4 35.7
4 66.6– 66.9 45.5– 45.8 78– 78.1 55.3– 55.4 9.0–9.1 9.1 2.0–2.1 2.1 127.8– 128.0 33.2– 33.8
67.2 45.9 78.2 55.5 128.3 34.0
5 66.2– 66.3 45.6– 45.8 77.4– 77.6 55.5– 55.6 9.5–9.8 9.6 1.1–1.2 1.2 118.0– 118.1 33.9– 34.1
66.4 45.9 77.7 55.7 118.3 34.4
6 65.9– 66.0 45.7– 45.6 77.8– 78.0 55.6– 55.8 9.1–9.3 9.2 0.7–0.8 0.8 123.6– 123.9 34.7– 35.0
66.2 45.6 78.1 55.8 124.1 35.2
CO
1 35.1– 35.4 28.7– 28.9 36.8– 37.1 31.8– 32.1 8.0–8.2 8.0 5.2–5.3 5.3 115.5– 116.0 26.8– 27.1
35.6 29.0 37.3 32.3 116.2 27.5
2 28.6– 28.9 22.5– 22.6 32.8– 33.1 26.5– 26.7 5.2–5.3 5.3 2.7–2.8 2.8 94.0– 94.3 19.7– 19.8
29.1 22.9 33.4 26.8 94.5 19.9
3 24.1– 24.6 18.2– 18.4 29.6– 29.9 19.0– 19.2 1.8–1.9 1.8 1.1–1.3 1.2 85.3– 85.6 12.2– 12.4
24.9 18.4 30.0 19.5 86.2 12.6
4 23.0– 23.2 15.1– 15.3 28.3– 28.6 18.7– 18.9 1.7–1.8 1.7 0.5–0.7 0.6 84.1– 84.4 8.7–8.9 8.8
23.5 15.5 28.9 19.1 85.0
5 23.5– 23.9 15.3– 15.6 27.6– 27.8 18.6– 18.7 1.7–1.9 1.8 0.4–0.5 0.5 82.6– 82.8 8.8–9.2 9.1
24.2 15.6 27.9 19.0 83.1
6 22.1– 22.2 15.0– 15.0 27.1– 27.2 18.6– 18.9 1.7–1.8 1.7 0.2–0.4 0.3 80.0– 80.4 8.0–8.1 8.0
22.3 15.1 27.5 19.0 80.6
Bright-Edge 80
1 80.9– 81.1 47.2– 47.8 84.4– 84.7 49.5– 49.8 32.4– 32.8 14.5– 14.6 61.6– 61.7 17.0– 17.1
81.5 48.1 84.9 50.0 33.0 14.8 61.9 17.3
2 78.4– 78.7 37.9– 38.1 81.0– 81.1 44.0– 44.2 26.9– 27.1 12.0– 12.2 58.5– 58.9 14.4– 14.6
78.9 38.5 81.3 44.6 27.4 12.5 59.1 14.9
3 73.5– 73.7 34.6– 34.7 79.5– 79.8 41.6– 41.7 24.6– 24.7 8.0–8.2 8.1 56.2– 56.4 10.4– 10.5
73.8 34.9 80.0 41.9 24.9 56.7 10.7
4 72.0– 72.2 31.8– 32.1 78.9– 79.1 39.4– 39.9 23.6– 23.7 6.7–6.9 6.8 54.2– 54.3 9.3–9.4 9.4
72.6 32.6 79.5 40.1 23.9 54.5
5 71.7– 71.8 31.7– 31.9 78.5– 78.8 39.8– 40.1 24.8– 24.9 6.0–6.1 6.1 54.3– 54.5 9.7–9.8 9.8
72.0 32.3 80.0 40.2 24.9 54.8
6 70.9– 71.1 31.8– 32.0 78.9– 79.0 39.5– 39.8 21.9– 22.2 6.3–6.4 6.3 53.3– 53.5 9.2–9.3 9.3
71.5 32.1 79.1 40.0 22.7 53.8

Note: all values in mg/L; initial oil concentration = 200 mg/L.

 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600 6599

Table 4 (2) M. rouxii biomass showed a better adsorption capacity for

Oil removals by biomaterials. oils compared to A. coerulea; however its capacity was lower
Oil pH Oil removals (%) than those of chitosan and walnut shell media.
M. rouxii A. coerulea Chitosan Walnut shell (3) Maximum adsorption capacity obtained using M. rouxii for
SMO, canola oil and Bright-Edge 80 were 77.2, 92.5, and
SMO
7.6 67 61 96 38
84 mg/g, respectively.
5.0 77 72 99 83 (4) Better removals for all three oils were obtained at a pH of 5.0
CO
than at a pH of 7.6 in the case of all four adsorbents.
7.6 89 87 99 60
5.0 93 91 99 96
Acknowledgements
Bright-Edge 80
7.6 65 61 89 73
5.0 84 80 97 96 The study was funded by a Grant from the Natural Sciences and
Engineering Research Council of Canada to the second author.
Note: initial concentration = 200 mg/L; time of contact = 6 h; adsorbent
dose = 0.2 g.
References

Ahmad, A.L., Sumathi, S., Hameed, B.H., 2005a. Adsorption of residue oil from palm
oil mill effluent using powder and flake chitosan: equilibrium and kinetic
Table 5
studies. Water Research 39, 2483–2494.
Cost of adsorbents required to treat 100 m3/d of oily water based on SMO data.
Ahmad, A.L., Sumathi, S., Hameed, B.H., 2005b. Residual oil and suspended solid
M. rouxii A. Chitosan Walnut removal using natural adsorbents chitosan, bentonite and activated carbon: a
coerulea shell comparative study. Chemical Engineering Journal 108, 179–185.
Aruldoss, J.A., Viraraghavan, T., 1998. Toxicity testing of refinery wastewater using
Adsorption capacity (mg/g) 77.2 72.1 99.6 82.5 Microtox. Bulletin of Environmental Contamination and Toxicology 60, 456–
Mass of adsorbent required 246 264 191 230 463.
(kg/d) Aserin, A., 2007. Multiple Emulsions: Technology and Applications. Wiley-
Cost of adsorbent ($/kg) 1–5a 1–5a 13b 3.84c Interscience, Hoboken, New Jersey, USA.
Cost of adsorbent required 246– 264– 2480 884 Bartnicki-Garcia, S., Nickerson, W.Y., 1962. Isolation, composition and structure of
($/day) 1231 1318 cell walls of filamentous and yeast-like forms of Mucor rouxii. Biochemistry and
Biophysics Acta 58, 102–119.
Note: initial concentration = 200 mg/L; final concentration = 10 mg/L. Biswas, N., 1973. Electrochemical Treatment of Oil Emulsions. MASc Thesis.
a
Cost of specifically cultured fungi was obtained from Kuyucak (1990). Department of Civil Engineering, University of Ottawa, Ottawa, Canada.
b
Cost of chitosan obtained from Chi and Cheng (2006). Blumenschein, C.D., Severing, K.W., Boyle, E., 2001. Walnut shell filtration for oil and
c solids. AISE Steel Technology (USA) 78 (4), 33–37.
Cost of walnut shell media provided by USFilter, USA.
CCRL, 2007. Project Proposal for Expansion Project – Section V and Revamps.
Consumers’ Co-operative Refineries Limited, Regina, Saskatchewan, Canada.
<http://www.environment.gov.sk.ca/2007-184EIA%28ProjectProposal%29>
(accessed 10.02.10).
removing the oils follows this order: CO, SMO, and Bright-Edge 80. Chi, F.H., Cheng, W.P., 2006. Use of chitosan as coagulant to treat wastewater from
The oil adsorption capacity by M. rouxii was lower when compared milk processing plant. Journal of Polymers and the Environment 14, 411–417.
Davoust, N., Persson, A., 1992. Effect of growth morphology and time of harvesting
with that of crab shell chitosan. The cell wall of M. rouxii was found
on the chitosan yield of Absidia repens. Applied Microbiology and Biotechnology
to contain chitosan at approximately 32% of its dry weight (Bartn- 37, 572–575.
icki-Garcia and Nickerson, 1962) and the fungal biomass has an Deschamps, G., Caruel, H., Borredon, M.E., Bonnin, C., Vignoles, C., 2003. Oil removal
adsorption capacity of 92.5 mg/g for canola oil at pH 5.0 while pure from water by selective sorption on hydrophobic cotton fibres. 1. Study of
sorption properties and comparison with other cotton fibre-based sorbents.
chitosan showed an adsorption capacity of 99.9 mg/g. Oil uptake Environmental Science and Technology 37, 1013–1015.
by M. rouxii is also influenced by other functional groups present Johnson, R.F., Manjreker, T.G., Halligan, J.E., 1973. Removal of oil from water
in the cell wall. surfaces by sorption on unstructured fibers. Environmental Science and
Technology 7 (5), 439–443.
By using the maximum adsorption capacity data of the four bio- Kapoor, A., Virarghavan, T., 1995. Fungal biosorption – an alternative treatment
materials for the particular oil-in-water emulsion, it is possible to option for heavy metal bearing wastewaters: a review. Bioresource Technology
calculate the amount of adsorbent required to reduce the oil in the 53, 195–206.
Knorr, D., Klein, J., 1986. Production and conversion of chitosan with cultures of
oily water to a desired concentration. The amount and cost of bioma- Mucor rouxii or Phycomycus blakesleeanus. Biotechnology Letters 8 (10), 691–
terials required to obtain an effluent concentration of 10 mg/L for 694.
SMO for a daily flow of 100 m3/d is shown in Table 5. Batch adsorp- Kuyucak, N., 1990. Feasibility of biosorbents application. In: Volesky, B. (Ed.),
Biosorption of Heavy Metals. CRC Press, Boca Raton, Florida, pp. 371–380.
tion systems, which are mostly operated on a fill-and-draw basis, are
Lange, A., 1973. In: John, A.D. (Ed.), Lange’s Handbook of Chemistry, 12th ed.
suitable for treating small wastewater volumes (Moazed and Virar- McGraw-Hill Book Company, New York, USA.
aghavan, 2005). The Consumer’s Cooperative Refineries Limited, Re- Mathavan, G.N., Viraraghavan, T., 1992. Coalescence/filtration of an oil-in-water
gina, Saskatchewan, Canada treats approximately 4700 m3/d of emulsion in a peat bed. Water Research 26 (1), 91.
Minitab, 2007. Meet Minitab 15 for Windows. Minitab Inc., USA.
effluent with an average initial oil concentration of 350 mg/L (Arul- Miyoshi, H., Shimura, K., Watanabe, K., Onodera, K., 1992. Characterization of some
doss and Viraraghavan, 1998; CCRL, 2007) and the treated effluent fungal chitosans. Bioscience, Biotechnology and Biochemistry 56, 1901–1905.
has an average oil concentration of 10–15 mg/L. A continuous Moazed, H., Viraraghavan, T., 2005. Removal of oil from water by bentonite
organoclay. Practice Periodical of Hazardous, Toxic, and Radioactive Waste
adsorption system with an immobilized fungal biomass medium Management 9 (2), 130–134.
(beads) may be required to treat such a large quantity of wastewater, Muzzarelli, R.A.A., 1977. Chitin. Pergamon Press Ltd., Oxford, England, UK.
if it is necessary to bring down the oil concentration further. Muzzarelli, R.A.A., Illari, P., Tarsi, R., Dubini, B., Xia, W., 1994. Chitosan from Absidia
coerulea. Carbohydrate Polymers 25, 45–50.
Mysore, D., Viraraghavan, T., Jin, Y.-C., 2005. Treatment of oily waters using
4. Conclusions vermiculite. Water Research 39, 2643–2653.
Owens, N., Lee, D., 2007. The use of micro bubble flotation technology in secondary
and tertiary produced water treatment – a technical comparison with other
The following conclusions were drawn based on the experimen- separation technologies. In: TUV NEL, 5th Produced Water Workshop, 30th–
tal study: 31st May, Aberdeen, Scotland.
Ozgen, O., Burcu, A., Yasemin, Y., 2006. Effect of oil type on stability of W/O/W
emulsions. Cosmetics and Toiletries 121 (7), 57–64.
(1) Non-viable M. rouxii biomass showed a strong potential to Pushkarev, V.V., Yuzhaninov, A.G., Men, S.K., 1983. Treatment of Oil-Containing
remove various oils from water. Wastewater. Allerton Press Inc., New York, USA.
6600 A. Srinivasan, T. Viraraghavan / Bioresource Technology 101 (2010) 6594–6600
Rahman, S.S., 1992. Evaluation of filtering efficiency of walnut granules as deep-bed
filter media. Journal of Petroleum Science and Engineering 7 (3–4), 239–246.
Rane, K.D., Hoover, D.G., 1993. Production of chitosan by fungi. Food Biotechnology
7, 11–33.
Reynolds, T.D., Richards, P., 1995. Unit Operations and Processes in Environmental
Engineering, second ed. PWS Publishing Company, Boston, MA.
Riddick, T.M., 1968. Control of Colloid Stability through Zeta Potential. Zeta-Meter,
Inc., New York, NY, USA.
Silva-Tilak, V., 2002. Method of Oil Cleanup Using Coconut Coir Pith, vol. 1258 (3).
US Patent and Trademark office.
Srinivasan, A., Viraraghavan, T., 2007. Biological processes for removal of oil from
wastewater – a review. Fresenius Environmental Bulletin 16(12a), 1532–1543.
Srinivasan, A., Viraraghavan, T., 2008. Removal of oil by walnut shell media.
Bioresource Technology 99, 8217–8220.
Sun, X.-F., Sun, R.-C., Sun, J.-X., 2002. Acetylation of rice straw with or without
catalysts and its characterization as a natural sorbent in oil spill cleanup.
Journal of Agricultural and Food Chemistry 50 (22), 6428–6433.
USFilter Corporation, 2005. Auto-ShellTM filter: Walnut Shell Filtration.
<www.Zimpro.usfilter.com> (accessed 05.03.07).
Uzun, I., 2006. Kinetics of the adsorption of reactive dyes by chitosan. Dyes and
Pigments 70 (2), 76–83.
Vesala, A., Rosenholm, J.B., Laiho, S., 1985. Increasing the stability of vegetable oil
solutions with the aid of monoglycerides and a cosurfactant. Journal of the
American Oil Chemists’ Society 62 (9), 1379–1385.
Volesky, B., 1993. Biosorption of Heavy Metals. CRC, Boca Raton, FL, USA.
White, S.A., Farina, P.R., Fulton, I., 1979. Production and isolation of chitosan from
Mucor rouxii. Applied and Environmental Microbiology 38 (2), 323–328.
Yan, G., Viraraghavan, T., 2000. Effect of pretreatment on the bioadsorption of heavy
metals on Mucor rouxii. Water SA 26 (1), 119–124.
Yan, G., Viraraghavan, T., 2003. Heavy-metal removal from aqueous solution by
fungus Mucor rouxii. Water Research 37 (18), 4486–4496.
Yang, Y., Zhang, X., Wang, Z., 2002. Oilfield produced water treatment with surface-
modified fiber ball media filtration. Water Science and Technology 46 (11–12),
165–170.