ARTICLE IN PRESS

Water Research 38 (2004) 579–584

Treatment of pulp mill and oil sands industrial wastewaters by

the partial spray freezing process
W. Gaoa,*, D.W. Smithb, D.C. Segob
a
Department of Civil Engineering, Lakehead University, Thunder Bay, Ont., Canada P7B 5E1
b
Department of Civil and Environmental Engineering, University of Alberta, Edmonton, Alta., Canada T6G 2G7
Received 18 July 2002; received in revised form 7 October 2003; accepted 28 October 2003

Abstract

The spray freezing process, a natural freezing technology, was used to treat pulp mill effluent and oil sands tailings
pond water. The wastewaters froze partially or completely (i.e. with or without runoff generation) during the spraying
operation. Greater than 60% impurity reduction in the spray ice was obtained when 30% of the total volume of the
sprayed water was released as runoff. Organic and inorganic contaminants were rejected with different efficiencies. The
impurities were uniformly distributed within the ice columns when the spray ice was produced without generating any
runoff. While a significant increase in impurity concentration was observed at the bottom of the ice formed with runoff
production. The spray freezing process is an effective and economically feasible technique for wastewater treatment in
cold regions. To achieve higher impurity removal efficiency, the wastewater should be only partially frozen during spray
ice production.
r 2003 Elsevier Ltd. All rights reserved.

Keywords: Spray freezing; Wastewater treatment; Impurity separation

1. Introduction Both industries often operate in cold regions and

Industries and communities located in cold regions
often face different challenges in treatment of waste-
water from those in warmer regions. Low temperatures
create problems such as reduced efficiencies for the
conventional treatment processes and more frequent
maintenance and possible replacement of mechanical
equipment. The associated costs of treatments are often
higher. Development of treatment methods that are
practical and effective under cold temperatures helps
industries and communities in cold regions to meet the
every increasing discharge regulations. In this research
the spray freezing process was evaluated as a wastewater
treatment method for two industrial wastewaters: oil
sands tailings pond water and pulp mill wastewater.
*Corresponding author. Tel.: +1-807-343-8538; fax: +1-
807-343-8928.
E-mail address: wagao@mail.lakeheadu.ca (W. Gao).
generate large volumes of wastewater.
It has long been known that water can be purified by
freezing. When water freezes, ice crystals grow of pure
water and impurities (or contaminants) are rejected from
the ice structure and become concentrated in the
remaining liquid phase. Contaminants in a large volume
of dilute wastewater can be concentrated into a smaller
volume by freezing. This separated liquid volume can
subsequently be treated or disposed of. In recent years,
freezing technology has gained new interest for indus-
trial wastewater treatment. The role of freeze technology
as a practical and cost-effective waste or wastewater
treatment method has been examined by various
researchers (for e.g., [1–3]).
When freezing is carried out under natural cold
temperature conditions, the obvious advantage is the
savings in energy. Unlike mechanical freezing, natural
freezing usually does not require complex mechanical
facilities and thus is simple and less expensive to operate.

0043-1354/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2003.10.053
 ARTICLE IN PRESS
580 W. Gao et al. / Water Research 38 (2004) 579–584
For example, sludge conditioning by natural freezing
and thawing has been recognized for many years as a
cost-effective technique in cold regions. The spray
freezing process discussed in this paper takes advantage
of cold winter temperatures to freeze wastewater and
warm spring temperatures to melt the spray ice.
When water is atomized through a nozzle and sprayed
into the ambient cold air, the water jet breaks up into
small drops which supercool and then freeze as they
travel through the air to the ground. The large exposed
surface area of droplets greatly enhances the rate of heat
loss and increases the ice formation rate. The process
has been used for many years in building offshore ice
structures for exploratory drilling in the Arctic. How-
ever, few references are found in the literature pertaining
to impurity removal from industrial wastewater using
the spray freezing process.
2. Impurity separation by the spray freezing process
The sprayed water can turn into ice or snow
depending on the equipment (snowmaking systems or
water spraying systems) and the ambient temperature
conditions. Impurity (contaminant) removal from the
sprayed wastewater is achieved in one or two stages
depending on whether the sprayed water completely or
partially freezes during the spraying operation.
The first stage of the impurity removal is achieved
when the sprayed water only partially freezes and a
runoff is generated. After the feed (source) water is
sprayed, ice starts to grow on the surface of the
supercooled droplets once its surface temperature falls
below the ice nucleation temperature while traveling
through the air to the ground. The amount of ice formed
depends on factors such as ice nucleus concentration of
the water, droplet size, air residence time and ambient
temperatures. As freezing proceeds inwards from the
droplet surface, impurities are concentrated in the liquid
phase within the center of the droplet [4,5]. Further
concentration of impurities in the unfrozen or partially
frozen droplets occurs when the droplets contact with
cold ground surface or ice surface. The ice shell formed
may fracture and release the concentrated liquid. A layer
of ice-water mixture forms. The ice-water mixture may
further freeze when the layer is exposed to the atmo-
sphere as the nozzle sweeps back and forth during the
spraying. The excess water that cannot be held within
the ice mound drains downward to become runoff from
the base of the spray ice mound.
Impurities are concentrated in the liquid phase and
then carried away from the ice mound when the liquid
drains. The amount of the impurities removed by the
runoff is a function of the impurity concentration in the
feed water and the freezing rate. In the spray freezing
process, the flowrate and the impurity concentration of
the runoff directly affect the efficiency of the impurity
removal from the spray ice. There are two extreme
conditions: (1) the entire sprayed wastewater turns into
runoff, i.e. no ice is formed, therefore, no impurity
separation and the concentrations of the impurities in
the runoff is the same as the feed water and (2) no runoff
is generated during spraying. In this case, the freezing
rate is so high that all of the sprayed water turns into ice
or snow. All impurities are entrapped into the ice
structure; again, no impurity separation occurs during
the spraying operation. Therefore, for the purpose of
wastewater treatment, runoff generation during the
spray freezing process is desirable. To get high-quality
ice and maximum production, the spraying operation
should be controlled so that the runoff generated has the
highest impurity concentration but the lowest flowrate.
For a given air temperature, this optimum condition
may be achieved by adjusting the spray flow rate,
droplet size and droplet residence time in the cold air.
The second stage of impurity removal from the
wastewater begins as the spray ice mound melts. Most
impurities residing on the surface of the ice grains are
collected and removed with the initial meltwater.
The spray freezing process has been used to desalinate
brackish water and seawater [6,7,17]. The process was
effective in reducing salt content. However, the product
(melt) water quality was influenced by the impurity
content of the feed water [6] and the site selected to hold
the spray ice in the field operations if it was not chosen
carefully [17].
Snowmaking is also a spray freezing process in which
the sprayed water completely freezes before the droplets
land on the ground; therefore, it has only one stage of
impurity removal. Snowmaking technology has been
used as a treatment and disposal method for secondary
sewage effluent [8–10], liquid animal waste and food
processing wastewater [11].
The objectives of the present study are to: investigate
impurity removal by freeze concentration during the
spraying operation (i.e. first stage impurity removal),
determine the organic and inorganic impurity partition
into solid (spray ice) and liquid (runoff) phases, and to
investigate the distribution of impurities within the ice
columns formed under both the partial and complete
freezing conditions. Comparative study of the impurity
removal in the second (melting) stage of the spray
freezing process was carried out and the results are
available in Gao et al. [12].
3. Materials and methods
3.1. Materials
The two industrial wastewaters selected for this study
have different characteristics. The oil sands tailings pond
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W. Gao et al. / Water Research 38 (2004) 579–584 581

water is produced from the extraction of bitumen from Runoff was collected until the small hole located at the
the oil sands in Northern Alberta, Canada. The waste- bottom of the column was completely blocked with ice.
water contains high concentrations of suspended and When the ambient temperature was about
24 C, the
dissolved solids, oil and grease and chemical oxygen ice slurry produced was similar to ‘‘wet snow’’ and no
demand (COD) causing matter. The main contaminants runoff formed. Immediately after the spraying opera-
of pulp mill wastewater are suspended solids, oxygen tion, the ice columns were covered with plastic bags and
demanding substances (COD and biochemical oxygen stored in the cold rooms at the same temperatures as the
demand (BOD)) and color causing materials. The pulp spray ice was produced.
mill wastewater used in this study was the effluent of an
aerated stabilization basin of a kraft pulp mill waste- 3.3. Sample analyses
water treatment system. The compositions of the
wastewaters are listed in Table 1. The feed water, runoff and ice core samples were
collected. The ice core samples were obtained from the
replicate ice columns using a 100 mm diameter Cold
3.2. The spray freezing test
Regions Research and Engineering Laboratory
(CRREL) core barrel. pH, total organic carbon
The spray ice was produced under field conditions.
(TOC), COD, conductivity, color, Cl
, and SO2
4
The wastewaters were sprayed in a field at the Ellerslie
concentrations of the samples were measured. Standard
Research Station, University of Alberta, Edmonton,
Methods for the Examination of Water and Wastewater
Alta., Canada during winter. The spraying operation
[14] were followed for all chemical analyses. Table 2
was performed under two ambient temperature condi-
summarizes the analytical methods used.
tions:
10 C and
24 C.
The equipment consisted of a spray gun with a
3.17 mm diameter circular nozzle and a pump operated
at 600–650 kPa pressure. The wastewater contained in 4. Results and discussions
200 L barrels was sprayed onto a tarp hung between two
poles. The spraying method was chosen to avoid 4.1. Impurity content of runoff samples
contaminating the surrounding areas with the waste-
waters. The impurity content of various samples collected is
Before the spraying operation, the droplet size expressed as a concentration ratio, the ratio of the
distributions of the sprayed wastewaters were deter- impurity concentration in the runoff or spray ice (C) to
mined under working conditions using the method the impurity concentration of the feed water (Co ). The
described by Laws and Parson [13]. Approximately
56% of the droplets had a diameter less than 1.6 mm and Table 2
Summary of sample analytical methods
the diameter of the remaining droplets was in the range
of 1.7–2.8 mm. Test Method
The mixture of ice and water formed after spraying
Chemical oxygen demand Standard methoda 5220 (B)
was collected and placed into Plexiglas columns with an
(COD)
inside diameter of 240 mm and a height of 300 mm. Cl
Standard method 4500-Cl
(D)
Drainwater (runoff), if formed, was collected from the Color Standard method 2120 (C)
bottom of the columns. City of Edmonton tap water was Conductivity Standard method 2510
also sprayed under the same conditions to serve as a pH Standard method 4500-H+
‘‘blank’’. Total organic carbon (TOC) Standard method 5310 (B)
At
10 C, the sprayed wastewater only partially froze SO2

4 Standard method 4500-SO2

4
and approximately 30% of the total volume of the (B)
sprayed water was released as runoff. Freezing con- a
Standard Methods for the Examination of Water and
tinued after the ice slurry was put into the columns. Wastewater (American Public Health Association, 1995)

Table 1
Composition of the pulp mill effluent and oil sands tailings pond water before the spray freezing process

Wastewater pH TOC COD Color Conductivity Cl
SO2

4
(mg/L) (mg/L) (CU) (mO/cm) (mg/L) (mg/L)

Pulp mill effluent 7.2–7.6 231–274 520–682 1305–1401 2450–2800 N/A N/A
Oil sands tailings pond water 8.2–8.7 134–158 354–476 N/A 2400–3640 343–476 108–165

N/A—the wastewater was not analyzed for the parameter.

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582 W. Gao et al. / Water Research 38 (2004) 579–584
impurity concentration ratios of the runoff samples are
listed in Table 3. As expected, all concentration ratios of
the runoff samples were greater than 1 because the
impurities rejected by the growing ice crystals were
concentrated in the liquid phase, i.e. runoff. The
concentration ratios of runoff of the pulp mill effluent
were in the range of 1.01–1.53. The separation efficiency
of organic contaminants from the spray ice was slightly
higher than that of the ionic species (estimated by
conductivity) as concentration ratios of color, TOC,
COD were 1.46–1.53 as compared to 1.42 for con-
ductivity. Reduction in H+ ion concentration was
observed in all runoff samples. The pH of the runoff
of pulp mill effluent increased by 0.5 units while the
increase was smaller for the runoff of oil sands tailings
pond water. More discussions will be given regarding the
changes in sample pH later. For the oil sand tailings
pond water which contains relatively higher concentra-
tions of inorganic substances, higher concentration
ratios in runoff were obtained for SO2
4 and COD (both
were 1.62). In general, the runoff of oil sands tailings
pond water had higher concentrations of impurities than
that of the pulp mill effluent. The individual removal
efficiency of organic and inorganic contaminants was
influenced by the chemical characteristics of the sprayed
wastewater. Malo and Baker [15] found that nonionized
substances were usually rejected more efficiently from
the ice than ions; however, in a complex system
containing both organic and inorganic solutes the
inorganic solutes would interfere with the rejection of
organic solutes.
The drainage conditions of runoff directly influence
the quality of spray ice produced and so the overall
impurity removal efficiency of the spray freezing
process. The runoff concentration ratios from this
experimental study were lower than those obtained
from a field test of oil sands tailings pond water [16],
where the concentration ratios of runoff were at least 2.0
for all parameters (except for pH) examined. The higher
separation efficiency of impurities obtained under field
Table 3
Impurity concentration ratios and reduction efficiency (spray ice formed at
10 C)
Parameters Pulp Mill Effluent
Runoff Ice cores Impurity reduction
(C=Co ) (C=Co ) in ice (E) (%)
COD 1.46 0.59 59
TOC 1.53 0.44 63
Conductivity 1.42 0.38 71
Color 1.48 0.37 65
Cl
N/A N/A N/A
SO2

4 N/A N/A N/A
pH 1.01 1.33 N/A
N/A—the wastewater was not analyzed for the parameter.
conditions could be caused by the better drainage of
runoff. Under field conditions, the runoff could flow
freely through the sloped containment area to the
collector pipes thus there was less interference of the
runoff. When the ice slurry was placed in the Plexiglas
columns, the runoff (drainwater) could only be dis-
charged through the small drainage hole located at the
center of the container bottom. The runoff flow was
interrupted when the hole was blocked by ice before the
ice slurry completely froze.
4.2. Ice core samples
As shown in Table 3, the spray ice formed at
10 C
had much lower impurity content than the feed water.
The concentration ratios of ice cores formed from pulp
mill effluent were from 0.37 (for color) to 0. 59 (for
COD) and 0.37 (for conductivity) to 0.50 (for COD) for
the ice cores of oil sands tailings pond water (without
including pH values).
For the spray ice produced at
24 C, the impurity
concentrations in the ice core samples were similar to
those in the feed water. The impurity concentration
ratios were from 0.85 to 1.10 for ice cores of pulp mill
effluent and 1.00–1.10 for ice cores of oil sands tailings
pond water. This is expected as the wastewaters
completely froze when sprayed at
24 C. Because no
runoff was produced, all impurities in the wastewater
were trapped within the spray ice. The discrepancy of
the impurity concentration ratio from the value of 1 was
due to the different evaporation rates of water and
impurities occurred during the spraying.
Obvious increase in pH values was observed in all ice
samples. The concentration ratio of pH of the ice
samples was 1.10–1.20 for oil sands tailings pond water
and 1.30–1.40 for pulp mill effluent. The increase in pH
values implied the loss of acidity in spray ice and runoff
samples. Similar to the aeration process, spraying of
wastewater into atmosphere might cause oxidation of
volatile organic compounds and stripping of the gases
Oil sands tailings pond water
Runoff Ice cores Impurity reduction
(C=Co ) (C=Co ) in ice (E) (%)
1.62 0.50 70
1.55 0.48 77
1.45 0.37 78
N/A N/A N/A
1.57 0.43 67
1.62 0.46 64
1.01 1.19 N/A
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W. Gao et al. / Water Research 38 (2004) 579–584
such as CO2, H2S, which could have induced the change
of pH in the sprayed water. pH of the sprayed water
could also be increased by losing of bicarbonate, HCO
3 The impurity reduction efficiency in the spray ice was
(2HCO
3 -CO3 +CO2m+H2m) during spray freezing
2

[17]. The extent of pH increase appeared to be waste-
water dependent, greater increase in pH occurred for the
runoff and ice samples of pulp mill effluent. We can only
speculate that the greater increase in pH values of runoff
and ice samples of pulp mill effluent was due to the fact
that the pulp mill effluent contained higher concentra-
tions of organic compounds; therefore, more organic
acids and/or volatile compounds were oxidized or
stripped during the spraying.
The distribution of impurities within the spray ice
columns was examined (on macro-scale) for the study of
the impurity elution during the melting process. The
distribution of impurities along the height of the
ice columns was distinctively different for the spray ice
formed with and without runoff generation. To check
impurity distribution, all ice core samples were cut into
three pieces (top, middle and bottom). For the ice
produced with runoff generation (at
10 C), impurity
concentrations increased dramatically from top to the
bottom of the ice core. The impurity concentrations of
the bottom section were several times higher than those
in the top and middle sections. It shows clearly in Fig. 1
by the increase in color intensity at bottom section of the
ice core produced from pulp mill effluent. For spray ice
produced at
24 C, there were no distinguishable
differences in the impurity content in all sections of
the ice cores. As shown in Fig. 2, the color of the ice was
uniform along the ice core, which was obviously
different from the one shown in Fig. 1.
Fig. 1. Ice core of spray ice made from pulp mill effluent at

10 C.
Fig. 2. Ice core of spray ice made from pulp mill effluent at

24 C.
583
4.3. Impurity reduction in spray ice
determined by the following equation:
 
Ci Vi
Eð%Þ ¼ 100  1
; ð1Þ
Co Vo
where Ci and Vi are impurity concentration and the
volume of spray ice and Co and Vo are the impurity
concentration and the total volume feed water, respec-
tively. Although the volume lost due to evaporation
and other reasons (such as blowing away by wind or
could not be collected after it landed on the tarp, etc.)
could be estimated, an accurate mass balance could
not be obtained as the impurity concentrations in the
evaporated volume were unknown. The impurity reduc-
tion efficiencies in the spray ice produced at
10 C
were listed in Table 3. The conductivity reduction in the
spray ice reached 71% for pulp mill effluent and 78%
for oil sands tailings pond water, the highest reduction
among all parameters tested. The acidity lost during the
spray freezing of the wastewater could have contributed
to this higher reduction efficiency. Runoff removed
more color (65%) and TOC (63%) causing materials
from the pulp mill effluent than COD (59%) causing
substances. For the oil sands tailings pond water, the
reduction efficiency of TOC (77%) was also higher than
COD (70%) while both TOC and COD reduction were
higher than the reduction of Cl
and SO2
4 , the
inorganic substances monitored. Organic and inorganic
contaminants were separated from ice at different
efficiency.
There was no significant impurity reduction for the
spray ice formed without runoff generation. The two
most important criteria that should be used to evaluate
the spray freezing process are the volume and quality of
the final product (purified) water. The results obtained
from this study indicated that the runoff (which was
about 30% of the total volume of the feed water)
resulted in above 60% impurity removal in the spray ice.
Most of the meltwater from the spray ice formed under
partial freezing conditions can be classified as high-
quality product water. On the other hand, the spray ice
produced without runoff generation, almost all impu-
rities in the feed water were trapped in the ice columns.
To achieve the same level of product water quality as the
partial freezing condition, much more meltwater has to
be wasted to carry away the large amount of impurities
remaining within the ice columns, therefore less final
product water [18]. In order to achieve the maximum
volume of high-quality product water, a certain volume
of runoff should be generated. The objective is to
control the spraying conditions to generate a small
volume of runoff with the highest impurity concentra-
tions possible.
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584 W. Gao et al. / Water Research 38 (2004) 579–584
5. Summaries and conclusions
Experimental results obtained from this study have
demonstrated that partial freezing by spraying is a
simple and effective method to treat the selected
industrial wastewaters.
Partial freezing by spraying can effectively reduce
organic and inorganic contaminants present in the pulp
mill effluent and oil sands tailings pond water. Greater
than 60% impurity reduction was achieved in the spray
ice formed when about 30% of the total volume of feed
water was released as runoff. The individual impurity
removal efficiency was different. The order of increasing
removal efficiency for pulp mill effluent is conductivity,
color, TOC, and COD. For oil sands tailings pond
water, it is conductivity, TOC, COD, Cl
and SO24. To
achieve higher impurity removal efficiency the sprayed
water should only partially freeze and the runoff
removed.
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