INNOVATIVE WATER PURIFICATION

METHOD AND DEVICES

V. Gevod, I. Reshetnyak, S. Gevod, I. Shklyarova and A. Rudenko

Ukrainian State Chemical-Technology University, 8 Gagarin Ave., Dnepropetrovsk 49005,

Ukraine

ABSTRACT
The main sources of drinking water are often polluted by industrial
and municipal chemicals. Water treatment plants reduce the concentrations
of harmful chemicals in water to a safe level and mandatory disinfection
renders water non-hazardous from a bacteriological standpoint. However,
conventional water treatment technologies using chlorine result in formation
of disinfectant by-products. They have been proved to be strongly
carcinogenic. Additionally, water quality deteriorates through the
distribution networks. This is due to reproduction and decay of different
microorganisms inside the water mains. Thus, at the endpoints of water
networks, the concentrations of trihalomethanes, surface-active substances,
iron compounds, etc., may exceed the maximum permissible concentration
(MPC) by several times, and those of heterotrophs – up to hundred times.
Contaminated water causes at least 80% of human diseases, therefore,
innovative technologies for water treatment are urgently needed. There is
also a worldwide demand for cost-effective means to prevent consumption
of secondary contaminated tap water. Currently, the problem is being solved
by manufacturing purified bottled water and by installing adsorption-
filtering and osmotic systems. These systems are expensive both to operate
and to maintain.
A novel bubble-film extraction system for water treatment is an
alternative to the above-mentioned systems. The principle of the innovation is
based on the following fact: inherent secondary produced surface-active water
contaminants act as water cleaning agents during its treatment by the stream
of air bubbles in a space of special geometry. This method has been shown to
purify water by 10-100 times more economically than by filtering through

137

A. Omelchenko et al (eds.),
Modern Tools and Methods of Water Treatment for Improving Living Standards, 137–149.
© 2005 Springer. Printed in the Netherlands.
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charcoal. The quality of purified water satisfies the WHO requirements. Pilot
scale bubble-film extraction water purifiers were produced and tested. The
method can be applied for groundwater conditioning and wastewater post-
purification. For advanced purification, very small amounts of special
surface-active additives could be used to accelerate adsorption of pollutants
to the interface and, hence, increase the degree of water purification. The
additive serves as a disinfectant and additional carrier of contaminants such
as bacteria, viruses, humic matter, iron and arsenic compounds, etc. The
method could be used either in combination with conventional systems or
instead of them.

WHAT IS THE PROBLEM?

Surface and ground waters constitute the main sources of drinking
water worldwide. These water sources are often polluted by industrial and
municipal chemicals. Water treatment plants reduce the concentration of
harmful chemicals in water to non-toxic levels and mandatory disinfection
renders water non-hazardous from a bacteriological standpoint. However,
conventional water treatment technologies using chlorine result in the
formation of disinfectant by-products. Chlorine-based organic derivatives
have been proved to be strongly carcinogenic. An additional problem arises
from water pollution inside the distribution systems. It is due to the
reproduction and decay of different microorganisms in water mains. This
phenomenon can take place everywhere regardless of the initial water
disinfection.
The relationship between the concentration of chloramines (sterilizing
agent) and heterotrophic cells, which are the products of secondary tap water
bio-pollution, has been studied extensively in the water network in New
Jersey (USA) (Woolschlager et al. 2000). It was found that the concentration
of chloramines decreases and heterotrophic counts increase significantly as
water passes through the distribution system. The average chloramine
concentration in the water leaving the treatment plant was about 3 mg/L and
it dropped to 0.36 mg/L after 8 kilometers. This loss of chloramine residuals
was due to auto-catalytic reactions, in which chloramines spontaneously
decay in the bulk water and at the pipe surface, oxidation reactions with
reduced forms of organics and iron, and biologically catalyzed reactions,
such as reactions with nitrite produced by nitrifiers as well as direct co-
methabolism of chloramines by nitrifiers.
At the same time, the heterotrophic counts reached 105 cells/mL within
the distribution system. The comparison of chloramine and heterotrophs
concentrations revealed a very important trend – the concentration of
heterotrophs is not strongly related to chloramine concentration. Many areas
of the distribution system had bacteria concentration in excess of 103 cells/mL
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in the presence of over 2 mg/L of chloramine. Taking into account that the
dry weight of a medium size bacterium is about 4u10-9 mg, one can calculate
the concentration of heterotrophic cells:

C = 4˜10-9 u 105 u103 = 0.4 mg/L

This concentration is not extremely alarming. However, it could cause

significant accumulation of bacterial biomass as biofilm inside the water
mains up to 500 mg/m of pipe length per year. Any disturbance of the
biofilm inside the pipe initiates the release of organic matter into the
transported water. This organic matter interacts with dissolved chlorine
forming chloroorganic derivatives. Additionally, organic substances
accelerate corrosion of the pipes in the water supplying system increasing
the amount of iron and other extrinsic admixtures in the tap water.
The above effects could take place anywhere; however, they are
especially strongly manifested inside lengthy water supply networks. The
water distribution system existing in Dnepropetrovsk, Ukraine, is a typical
example of such a network. In Dnepropetrovsk, the total length of
distribution water pipes exceeds 6000 kilometers. Through these pipes, the
tap water is supplied to more than one million inhabitants. In summer, there
is a water shortage in the town. The deficiency reaches 105 m3 per day. As a
result, the water pressure is reduced and water does not reach peripheral
districts. In this case, air penetrates into the unfilled water pipes and
promotes their destruction due to bio-corrosion and corrosion with oxygen
depolarization. The water in the pipes becomes saturated with iron
hydroxides and other contaminants. Simultaneously, water undergoes
degassing with respect to "active" chlorine. Therefore, the growth of fungi
and bacteria accelerates. These processes have an influence on the
permanganate water oxidation susceptibility, the concentration of surface-
active substances (SAS) and other water quality parameters.
The situation is the same in other big cities. Summarized data on the
deviation of water quality from hygienic requirements in Dnepropetrovsk
and Kiev is given in Figure 1. It can be seen that water quality must be
improved with respect to turbidity, color, permanganate index, concentration
of chlorine organic derivatives, SAS, iron and aluminum compounds.
Therefore, it is absolutely necessary to post-purify the tap water at the points
of its immediate consumption.

HOW IS THE PROBLEM SOLVED AT PRESENT?

There are many methods of water quality improvement. The majority
of them are based on water filtration through membranes, carbon adsorption
and ion exchange. The commercial devices are manufactured and supplied
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worldwide by the leading companies, such as Brita, Inno-Water, etc. Both

theoretically and practically these systems purify water to an extremely high

Figure 1. The deviations of tap water quality from hygienic requirements in Dnepropetrovsk
and Kiev, Ukraine.

degree. However, some important drawbacks become apparent during their

use. In particular, when charcoal or other adsorbents lose their adsorption
capacity they also lose the purification ability and become a good substrate
for reproduction of different microorganisms. As a result, filtered water
becomes more contaminated than entering water. It is also known that ultra-
filtration and osmotic membranes cannot serve as efficient barriers to
dissolved gases and they are very sensitive to water hardness. Therefore, it is
necessary to combine adsorption-filtering and osmotic systems. However,
such combinations require regular maintenance and are very expensive in the
long run. These disadvantages are critical for Ukraine. Thus, there is a need
for new more economical and effective methods of water purification, which
are able to give high quality purified water but lack the above-mentioned
disadvantages.

WHAT SYSTEM CAN BE CONSIDERED AS AN

ALTERNATIVE?
A bubble-film extraction system can be considered as an alternative to
the known systems. The bubble-film extraction process is based on the ability
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of SAS to act as water cleaning agents. The driving force of the purifying
process is a stream of air bubbles. This system is very economical and
maintains water purification efficiency during use. The bubble-film
extraction is similar to flotation in terms of principle of action, but its
separation efficiency with respect to SAS removal is about two orders of
magnitude higher than that of flotation (Gevod et al. 2002).
The mechanism responsible for the bubble-film extraction is rather
simple. Step by step, it is described schematically in Figure 2.

Figure 2. The behavior of air bubbles in air-water system under various experimental
F
conditions.
In particular, Fig. 2a shows the initial stage: air bubbles are produced
by appropriate means in the bulk, contaminated water. While passing
through the bulk water, these bubbles adsorb surface-active contaminants
and deliver them to the planar air-water interface. As a result, the interface
becomes filled with an excess of surface-active matter. Subsequently, the air
bubbles transferred through the interface saturated with SAS form large
hemispherical formations in the shape of half-bubbles. The internal and
external surfaces of these formations are covered and stabilized by
monolayers of SAS. Herein, the concentration of surface-active
contaminants in the liquid body of these formations is much higher than in
the bulk water. The structure of half-bubbles is depicted in Figure 2b.
When the above-mentioned formations appear at the air-water
interface separated from its surroundings by a pipe with a suitable diameter,
the following additional effects occur. First of all, some of the initially
formed hemispheres collapse inside the pipe and its interior surface becomes
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moistened by a solution of SAS. This allows a sliding movement of newly

formed half-bubbles upwards along the wetted pipe’s surface. This process
is accompanied by the transformation of hemispheres into a series of flat thin
liquid films (membranes) consisting of a concentrated solution of SAS. Each
flat liquid film occupies the cross-section area inside the pipe. Neighboring
films are separated from each other by air released from collapsed bubbles.
In such a way, a thin liquid film-air dynamic system is formed inside the
pipe. It is schematically shown in Figure 2c.
The rate of formation of flat liquid films and their life span until
spontaneous collapse are dependent upon the shape and area of the pipe’s
cross-section, SAS concentration, ionic strength and temperature. A
cylindrical pipe with an internal cross-section area in the range 2-4 cm2 is the
most suitable. At larger cross-sections (see Figure 2d), the rate of formation
of flat liquid films is sharply decreased. At much smaller cross-sections, the
air bubble stream does not form flat films at all. It moves inside the pipe like
a continuous gas-liquid mixture as is shown in Figure 2e.
Thus, a pipe of optimum diameter attached to an inverted funnel and
installed vertically above the flow of air bubbles is a prototype of the, so-
called, bubble-film extractor.

DESIGN AND MODE OF OPERATION OF THE

ELEMENTARY BUBBLE-FILM EXTRACTOR
The elementary bubble-film extractor represented in Fig. 3 consists of
3-shaped pipe with conjugation zone of confuser and diffuser. This part of
the pipe is connected to an inverted funnel. The device operates as follows.
The air bubbles are fed into SAS contaminated water. Passing through the
bulk water, they adsorb the molecules of surface-active substances and enter
the funnel. This results in the formation of a bubble-liquid column in the
bottom part of the device. Inside the column, the rate of vertical motion of
each air bubble is sharply reduced compared to their upward movement in
the bulk water. The concentration of SAS in the bubble-liquid column is
increased as compared to the bulk water, especially at the top of the column.
Therefore, when the bubble-liquid column moves through the conjugation
zone, it is transformed into a series of thin flat liquid films, as described
above. These films consist of concentrated SAS solution and their surfaces
are stabilized by monolayers of removed SAS.
Inside the 3-shaped pipe, the films move under the action of pressure
released from the collapsed bubbles. The thickness of the films decreases as
long as they move towards the exit from the bubble-film extractor. The
concentrate of SAS is released from the collapsed films at the output of the
device.
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Figure 3. The design of elementary bubble-film extractor: 1 – vessel with treated

F
water, 2 – air sprayer, 3 – internal ttube, 4 – entrapping funnel, 5 – confuser, 6 –
diffuser, 7 – 3-shaped pipe.

THE RESULTS OF THE TEST OF THE ELEMENTARY

BUBBLE-FILM EXTRACTOR
The tests of the elementary bubble-film extractor were carried out
using sodium decylsulphate and other detergents such as lipid and protein
solutions of various concentrations. Tests of ordinary tap water were also
conducted. It was found that the elementary bubble-film extractor allows a
reduction of the concentration of various surface-active substances in water
by about three orders of magnitude.
The use of the bubble-film extractor is not limited to treatment of
solutions of SAS only. The method is also effective in treating aqueous
dispersed systems stabilized by SAS, such as polyvinyl acetate emulsion,
denatured solution of egg whites, dispersion of hydrolysed aluminium
sulphate in the presence of anionic SAS, and other colloid systems. Perfect
separation was observed in all cases studied (Gevod et al. 2002).
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In general, the post-purification process by means of bubble-film extraction

could be schematically described as follows:

Bulk water with SAS and other contaminants

p
Air bubbles are fed into contaminated water
p
Surface-active and complementary contaminants are adsorbed on uprising
air bubbles
p
Bubbles with adsorbed contaminants are transformed into thin liquid films
flowing inside the bubble-film extractor
p
Pollution is removed through the bubble-film extractor in the form of a thin
liquid film flow.

The bubble-film extraction has an important advantage as compared

to regular flotation, microflotation, ionic flotation, and foam separation.
During the bubble-film extraction, a special channel isolates the stream of
floated products from the water surface. Thus, the adsorbate is completely
transferred into thin liquid films, and does not dissolve back into the aerated
water. This results in very high efficiency of the bubble-film extraction. For
example, the concentration of targeted contaminants could be decreased to
the limit of their analytical determination. The concentration profiles of
different contaminated waters in air bubble–water systems vs. time of the
bubble-film extraction process are presented in Fig. 4.
Experiments conducted in our laboratory have shown that the bubble-
film extraction is able to improve tap water quality with respect to a number
of parameters. The results of these experiments are summarized in Table 1.
The experimental details were as follow. The treated volume of water
was 3 liters. The air-sprayer was placed 10 cm below the capturing funnel.
The rate of the air discharge for bubbling was about 1 L/min. The water
samples were treated for 20 minutes. The chemical and microbiological
analyses were carried out in accordance with standard methods.
Comparison of the results obtained with hygiene standards shows that
bubble-film extraction improves water quality with respect to all tested
parameters. The advantage of this method becomes especially obvious if the
low energy consumption required running the bubble-film extractor is
considered. Typically, the power consumption does not exceed 1 Wuh per
liter of treated water.
It is worth noting that the efficiency of bubble-film water purification
is directly proportional to the degree of water pollution by endogenous SAS.
Their concentration in the tap water of big cities is usually sufficient for
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Figure 4. The concentration profiles of different contaminated waters in air bubble – water
systems vs. time of bubble-film extraction.

Table 1. The efficiency of water treatment by bubble-film extractor.

Parameter Initial water Treated water Standard

Colouration, degree 20 – 50  20 20
Odour, points 2–3 1 2
Turbidity, mg/L 4 – 14 0.87 – 3 1.5
pH 7.25 r 0.3 7.32 r 0.1 6.0 y 9.0
Taste and aftertaste, points 2–3 1 2
Residual chlorine, mg/L 1.2  0.6 0.8y1.2
Chloroform, mg/L 0.1 Unfound 0.06
Tetrachloride, mg/L 0.004 – 0.006 Unfound 0.005
Aluminium, mg/L 0.24r0.02 0.11 r 0.001 0.5
Iron, mg/L 3.0 – 14.0 2.0 – 11.0 0.3
Cadmium, mg/L 0.0005 Unfound 0.001
Strontium, mg/L 0.103 0.09 2.0
Ammonia, mg/L  0.04 Unfound 2.0
SAS, mg/L 3.0 0.025 1.0
SAS, mg/L* 0.5 0.04 0
Arsenic, mg/L 0.005r0.0001 Unfound 0.05
TMA (per 1 mL) * 63–630 27 – 150 100
Coli-index* 100000 50000 <3
* Loading experiment.

effective water quality improvement. If water does not contain a sufficient

amount of endogenous surface-active contaminants, it is necessary to inject
into the water some surface-active reagent. This increases the degree of
removal of various «target» contaminants from treated water.
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This innovative approach is currently under investigation in our

laboratory. So far, it has been found that a small amount of special surface-
active chemical added to the treated water accelerates adsorption of
contaminants and, hence, increases the degree of water purification by
bubble-film extraction. This additive acts as a disinfectant, additional
collector and carrier of «target» contaminants, such as bacteria, viruses,
humic matter, iron and arsenic compounds, etc. This innovation increases
the efficiency of bubble-film extraction. Water is treated more effectively in
a single unit and in one step.
WATER PURIFIERS BASED ON BUBBLE-FILM
EXTRACTION
A number of novel water purifiers based on bubble-film extraction
were designed in our laboratory and manufactured. These devices are
intended for personal and communal use. Three very economical and
convenient devices for personal use are shown in Fig. 5. Fig. 5a shows the
water purifier for post-purification of secondary polluted tap water with an
output rate of about 1.5 L/hour. This device consists of three main parts: the
purifying module (I), the vessel for purified water (II), and an air pump with
a flexible pipe (III). The purifying module comprises a bubble-film extractor
connected to a funnel and a collector of wastes with a removable cover made
of plastic used for foodstuffs. This water purifier is installed on the top of a
special reservoir filled with water. The purification process begins from the
moment the air pump is turned on.
At the beginning of operation, the initial concentration of surface-
active and other contaminants in the bulk water is large. The bubbles
flowing inside the bubble-film extractor form the bubble-liquid column,
which is transformed into the liquid films at the upper part of bubble-film
extractor. This column moves upwards inside the pipe (stem of the funnel)
and breaks down at the upper opening of the pipe, releasing wastes into the
waste collector. The intensity of generation of the liquid film is reduced as
the concentration of SAS is decreased. When water does not contain SAS
the thin flat liquid films of concentrated contaminants are not formed inside
the bubble-film extractor. To complete water decontamination, it is
necessary to achieve a ratio of treated water volume to total air bubble
volume not less than 1:40. Therefore, the treatment lasts for about two hours
for 3 L of water and air pump capacity of 1 L/min of compressed air.
Water purifiers shown in Fig. 5 b and c are equipped with the same
purifying module, but, in the device b, the air bubble stream is produced by a
special impeller, which is driven by an electric motor consuming about 2 Wuh
of power. In the device c, the air stream is generated by a special injector.
This device allows post-purification of 3-50 L of water, depending on the type
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Figure 5. The assortment of the bubble-film water purifiers.

of vessel used. In this device a submersible pump consuming 12-15 Wuh is

used.
A more complex and powerful water purifier is represented in Figure
6. This is a flowing bubble-film water purifier and it is capable of producing
up to 3 m3 of purified water per day. In this device, water is treated under
stationary conditions with a flow rate of about 2 L/min. The volume of
collected wastewater does not exceed 3% of treated water. Compressed air is
created by a membrane air pump producing about 140 L/min of air at a
pressure of 0.35 MPa. The air discharge in each column is 35 L/min.

SUMMARY
The bubble-film extraction method and bubble-film water purifiers are
mainly designed for tap water post-purification as an alternative to existing
systems. In contrast to the osmotic and adsorption-filtering devices, the
bubble-film water purifiers do not require any replacement parts. During the
bubble-film extraction, the air bubbles fed into water adsorb the surface-
active substances together with other surface-inactive compounds.
Subsequently, the bubble flow is transformed into a flow of thin flat liquid
films (membranes). Each membrane consists of a concentrated solution of
water contaminants. The amount of adsorbate, Q, inside each film is
described by the equation:
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Figure 6. Flowing bubble-film water purifier with productivity up to 3 m3 of

F
purified water per day.

Q Sr 2 kCnW

Here, r is the radius of an air bubble, k is the rate constant of

adsorption of water contaminants at the air bubble surface, C is the bulk
concentration of contaminants, n is the number of air bubbles forming one
liquid film, W is the residence time of an air bubble in the bulk water.
The rate of bubble-film water purification is directly proportional to
the concentration of SAS, intensity of bubbling, and the length of air bubble
pathway in the bulk water. Thus, optimisation of the process is possible by
changing the bubbling intensity, the length of the air bubble pathway and by
increasing the number of removing channels in the bubble-film extractor at
given water flow. Doing so, it is easy to achieve the required degree of water
purification at minimal power and material consumption.
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REFERENCES

Gevod V, Reshetnyak I, Shklyarova I, Khokhlov A, S Gevod. 2002: Surface-active and other

contaminants of tap water. Properties, monitoring, the reasons of accumulation and effective
removal. USCTU. Dnepropetrovsk.

Woolschlager J, Rittmann B, Piriou P, Kiene L and B Schwartz 2000: A comprehensive

disinfection and water quality model for drinking water distribution systems. First World
Water Congress of IWA; 2000 July 3-7; Paris. ISBN: 2-9515416-0-0. EAN: 9782951541603;
NP-119.