586 Bonding of Toxic Metal Ions

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586 BONDING OF TOXIC METAL IONS
4. Durán-Domı́nguez-de-Bazúa, M.C. (1992). Procedure for Cook- When discharged directly into rivers, polluted wastew-
ing Cereals and Other Grains (Legumes and Oilseeds) by Alka- ater poses a great risk to the aquatic ecosystem, and dis-
line Extrusion/Procedimiento para Cocer Gramı́neas (Cereals, charge into a sewage system negatively affects biosludge
Leguminosas y Oleaginosas) por Extrusion Alcalina. Patent activity and leads to contamination of the sludge to be
requested on May 13. Dir. Gral. Invenciones y Marcas. Dept. disposed of. As a result of the standards specified in
Patentes. Secretarı́a de Patrimonio y Fomento Industrial, the Water Resources Act, which was amended in 1986,
México D.F. Mexico.
industry takes precautions against these risks by treating
5. Durán-Domı́nguez-de-Bazúa, M.C., Sánchez-Tovar, S.A., and dangerous components in a partial stream before mixing
Solı́s-Fuentes, J.A. (2002). Procedure for Cooking Grains (Cere-
with other types of wastewater. So, research was focused,
als, Legumes, and Oilseeds) and Agroindustrial by-Products
among others, on the development of highly selective bond-
by Alkaline Extrusion/Procedimiento Para Cocer Gramı́neas
(Cereals, Leguminosas y Oleaginosas) y Subproductos Agroin- ing agents (often denoted as BA) with fast reaction kinetics
dustriales por Extrusion Alcalina. Patent requested on Novem- for removing heavy metal ions (Fig. 1a). The latter may
ber 16. Instituto Mexicano de la Protección Industrial, México lead to better use of the capacity of bonding agents, result-
D.F. Mexico. ing in smaller units and low residual concentrations of
6. Durán-de-Bazúa, C. and Hartmann, L. (1979). Produktion Von toxic metals in treated water streams, to comply with indi-
Biomasse aus Prozessabwaessern Der Lebensmittelindustrie. vidual standards for water reuse or discharge—sorption
Internationales Seminar, Universität Karlsruhe, 7 IIBB- kinetics constitutes another article in this Encyclopedia
UNIKA, Karlsruhe, German Federal Republic. of Water.
7. Durán-Domı́nguez-de-Bazúa, M.C. (1987). Effluents of the food In addition to zeolites (1,2), other typical materials
industry in México: Environmental impacts on soil and water extensively used are apatites (3,4) and various iron sor-
resources and possible solution using the biotechnological bents (5,6). These BA materials are broadly classified in
approach. Case problem: The corn industry. In: Global three classes: carbon sorbents (active carbons, activated
Bioconversions. Vol. II, Chap. 4. CRC Press, Boca Raton, FL, carbon fibers, molecular carbon sieves, fullerenes, hetero-
pp. 75–119.
fullerenes, nanomaterials), mineral sorbents (silica gel,
8. Durán-Domı́nguez, M.C., Pedroza-Islas, R., Rosas-Vázquez, C., activated alumina, oxides of metals, hydroxides of met-
Luna-Pabello, V.M., Sánchez-Zamora, A., Capilla-Rivera, A.,
als, zeolites, clay minerals, inorganic nanomaterials) and
Paredes-Gómez, L., Valderrama-Herrera, S.B., and Vázquez-
others (synthetic polymers, composite sorbents, mixed sor-
Cedeño, I. (1991). Producción de alimentos para peces:
Utilización de subproductos del tratamiento de aguas resid- bents, etc.).
uales. In: Premio Nacional Serfı́n El Medio Ambiente. J.J. De A review paper on bonding agents recently presented
Olloqui (Ed.). Futura Eds., Villa Nicolás Romero, Méx., Mexico, to a conference (7) also mentioned new types such as
pp. 79–106. mesoporous materials and chelating resins and their
potential applications to metal bonding from aqueous
solutions. It also presented the equilibrium sorption
BONDING OF TOXIC METAL IONS capacity for metal ions of certain sorbents and stated
that the functionalized silica materials have shown higher
E.N. PELEKA uptake capacity than that of other materials found in the
KOSTAS A. MATIS literature. An inherent disadvantage of these materials is
Aristotle University their low loading capacities and relatively small metal ion
Thessaloniki, Greece binding constants.
To circumvent these limitations, promising heavy
T. ERWE metal sorbents have been prepared by coupling chelating
V. MAVROV ligands (e.g., thiol, amine, or crown ether functions)
Saarland University to support matrices consisting of inorganic oxides (e.g.,
Saarbrücken, Germany silica, alumina, or clay) or organic polymers (e.g.,
polystyrene, cellulose, or polymethyl-methacrylate). Such
functionalized materials have relatively high metal ion
Worldwide environmental problems are becoming more loading capacities and strong binding affinities for selected
and more acute. It is known that many specific industrial metal ions. This performance can be attributed to the
wastewater streams with large flows contain toxic metals presence of the surface-bound ligands, which can be
in concentrations up to 500 mg/L, which have to be specifically tuned to accommodate the selective sorption
removed prior to water recycling, indirect discharge into a of targeted metal ions. Although superior in performance
sewage system, or direct discharge into surface waters. to conventional ion exchangers, functionalized matrices
Some examples are (1) rinse water in metal working remain relatively inefficient because only a fraction of the
enterprises, containing Cu, Ni, Zn, Sn, Cd, Pd, Ag, Al, Au, immobilized ligands is accessible for metal complexation.
Cr, Mo, etc.; (2) rinse water in the semiconductor industry, The discovery of mesoporous metal oxide molecular sieves
containing Cu, Sn, Pb, Sb; (3) wastewater from the copper (by Mobil researchers) and organoceramic sorbents has
industry, containing As, Se; (4) other types of water in given rise to new prospects for sorbent and catalyst
which the presence of toxic metals causes problems; design (7).
(5) drinking water from ground water contaminated with The knowledge of the governing chemical state of
As; and (6) mine water contaminated with different toxic the metal ion to be removed is a prerequisite, so that
metals (e.g., U, Ra, As). any new development is based on a solid scientific
BONDING OF TOXIC METAL IONS 587
(a) 100
80
R% Zn(II)
60
40
0.5 g/L zeolite CA 150

20 2 g/L zeolite CA 150
0.5 g/L Lewatit TP 208
2 g/L Lewatit TP 208
0
0 20 40 60
time min
(b)
Bonding and recycling stage Separation stage
Low contaminated Bonding agents Purified water

water with for reuse or
toxic metal ions Selective Membrane discharge
bondage filtration
of metal ions (MF / UF)
Recycled
bonding agent
Regenerator/
separator
Figure 1. (a) Removal of zinc (50 mg/L, pH 6) by

an ion exchange resin and zeolites for comparison
Metal ion (unpublished data). (b) Membrane separation of bond-
concentrates ing agent/metal complexes for wastewater (METASEP
for reuse project). Reprinted with gratitude from Reference 10.
foundation (8). The impact of chemical speciation is area and defined pore size distribution. The synthesis of
important in any process, including adsorption, ion these materials involved hydrolyzing aqueous solutions
exchange, or precipitation. These often act together, and of ferric salts followed by membrane purification and
the dominance of one specific is often hard to distinguish freeze drying (6). Sorption, in general, depends on the
without careful chemical measurements and advanced solution pH and its ionic strength. These macroscopic
analytical techniques. Identifying the bonding mechanism observations were used to differentiate between the
of metals on the agent/sorbent used is significant because, kind of adsorption, physical or chemisorption (13). Other
for example, the mechanism could dictate the mobilities of additional indications were obtained by examining the
the species in their existing environment. influence of temperature during equilibrium experiments
A new treatment process aimed at water and metal and/or calculating (from the van’t Hoff equation) the
reuse was developed for the selective separation of heavy change of the respective enthalpy.
metals from wastewater to reduce costs and mitigate
the environmental impact of wastewater pollutants (9).
One of the variants, divided into three stages (shown as Table 1. Information about Industrial Effluentsa
Fig. 1b), was the separation of BA-metal complexes by
cross-flow microfiltration/ultrafiltration from wastewater Wastewater Metal
that has metal concentrations less than 50 mg/L. This from Targeted Cationic Anionic Cleaning Recovery
project was a contribution to the key action of European Open pit copper Cu X X X
Union ‘‘Waste water treatment and re-use,’’ in the 5th mine
Framework programme. Copper foil Sb, Cu X X X X
The use of iron-based bonding materials, such as production
goethite and akaganėite, was successful because they Groundwater As (as X X
are inexpensive, easily synthesized, suitable for both AsF6 − )
Copper Se, As X X
cation and anion sorption, and present low risks of
production
adding a further pollutant to the system. Typical results
are presented in Fig. 2; the sorbents had high surface a
Reference 10.
(a) 100
80
60 Cr(VI) - new synthesis

Cr(VI) - goethite
R%
Cr(VI) - existing goethite
Zn(II) - new synthesis
40
20
0
3 4 5 6 7 8 9 10 11
pH
(b) 100
80
60
R%
40
Figure 2. (a) Sorption of chromates (10 mg/L) and zinc ions
(50 mg/L) by various goethite adsorbents, as a function of
20
solution pH (1 g/L goethite, 2 h contact time). Reprinted I = 0 M KNO3
with permission from Reference 11; copyright (2004) Scientific I = 0.01 M KNO3
Journals. (b) Effect of pH on the adsorption of cadmium onto I = 01 M KNO3
akaganéite for different values of ionic strength. Reprinted 0
3 4 5 6 7 8 9 10 11 12 13
with permission from Reference 12; copyright (2004) Technical
Faculty and Copper Institute, Bor Serbia. pH
The stability of a suitable bonding agent should be and solution pH modification. The aggregate, including
evaluated in a real process, for chemical and physical the metals, is usually then floated after the addition of a
stability as well as losses in the proposed flowsheet. suitable surfactant or collector (11).
The selected industrial effluents in the aforementioned The combination of flotation following sorption down-
research project (e.g., METASEP) are presented in Table 1. stream (termed sorptive flotation) for metal cation removal
An effective mode of a sorption process is based on by ion exchange materials, as the synthetic zeolites (of
a fixed-bed contactor configuration (14). The sorption MAP type), gave promise for an improved metal separa-
bed has to be porous to allow the liquid to flow tion process (16). A disadvantage of this is the application
through with minimum resistance but allow the maximum of surfactants, as flotation collectors; this represents an
mass transfer into the particles—see also the article enormous demand, as flotation also applied in mineral pro-
on Sorptive filtration in this Encyclopedia. Another cessing, is currently met by numerous chemicals, mainly
possibility for this solid/liquid separation stage of loaded petroleum-based, hence, substances that are usually toxic
ultrafine material, as adsorbents and ion exchangers are, to the environment and nonbiodegradable. For this reason,
constitutes flocculation, as examined for goethite (Fig. 3a). the successful application of biosurfactants was investi-
The dynamics of flocculation were studied by a technique gated (17).
based on measuring the fluctuations of transmitted light Regeneration of bonding agents is, of course, a
in flowing dispersions. prerequisite often overlooked. The following two modes
An alternative for metals removal is in situ production, for different BA regeneration were envisaged: (1) The
for instance, of ferric hydroxide (see Fig. 3b), which conventional, by changing the pH value; after separating
could be also conducted by electrocoagulation. Specifically, it from the treated effluent, the loaded sorbent was mixed
adsorbing colloid flotation is the process that involves with a solution containing a strong acid (or alkal in the
removing a solute from an aqueous solution by adsorption case of oxyanions) to shift the fixation equilibrium, to
on, coprecipitation with, or even occlusion in a carrier floc, recover the metal in the acidic solution, and to produce a
often produced from ferric or aluminum salts by hydrolysis regenerated agent, where the protons have replaced the
BONDING OF TOXIC METAL IONS 589
metal cations and could be recycled. (2) Electrodialysis (investigated under an EU-funded research programme,
with bipolar membranes for uncharged water-soluble too); the second-middle cycle represented flotation separa-
bonding agents and modified electrodialysis for powdered tion of the metal-loaded biomass. Biosorption, the uptake
agents (see Fig. 4). The loaded sorbent was fed into an of heavy metals by dead biomass, has gained credibility
electrodialysis reactor where, due to the electric field, during recent years, as it offers a technically feasible and
the metals were separated from the material. The metal economical approach. Several biological materials were
cations migrated in the electric field and crossed a cation- investigated for heavy metals removal, including bacteria,
exchange membrane to enter into an other compartment, yeasts, algae, and fungi.
where they reacted with hydroxyl ions generated by a Concluding, the ‘‘polluter pays’’ principle ensures
second bipolar membrane or by a cathode. The regenerated nowadays that companies have to pay the costs of
materials were recovered on one side, and a hydroxide environmental damage, or at least in part. Therefore, from
sludge was recovered on the other side (18). their point of view, an economical and effective solution is
Elsewhere (19), another multistage process was pro- required by developing techniques for improved treatment.
posed for removing aqueous cadmium consisting of, among On the other hand, many of the metal ions (cations or
others, elution at high concentrations of the sorbed metal oxyanions) that are target compounds in effluents could be
ion from the biomass (the BA used here), recycling sorbent further concentrated for recycling; incineration of toxic
and eluant, wherever possible, and recovering cadmium sludge should be avoided, as this entails transferring
electrochemically by a rotating cathode cell, in the form pollution from one state to another. The strategy is to
of metal powder as the end product. The flow diagram is reuse water and metals, so ‘‘end-of-the-pipe’’ solutions
shown with three cycles/routes for the combined process will no longer be necessary. Attempts have been made
to develop a more specific water treatment technique to
provide industrial process water as close as possible to the
source, applying quality assurance and efficiency control
(a) 7.5
techniques for operational management. An innovative
and cost-effective approach minimizes environmental
7.0 impact from wastewater and prevents potential damage
to health.
6.5 Acknowledgment
The financial help of the Energy, Environment and Sustainable
Ratio
Development programme of the European Union is gratefully

6.0 acknowledged (acronym METASEP, contract no EVK1-CT-2000-
00083).
pH
5.5 4.15 BIBLIOGRAPHY
6.05
6.98
1. Colella, C. (1999). Environmental applications of natural
5.0
zeolitic materials based on their ion exchange properties. In:
0 5 10 15 20 25 30
Natural Microporous Materials in Environmental Technology.
Time, min P. Misaelides, F. Macašek, T.J. Pinnavaia, and C. Colella
(Eds.). Kluwer Academic, Dordrecht, The Netherlands,
(b) 100
pp. 207–224.
2. Rees, L.V.C. (1997). Ion exchange in zeolites: Detergency and
80 catalytic systems. In: Progress in Ion Exchange—Advances
and Applications. A. Dyer, M.J. Hudson, and P.A. Williams
(Eds.). RSC, pp. 393–402.
60 3. Ma, Q.Y., Traina, S.J., Logan, T.J., and Ryan, J.A. (1994).
R%
Effects of aqueous Al, Cd, Cu, Fe(II), Ni, and Zn on Pb

immobilization by hydroxyapatite. Environ. Sci. Technol. 28:
40
1219–1228.
4. Mandjiny, S., Zouboulis, A.I., and Matis, K.A. (1995). Re-
20 moval of cadmium from dilute solutions by hydroxyapatite.
R% Cr(VI)
Part I. Sorption studies. Sep. Sci. Tech. 30: 2963–2978.
R% Zn(II) 5. Lo, S., Jeng, H., and Lai, C. (1997). Characteristics and
0 adsorption properties of iron-coated sand. Water Sci. Technol.
0 200 400 600 800 1000 35(7): 63–70.
Fe(III), mg/L 6. Bakoyannakis, D.N. et al. (2003). Akaganeite and goethite-
Figure 3. (a) Flocculation of synthetic goethite (0.5 g/L) fines by type nanocrystals: Synthesis and characterization. Microp-
polyelectrolyte in the presence of As (III) (10 mg/L). Reprinted orous Mesoporous Mater. 59: 35–42.
with permission from Reference 15; copyright (1999) Kluwer. 7. Asouhidou, D.D., Lazaridis, N.K., and Matis, K.A. (2004).
(b) Removal of chromates and zinc as a function of Fe(III) con- Sorbent materials for metal ions removal from aqueous
centration by in situ coprecipitation. Reprinted with permission solutions: A review. Int. Conf. Protection Restoration Environ.
from Reference 11; copyright (2004) Scientific Journals. VII, NTUA & Stevens Inst. Tech., Myconos, Greece.
(a) Loaded bonding agent

BA-Me
Acid cycle Base cycle
BPM CEM BPM

BA-Me
OH H+ Me+ OH H+ -
+
Me+
BA-H MeOH
Electrode rinsing
Recycled bonding agent Heavy metal as

BA-H MeOH sludge
(b) Loaded bonding agent

BA-Me
Acid cycle Base cycle
A CEM CEM C
Ba-Me
O2 H2
+ -
H+ H+ 1 Me2
2 OH-
1 Me2+
2
1 Me(OH)
2
Ba-H 2
Figure 4. (a) Regeneration of water-soluble

bonding agent by electrodialysis with bipolar
membranes. (b) Regeneration of powdered Recycled bonding Heavy metal
bonding agent by modified electrodialysis. agent as
BA-H Me(OH)2 sludge
Reprinted with gratitude from Reference 10.
8. Evanko, C. and Dzombak, D. (1997). Remediation of Metals- 13. Hayes, K.F., Papelis, Ch., and Leckie, J.O. (1988). Modelling
Contaminated Soils and Groundwater. Ground-Water Reme- ionic strength effects on anion adsorption at hydrous
diation Technologies Analysis Center, Pittsburgh, PA. oxide/solution interfaces. J. Coll. Interface Sci. 125: 717–726.
9. Mavrov, V., Erwe, T., Blöcher, C., and Chmiel, H. (2003). 14. Lehmann, M., Zouboulis, A.I., and Matis, K.A. (2001). Mod-
Study of integrated processes combining adsorption, mem- elling the sorption of metals from aqueous solutions on
brane separation and flotation for heavy metal removal from goethite fixed-beds. Environ. Pollut. 113: 121–128.
wastewater. Desalination 157: 97–104. 15. Matis, K.A., Zamboulis, D., Zouboulis, A.I., and Lazaridis,
10. EU FP 5 Project METASEP. (2004). Public Report. Brussels. N.K. (1999). Goethite mineral as a sorbent for heavy metals.
11. Deliyanni, E.A., Lazaridis, N.K., Peleka, E.N., and Matis, In: Natural Microporous Materials in Environmental Technol-
K.A. (2004). Metals removal from aqueous solution by ogy. P. Misaelides, F. Macašek, T.J. Pinnavaia, and C. Colella
iron-based bonding agents. Environ. Sci. Pollut. Res. 11: (Eds.). Kluwer Academic, The Netherlands, pp. 425–433.
18–21. 16. Matis, K.A. et al. (2004). Application of flotation for the
12. Deliyanni, E.A., Bakoyannakis, D.N., Zouboulis, A.I., and separation of metal-loaded zeolites. Chemosphere 55: 65–72.
Matis, K.A. (2004). Development and study of iron-based 17. Zouboulis, A.I., Matis, K.A., Lazaridis, N.K., and Golyshin,
nanoadsorbents. 36th Int. Oct. Conf. Min. Metall. Serbia- P.N. (2003). The use of biosurfactants in flotation: Application
Montenegro. for the removal of metal ions. Miner. Eng. 16: 1231–1236.
APPLICATION OF MICROFILTRATION TO INDUSTRIAL WASTEWATERS 591
18. Schlichter, B., Mavrov, V., Erwe, T., and Chmiel, H. (2004). Such a combination could, for instance, have as
Regeneration of bonding agents loaded with heavy metals the first step the use of a suitable bonding agent
by electrodialysis with bipolar membranes. J. Membrane Sci. followed by another separation technique downstream
232: 99–105. as a membrane process (3); see also the article on
19. Butter, T.J. et al. (1998). The removal and recovery of Bonding of toxic metal ions in this Encyclopedia of
cadmium from dilute aqueous solutions by biosorption and Water. Metal ion recovery by membrane technologies
electrolysis at laboratory scale. Water Res. 32: 400–406. from aqueous waste streams was reviewed by several
vendors in the field (4). At a lower particle size range
than that for microfiltration, as aforementioned, other
APPLICATION OF MICROFILTRATION TO membrane processes are applied. Some examples of these
INDUSTRIAL WASTEWATERS applications involve, among others, ultrafiltration (UF)
of fruit juices using tubular configuration polymeric
T. ERWE and ceramic membranes (5) and reverse osmosis in
C. BLÖCHER treating sugar beet press water (6). Different polymeric
V. MAVROV membranes from commercial companies were tested for
Saarland University wine clarification (7), and the ceramic membranes were
Saarbrücken, Germany compared with polymeric ones for removing of natural
organic matter from drinking water sources (8).
KOSTAS A. MATIS Ceramics are good materials for producing membrane
Aristotle University filtration tubes (9). The advantages of ceramic membranes
Thessaloniki, Greece compared to polymer membranes include resistance to
high temperatures up to 280 ◦ C (in specially developed
modules and systems up to approximately 700 ◦ C); good
The examination of membrane processes started mostly corrosion resistance: resistance to organic solvents and
as a search for effective product separation that is a wide pH range; suitability for cleaning and steam
crucial to economical operation in process industries. sterilization; high mechanical strength: the possibility
Certain types of materials are inherently difficult to to back pulse, resulting in efficient removal of the dirt
separate, and their processing has become of increased layer and the possibility of treating fluids with high
importance in recent years, especially due to the growth viscosity; chemical inertness: a wide range of application
of the biotechnological industry (1) This new technology possible in the chemical industry; long operational life;
using synthetic membranes for process separations has and high membrane flux from a composite structure.
developed rapidly. Industrial membrane processes are The disadvantages of ceramic membranes compared to
classified according to the size range of materials, which polymeric membranes are brittleness and so they must be
they are to separate, and the driving force used in handled with care; the surface area/volume ratio is low
separation. The most common pressure-driven process is so systems have larger dimensions; and the investment in
microfiltration (often denoted as MF) (2). This technique ceramic membranes is high.
separate a size range of 10–0.1 µm; typical examples of Microfiltration constitutes a physical barrier to solid
materials separated are small particles, large colloids, and particles (as bonding agents), but has limitations because
of increased fouling at high concentrations. Convention-
microbial cells.
ally, cross-flow processes are applied, where high shear
Conventional processes for treating wastewater, pre-
rates on the membrane surface are created to prevent
cipitation, precipitation/reduction, ion exchange/sorption
fouling of membranes. The corresponding high energy
bed filtration, etc., often have disadvantages such as high
consumption led to the development of so-called low-
use of treatment chemicals; large quantities of sludge
energy systems (10), which are characterized by immersed
produced that has to be treated and disposed of; inad-
membranes operated by vacuum or hydrostatic pressure.
equate selectivity; slow kinetics of the metals and their Fouling is often controlled by air blowing from below the
oxyanions and therefore, large water treatment units membranes, creating shear forces near the membrane
and high investment costs are required; low capacity of surface. The energy consumption of these systems is con-
ion exchangers and sorbents; the residual metal concen- siderably lower than that of cross-flow systems, yet still
tration in the treated water streams can be high and significant (11). Furthermore, flux is also low, especially
water reuse or discharge is problematic; fouling and scal- at higher concentrations of suspended solids in the reac-
ing problems, very low membrane permeability, and low tor. Immersed membranes have been used for a variety of
water yield (up to 75%) are problems often encountered applications, mainly biological wastewater treatment and
in conventional membrane processes; treatment processes drinking water production (12).
are periodic and not continuous, followed by a regener- New MF/UF membrane modules were developed (13)
ation step in which regeneration chemicals and rinsing with emphasis on crossflow or submerged operation,
water are employed, ultimately generating a new quan- optimized hydrodynamics (in contrast to commercial
tity of wastewater; treatment of wastewater streams with hollow fiber or spiral-wound modules) to work at higher
large volume flow and high concentrations is mostly not bonding agent (BA) concentration in water, high fluxes
cost-effective. So, combinations of treatment processes are in real process water, low fouling tendency, easy cleaning
usually applied in practice. suited for backwashing, and low production costs. Both
(a)
(b)
(c) 58 98
1.1. Retentate
1.3. Permeate
extraction
550
1.2. Feed
52° 60°
150
60° 52°
1.4. Flow
(d)
Figure 1. (a) PP membranes of 0.1 µm pore

size produced by Eidos (and delivered via VUT
Brno). (b) Membranes developed by S. Search:
multichannel, flat sheet membranes (0.3 µm
pore size), used for submerged modules and
capillary outside skinned MF membrane. (c)
Cross-flow module with PES, multichannel, flat
sheet membranes. (d) Lab-scale transverse-flow
membrane module by TNO, and picture of
submerged module with ceramic multichannel
flat sheet membranes.
592
APPLICATION OF MICROFILTRATION TO INDUSTRIAL WASTEWATERS 593
F1
Permeate
Desinfectant V V
Tank F1 10 9
B3 B2
P2 P3
V V P1
11 P1 F1 T1 P1
1 V V
Feed 3 5
V
P1 2 Prefilter
F1
Feed- V V P1
13 7
V tank
12 V
F1 F1
B1 P4 V V 4
8 6
Bleed
Figure 2. Process scheme of a bench-scale MF plant.
Filtration at 0,5 bar with cross-flow 30 min (BF 30 sec; FF 20 sec)

120 1 g/l Bentonite
100
Relative permeability, %
80
60
40
20
0
0 120 240 360 480 600 720 840 960 1080
Figure 3. Filtration of bentonite suspension with PP
Elapsed time, min membrane module in back-flush mode.
polypropylene (PP) as well as polyethersulphone (PES) tend to break because of the high stress at the potting-
based membranes were developed (see Fig. 1). PP fibers membrane interface. Much improved capillary membranes
have a symmetrical wall, low flux and are inexpensive. were developed. They possess three times the tensile
PES capillaries have an asymmetrical wall, and higher strength at break (13). This was the result of adding
flux, but are more expensive. Because of this trade- a component to the extrusion mixture that resulted in
off, both membranes are of much interest in research. a tighter sponge in the support layer. Figure 1d, left,
These PP fibers were used in common longitudinal shows the TFM module consisting of 10 active layers of 8
membrane modules, as shown in Fig. 1a–d with bench- membranes next to each other in a grid.
scale modules. Figure 1c shows a cross-flow module with The process scheme of the bench-scale plant used is
PES multichannel, flat sheet membranes. presented in Fig. 2, based on feed-and-bleed processing;
The PES capillary membranes were used for the automatic back-flush was incorporated. Experiments with
transversal flow membrane module (TFM). Previous bentonite and the PP membrane modules in longitudinal
studies showed that within TFM modules, membranes outside mode showed that relative permeability decreased,
594 APPLICATION OF MICROFILTRATION TO INDUSTRIAL WASTEWATERS
150
malfunction of collector dosing
Transmembrane pressure, mbar

100
(3)
(2)
50
(3) 80 Lm−2h−1, with back-flush

Figure 4. Transmembrane pressure as a function of
(1) (2) 40 Lm−2h−1, back-flush starting after 26 hours
time for the hybrid process at various operating modes, (1) 20 Lm−2h−1, no back-flush
0
under the following conditions: c(zeolites) = 8 g/L,
0 12 24 36 48 60
c(CTABr) = 20 mg/g, ug = 0.33 cm/s, back-flushing (if
applied) every 30 min for 10 s. Operating time, h
when the transmembrane pressure was increased. Some- A parallel economic study showed that the capital
what surprising, but very promising was that the back- investment for the hybrid unit would be of the order of
flush mode has been very effective. At least during 22 0.92 M¤. The operating cost of the plant is about 1.42 M¤
hours, permeability was constant (Fig. 3). When selecting per year. Comparison with separate systems (MF following
membranes for efficiency and rejection of substances, per- flotation) showed that the hybrid system has a lower
meability and pore size or molecular weight cutoff were capital cost and lower operating costs. The former also
examined as important criteria (14). requires larger membranes.
Today, there is a tendency for combined and more com- The advantageous influence of flotation may be appar-
pact processes as, for example, membrane bioreactors (15). ent from Fig. 4. Membranes were operated at constant flux
Membrane fouling was also said to be the main limitation in all experiments. For an initial zeolite concentration of
to the faster development of the latter. A newly developed 8 g/L the membranes could be operated at 20 L/m2 h with-
type that has the further advantage of energy saving is out back-flushing. Resulting transmembrane pressure was
the submerged membrane bioreactor. as low as 15 mbar. However, to achieve stable membrane
A large number of techniques have been used to limit performance at higher fluxes, back-flushing was necessary.
membrane fouling, such as cross-flow liquid velocity, the A cycle of 10 s back-flushing every 30 min was sufficient,
use of baffles, back-flushing, transmembrane pressure resulting in TMP of 45 and 90 mbar (the mean of two
(TMP) pulsing, and air sparging (16). Depending on the cycles between backwashing) for imposed fluxes of 40 and
membrane process, the function of air can be different: 80 L/m2 h, respectively. The relatively long time between
back-flushing resulted in a permeate loss of less than 5%
a gas back-flush detaches and carries away deposited
due to backwashing (19).
particles, the formation of a particle or concentration
In Fig. 4, it can also be seen that the increase in
polarization may be prevented or limited, and even a
transmembrane pressure when operating the membranes
compound may be transferred by gas to a liquid phase.
at 40 L/m2 h without back-flushing was fully reversible.
Air bubbling, under appropriate conditions, could also
Switching the operating mode of a membrane, that had
be used as the transport for flotation, which is another effi-
been operated in continuous permeate withdrawal for 24
cient separation method applied in water treatment (17).
hours, to back-flushing resulted after less than 1 hour in
The aim of this innovative idea was integrating both
the same transmembrane pressure as a membrane, which
processes in the same tank, taking advantage of dispersed- had been operated with back-flushing from the beginning.
air flotation combined with microfiltration by submerged This proves that the loss in membrane performance was
membranes. For this, ceramic flat-sheet membrane mod- attributed to an easily removable cake layer, which was
ules with multichannel geometry were tested; the pore also visually observed. The resistance-in-series model (20)
size was 0.3 µm, pure water flux 3000 L m−2 h−1 bar−1 , may be used in this case, which describes filtration
the material of permeate collector polystyrene, and seal- resistance as the fraction of TMP to flux; the resistance of
ing material epoxy. The membrane distance was 20 mm, the cake layer can be evaluated according to
geometry 100 × 100 and area 0.054 m2 (Fig. 1d, right). The
hybrid cell was tested on-site at the Assarel-Medet open pit TMP
copper mine effluent, near Panagyurishte, Bulgaria (18). J= 3.6 × 108 , (1)
η(RM + RC )
The flotation separation techniques employed and inves-
tigated were based on three different mechanisms: (1) ion where J is permeate flux, RM is membrane resistance,
flotation using xanthates, (2) precipitate flotation gener- RC is the resistance of the cake layer or, in general,
ating copper hydroxide, and (3) sorptive flotation using fouling resistance; and η the viscosity of water to be
zeolites as sorbent material—see also the article on Flota- filtered. Cake resistance is of the same magnitude as
tion in this Encyclopedia. membrane resistance and thus, quite low, which can be
WATER TREATMENT IN SPENT NUCLEAR FUEL STORAGE 595
attributed to a highly permeable cake layer that zeolites 9. Scott, K. (1997). Handbook of Industrial Membranes. Else-
form. These results could be also considered in terms of the vier, Oxford, UK, p. 413.
concept of ‘‘critical flux’’ (the flux up to which the relation 10. Côté, P.L., Smith, B.M., Deutschmann, A.A., Rodrigues,
between flux and TMP is linear), which is currently often C.F.F., and Pedersen, S.C. (1994). Frameless array of hollow
applied to microfiltration processes (21). Although this fibre membranes and method of maintaining clean fiber
surfaces while filtering a substrate to withdraw a permeate.
concept does not imply back-flushes, from a process point
World Patent WO 94/11094, Zenon Environmental Inc.
of view, it can also be concluded that the membranes in
11. Guibert, D., Ben Aim, R., Rabie, H., and Côté, P.L. (2002).
our process were operated in the subcritical flux region.
Aeration performance of immersed hollow-fibre membranes
In all investigations, the air supply was determined by in a bentonite suspension. Desalination 148: 395–400.
that required for flotation. No additional aeration of the
12. Côté, P.L., Mourato, D., Güngerich, C., Russell, J., and
membranes was carried out. This has to be considered Houghton, E. (1998). Immersed membrane filtration for the
when relating membrane performance to conventional production of drinking water: Case studies. Desalination 117:
immersed membrane systems because the superficial air 181–188.
velocity used in the hybrid cell was about 10 times lower 13. EU FP 5 Project METASEP. (2004). Public Report, Brussels.
than that usually applied in these systems. 14. Schlichter, B., Mavrov, V., and Chmiel, H. (2000). Compara-
Concluding, one of the main objectives of environmental tive characterization of different commercial UF membranes
technology today is to design and implement processes for drinking water production. J. Water Supply: Res. Tech.-
to clean effluents from industrial production; recycling AQUA 49: 321–328.
valuable materials and microfiltration has certainly a 15. Blöcher, C. et al. (2002). Recycling of spent process water
definite role having presented very promising results. in the food industry by an integrated process of biological
Product recovery and waste recycling have been addressed treatment and membrane separation. Desalination 144:
by providing novel integrated processes for reusing water 143–150.
and the possibility of metal recycling, aiming to meet 16. Matis, K.A. et al. (2004). Air sparging during the solid/liquid
regulatory requirements with environmental benefits, not separation by microfiltration: Application of flotation. Sep.
merely by reducing risks. Puri. Tech.. 40: 1–7.
17. Lazaridis, N.K., Blöcher, C., Dorda, J., and Matis, K.A.
(2004). A hybrid MF process based on flotation. J. Membrane
Acknowledgments
Sci. 228: 83–88.
The financial help of EU is gratefully acknowledged (contract
no. EVK1-CT-2000-00083, acronym METASEP); all figures in 18. Lazaridis, N.K., Peleka, E.N., Karapantsios, Th.D., and
this article are from the Public Report (13) of this project. Many Matis, K.A. (2004). Copper recovery from effluents by various
thanks are due to our partners for their help and collaboration. separation techniques. Hydrometallurgy 74: 149–156.
19. Blöcher, C. et al. (2003). Hybrid flotation-membrane filtration
process for the removal of heavy metal ions from wastewater.
BIBLIOGRAPHY Water Res. 37: 4018–4026.
20. Cheryan, M. (1998). Ultrafiltration and Microfiltration Hand-
1. Coulson, J.M., Richardson, J.F., Backhurst, J.R., and book. Technomic, Lancaster, PA.
Harker, J.H. (1991). Chemical Engineering. 4th Edn. Vol. 21. Cho, B.D. and Fane, A.G. (2002). Fouling transients in nomi-
2. Pergamon, Oxford, UK. nally subcritical flux operation of a membrane bioreactor. J.
2. Porter, M.C. (1986). Microfiltration. In: Synthetic Membranes: Membrane Sci. 209: 391–403.
Science, Engineering and Applications. P.M. Bungay,
H.K. Lonsdale, and M.N. de Pinho (Eds.). D. Reidel,
Dordrecht, pp. 225–247. WATER TREATMENT IN SPENT NUCLEAR FUEL
3. Mavrov, V., Erwe, T., Blöcher, C., and Chmiel, H. (2003). STORAGE
Study of new integrated processes combining adsorption,
membrane separation and flotation for heavy metals removal
from wastewater. Desalination 157: 97–104.
SAMUEL C. ASHWORTH
Idaho National Engineering and
4. Radecki, P.P., Crittenden, J.C., Shonnard, D.R., and Bul-
Environmental Laboratory
loch, J.L. (Eds.). (1999). Emerging Separation and Sep-
Idaho Falls, Idaho
arative Reaction Technologies for Process Waste Reduc-
tion—Adsorption and Membrane Systems. AIChE, Center
for Waste Reduction Technologies, New York, pp. 199–219. Many facilities are changing their storage to dry mode,
5. Capannelli, G., et al. (1994). The use of membrane processes but in 1996, there were 100,000 tons of Zircaloy-clad
in the clarification of orange and lemon juices. J. Food Eng. spent nuclear fuel (SNF) in wet storage (1). Much of this
21: 473–483. fuel is stored in extended mode, beyond the period of
6. Hinkova, A., Bubnik, Z., Kadlec, P., and Pridal, J. (2002). time originally planned. Thus, this extended storage can
Potentials of separation membranes in the sugar industry. create problems.
Sep. Purific. Tech. 26: 101–110. A typical spent nuclear fuel pool storage system is
7. Urkiaga, A., Fuentes, de las L., Acilu, M., and Uriarte, J. shown in Fig. 1. The main functions of water storage
(2002). Membrane comparison for wine clarification by pools are to contain the fuel and any radionuclides
microfiltration. Desalination 148: 115–120. that leak and to remove heat generated by radionuclide
8. Lee, S. and Cho, J. (2004) Comparison of ceramic and decay. Water is withdrawn from pools via overflow sumps
polymeric membranes for natural organic matter (NOM) and pumped through a filter to remove solids including
removal. Desalination 160: 223–232. microorganisms. The water is treated by ion exchange
596 WATER TREATMENT IN SPENT NUCLEAR FUEL STORAGE
Transfer
channel
Storage Vent
pools Unloading pools
Contacting/
Offgassing
Sump
Cation IX
Ozone
Mixed IX
Heat UV unit destructor

exchanger
Air cooling
Filters unit Air dryer
Solids
Ozone
generator
Resins
Figure 1. Typical spent fuel storage schematic.
to remove radionuclides and other dissolved substances. The first substances on a surface during biofilm
Heat exchangers remove the decay heat that the spent formation are trace organics (2). Almost immediately after
fuel transfers to the water. Some systems have ultraviolet the clean pipe surface comes into contact with water,
(UV) light systems that kill microorganisms. An ozonator an organic layer deposits on the water/solid interface (3).
is also shown in Fig. 1, even though many systems do These organics form a conditioning layer that neutralizes
not have this. The supply makeup water normally has excessive surface charge and surface free energy that may
very low conductivity (κ≤1 µS/cm), so there is very little prevent a bacterial cell from approaching near enough
ion exchange capacity used up unless the fuel is in very to initiate attachment. In addition, the absorbed organic
bad shape and is leaking. There is also a need to provide molecules often serve as a nutrient source for bacteria.
basin chemistry/corrosion control to minimize corrosion Some planktonic (free-floating) bacteria approach the
of SNF, parts, and equipment. The following are typical pipe or equipment wall and become entrained within the
limits imposed to minimize corrosion: 5.0 < pH < 8.0, boundary layer. Some of these cells strike and adsorb to
exclusion of heavy metals or their salts including Cu, the surface for some finite time and then desorb. This
Pb, Sn, Hg, Ni, and Co, keeping Cl− < 10 ppm, and initial attachment is based on electrostatic attraction and
limiting conductivity <10 µmho/cm (µS/cm). There may physical forces. Some of the reversibly adsorbed cells begin
be a potential for microbiologically induced corrosion forming structures that may permanently bond the cell
(MIC) in storage pools, so it is important to control to the surface. These cells become irreversibly adsorbed.
microorganisms. This article focuses on microbiological Figure 2 provides a schematic of this stage of biofilm
control that presents the biggest challenge facing pool development.
storage systems. The corrosion of fuel element cladding
must be minimized to ensure containment of radionuclides
and worker protection. The general outline is a discussion
of mechanisms, rationale for treatment, and treatment
methods for storage pools.
MICROBIOLOGICAL MECHANISMS Desorption
Some of the variables that affect the growth of microorgan- Transport Transport
isms include food/nutrient availability, temperature, pH,
biocide concentrations, radiation, makeup water microor-
ganism concentration, and predation. There are practical
limitations to the types of activities that can be used to
control microorganisms, for example, restricting the use Reversible adsorption Irreversible adsorption
of biocides or pH out of the range of water chemistry
requirements. Figure 2. Biofilm development.
Biofilm bacteria excrete extracellular, polymeric sub- to permit microbial growth and reproduction. Bacteria
stances that contain the biofilm and attach it to a wall. and other organisms capable of growth in nutrient-limited
These polymer strands trap scarce nutrients and protect environments are called oligotrophs. Bacteria have evolved
bacteria from biocides. Attachment is mediated by extra- the means to find and attach to surfaces to increase the
cellular polymers that extend outward from the bacterial chances of encountering nutrients.
cell wall (3). The polymeric material, or glycocalyx, con- In a study on the attachment of Pseudomonas to
sists of charged and neutral polysaccharide groups that stainless steel surfaces (8), researchers put cells in a
facilitate attachment and also act as an ion-exchange sys- blender to remove the flagella. They found that the rate
tem for trapping and concentrating trace nutrients from of cell attachment decreased at least 90% when flagella
the overlying water. As nutrients accumulate, the pioneer were removed.
cells proceed to reproduce. The daughter cells then pro- Many organisms faced with the starvation conditions
duce their own glycocalyx, greatly increasing the volume of encountered in purified water systems respond by altering
ion-exchange surface. A viable colony of bacteria is thereby their cell wall structure to increase their affinity for
established (4). surfaces. By altering the protein and lipid composition of
A biofilm-covered surface is gelatinous and slippery the outer membrane, the charge and hydrophobicity can be
because the glycocalyx matrix holds water (75–95%) (5). changed. The cell wall becomes hydrophobic. Once in the
The glycocalyx net also absorbs other types of microbial boundary layer, they are attracted to a pipe surface (4).
cells through physical restraint and electrostatic interac- Recent research has dispelled some earlier assumptions
tion. These secondary colonizers metabolize wastes from about bacteria and biofilms. In the past, microbiologists
the primary colonizers and produce their own waste that assumed that biofilms contained disorderly clumps of
other cells then use in turn. Bacteria and other microor- bacteria located in no particular structure or pattern. In
ganisms develop cooperative colonies within the biofilm. most cases, the base of the biofilm is a bed of dense, opaque
An anaerobic biofilm may develop underneath the aerobic slime 5 to 10 µm thick. It is a sticky mix of polysaccharides,
layer. The biofilm thickness will reach equilibrium as flow- other polymeric substances, and water, all produced by the
ing water detaches cells extending out into turbulent flow. bacteria. Water currents that flow in channels between the
Different species live in the films, helping each other colonies carry nutrients and waste (9).
to exploit food supplies and to resist biocides through Past researchers assumed that biofilm bacteria behaved
synergistic interactions. Some species use toxic wastes much like solitary, free-floating microorganisms. Biofilm
produced by another species as food. By pooling their bio- bacteria have exactly the same genetic makeup as
chemical resources to build a colony, several species of their free-roving relatives, but their biochemistry is very
bacteria, each with different enzymes, can break down different because they activate a different set of genes. The
food supplies that no single species could digest alone. instant the bacteria dock to glass, they switch on certain
The biofilms are permeated at all levels by a network of genes involved in the synthesis of alginate (an unusually
channels through which water, bacterial wastes, nutri- sticky form of slime), switching them off again once the
ents, enzymes, metabolites, and oxygen travel. Gradients bacteria are engulfed in alginate. It is now estimated that
of chemicals and ions between microzones provide the as many as 30 to 40% of the proteins in bacterial cell walls
power to shunt substances around the biofilm (6). differ between sessile and planktonic bacteria. Some of the
A biofilm can spread at its own rate by ordinary cell targets for biocides are not there any more, so the bacteria
division, and it also periodically releases new pioneer cells become difficult to kill.
to colonize downstream sections of piping and equipment. Researchers are studying the chemicals (called sigma
As the film grows to a thickness that allows it to extend factors) which signal bacteria to change their biochemistry
through the boundary layer into zones of greater velocity, to life in a biofilm (9). If they can discover a reverse sigma
some cells are sloughed off. These later pioneer cells more factor which would change biofilm bacteria into planktonic
easily adsorb than their upstream predecessors because free-floaters, it might be possible to dissolve biofilms by
the parent film releases wastes into the stream that may sending the equivalent of an evacuation signal (6).
serve as either the initial organic coating for uncolonized The surface material has little or no effect on biofilm
pipe sections downstream or as nutrient substances for development. Stainless steel is just as susceptible as
other cell types (4). plastic pipe. Piping material to which microorganisms
The development of a mature biofilm may take several cannot adhere has yet to be discovered. Studies have
hours to several weeks, depending on the system (3). shown that microbes adhere to stainless steel, Teflon,
Pseudomonas aeruginosa is a common pioneering bacteria PVC, and PVDF (Kynar) nearly equally (4). Incorporating
and is used frequently in biofilm research. In one an antimicrobial additive into plastic to delay or reduce
experiment, researchers found that Pseudomonas cells the attachment of biofilm is possible (10). However, the
adhere to stainless steel, even to electropolished surfaces, chemicals used are not normally safe for drinking water
within 30 seconds of exposure (7). The association of supplies. Some ion exchange resins have been silver-
bacteria with a surface and the development of a biofilm coated to prevent microbial growth. However, silver-
can be viewed as a survival mechanism. Bacteria benefit tolerant bacterial populations can develop (11). There are
by acquiring nutrients and protection from biocides. no practical examples of toxic surface coatings for drinking
Potable water systems, especially high-purity water water piping.
systems, are nutrient-limited environments, but even One major factor influencing biofilm development in
nutrient concentrations too low to measure are sufficient purified-water systems is surface area. Industrial water
systems, unlike most natural environments (lakes and Table 1. Nutrients for Bacterial Growth Found in Pure
rivers), offer a tremendous amount of surface area for Water Systemsa
attachment. RO membranes, ion exchange resins, storage Nutrient Sources
tanks, cartridge filters, and piping systems all provide
surfaces suitable for bacterial attachment and growth (3). Organic carbon Humic and fulvic acids (source
Although smoother surfaces delay the initial buildup water), pipe plasticizers and
solvents, fiberglass-reinforced
of attached bacteria, smoothness does not significantly
plastics (FRPs), pump and gauge
affect the total amount of biofilm that attaches to a
lubricants, microbial
surface. No surfaces have been found that are exempt by-products, personnel, airborne
from biofouling (12). Surface structure influences the rate dust
of fouling, but only initially during the first few hours Nitrogen Humic and fulvic acids (source
of exposure. In general, smooth surfaces foul at a slower water), nitrates and nitrites
initial rate than rough ones, but biofilm formation after a (source water), microbial
period of days is inevitable. by-products, airborne dust
High water flow rates may alter biofilm growth but do Phosphorus Phosphates (source water),
not prevent the attachment of bacteria to pipe surfaces. microbial by-products, airborne
dust
Work by Mittelman (3), Patterson (13), and Meltzer (12)
Sulfur Sulfates (source waters), sulfuric
supports this conclusion. High flow does not prevent
acid (RO pretreatment),
bacterial attachment or remove an existing biofilm for membrane surfactants, airborne
the following reasons: dust
Trace metals and salts Source waters, process piping,
• Low flow in the boundary layer. The velocity is zero fiberglass-reinforced plastics
at the wall of a pipe or other surface. Near the (FRPs), stainless steel system
wall, a boundary layer exists that is controlled by components, RO pretreatment,
viscous effects, whereas outside the boundary layer, chemicals, personnel, airborne
the flow is not determined by viscous effects. Within dust
this boundary layer, for both laminar and turbulent a
Reference 3.
flow, particles and microorganisms can transport and
attach to surfaces. Regardless of the water velocity,
the velocity profiles are such that it flows most slowly
in the layers adjacent to pipe surfaces. The laminar be organic carbon sources for bacteria. Cellulose-based
sublayer thickness was calculated (14) for various RO membranes can also be a nutrient source. That is
flow velocities and for five pipe sizes. The shear forces why RO feedwater needs chlorination. Bacteria can also
within the laminar sublayer are much less than the obtain trace metal nutrients from stainless steel and other
forces produced in biofilm attachment. metal components.
• Strong adhesion by exopolymers. In water systems Currently available technology cannot reduce nutrient
where high-velocity flow is continuous, the bacteria levels completely; so total control of bacteria is not
that accumulate in a biofilm tend to be filamentous achievable by simply controlling nutrients. Similarly,
varieties (such as Pseudomonas) especially suited for very small quantities of oxygen will adequately support
attachment by filaments. bacterial growth, even if the bacteria do not revert
• Although high flow velocity does not prevent the to anaerobic respiration, which most bacteria can do.
attachment of bacteria to pipe surfaces, it does have Therefore, a thriving bacterial population can exist,
the following effects on the biofilm structure: even in high-purity water systems (14). Nutrient-limiting
• Denser biofilm. At higher flow rates, a denser, environments can actually promote the attachment
somewhat more tenacious biofilm is formed (3). of bacteria to surfaces because that is where the
• Limited biofilm thickness. The maximum thickness trace organics accumulate and extracellular polymers
of a biofilm can be considered the thickness of the in a biofilm capture trace nutrients. Although bacteria
laminar sublayer (see Table 1). cannot be completely starved out, nutrient-poor reverse
• Limited nutrients. Like other living creatures, osmosis water will support less biofilm than regular tap
bacteria require certain nutrients for growth water supplies.
and reproduction. Limiting these nutrients limits, Water samples collect only planktonic or free-floating
bacterial growth, but nutrient levels in high- bacteria. Free-floating bacteria in animal drinking water
purity systems are unequivocally sufficient to are either sloughed off the biofilm or pass through from
permit microbial growth and reproduction to a the incoming water supply. If a plate count test is low,
troublesome extent (15). Table 1 lists some sources one should not assume that bacteria are not present
of nutrients in purified water systems. in the watering system. More than 99% of the bacteria
in water systems are in biofilms attached to pipe and
Bacteria can get some of their nutrients from the pipe equipment surfaces. A mature biofilm may not slough off
and fittings in a water system (11). Most plastics are many cells into the drinking water if the integrity has not
not biodegradable, but pipe cements and plasticizers that been disrupted (e.g., by recent flushing or sanitization).
leach from epoxy resins, PVC pipe, and polyamide pipe can However, it is still there.
TREATMENT RATIONALE Turbidity versus sediment

70
Some of the main reasons to control microorganisms y = 1.2856x − 0.6701
60
Sediment, mg TSS/L
include: water clarity/turbidity, heat transfer surfaces R 2 = 0.9993
and other equipment problems, and microbiologically 50
induced corrosion. 40
30
Water Clarity/Turbidity
20
Very clear water is required to see the bottom of a
10
pool (≈10 m). Therefore, both algal and sedimentary,
particles must be removed so that required clarity can 0
be maintained. Turbidity refers to how clear the water is. 0 10 20 30 40 50 60
The greater the amount of total suspended solids (TSS) Turbidity, NTU
in the water, the murkier it appears, and the higher
Figure 4. Turbidity vs. sediment.
the measured turbidity. Algal turbidity varies seasonally
and with depth in a complex manner in response to
physical, chemical, and biological changes. Figure 3 shows
the effect of algae concentration on turbidity. A comparison Turbidity vs. visibility distance
with sediments is shown in Fig. 4. Turbidity is reported 1000
in nephelometric units (NTUs) referring to the type
of instrument (turbidimeter or nephelometer) used for
100
estimating light scattering from suspended particulate
Turbidity, JTU
material. The nephelometer, also called a turbidimeter,

has a photocell set at 90◦ to the direction of the light beam 10
to estimate scattered rather than absorbed light. This
measurement generally provides a very good correlation
with the concentration of particles in the water that 1
affect clarity.
Another inexpensive device is called a turbidity tube.
It involves looking down a tube at a black and white disk 0.1
(Secchi disk) and recording the depth of water that makes 1 10 100 1000
the disk disappear. Secchi disk depth, then, is a measure Distance, cm
of water clarity. There have not been many efforts to Figure 5. Turbidity vs. distance.
correlate distance clarity and turbidity. However, a rough
correlation is provided in Fig. 5. Turbidity units (NTU and
JTU) are interchangeable units. They differ only in that
their name reflects the device used to measure turbidity. piping, valves, pumps, and other equipment. Further,
One JTU is equivalent to 1 ppm of silica. biofilms can occur on ion exchange resins, filters, in-
basin structures, and spent nuclear fuel. Minimizing
Heat Transfer/Equipment Problems microorganisms and biofilms to help prevent this is highly
desirable. In general, water from natural sources leads
The waterside heat transfer systems of a treatment loop to poor cooling performance unless adequate steps are
heat exchanger are susceptible to a biofilm that can taken (16). The extent of the problem, however, depends
reduce the overall heat transfer coefficient and hence on the quality of the raw makeup water. Deposits on heat
efficiency. Microorganisms can cause biofilms to coat exchanger surfaces are complex, and are likely to include
particulate matter, crystalline salts, corrosion products,
and biofilms. It is necessary to counteract this problem
Effect of algae on turbidity of deposition onto surfaces to maintain heat exchanger
70 effectiveness.
Algae, µg chlorophyll/L
y = 1.1139x + 1.9975
60 When using natural waters, the presence of microor-
R 2 = 0.9156
50 ganisms is probably the predominant cause of poor heat
transfer efficiency. The conditions on the waterside of a
40
cooler are usually conducive to the growth of microorgan-
30 isms, notably bacteria, because of suitable temperature
20 conditions and the availability of nutrients. The coloniza-
10 tion of a heat transfer surface and the subsequent growth
0
of a biofilm may, under favorable conditions, lead to a
0 10 20 30 40 50 60
deposit 1 mm thick or more, unless preventive action is
taken. This layer represents resistance to heat transfer:
Turbidity, NTU
it acts as an insulating layer. The biofilm may also act as
Figure 3. Turbidity vs. algae. a trap for particulate matter and corrosion products. In
addition, the biofilm may encourage corrosion of the under- The following provides an alternate, more practical
lying metal due to biological activity, thereby adding to correlation for determining the laminar, flat plate
operating and maintenance costs. momentum boundary thickness (21):
The shape and structural arrangement of a biofilm
growing in a flowing fluid influences the mass transfer νx
δm ≈ 5 . (1)
characteristics of the biofilm system as well as the drag ν∞
force exerted on individual biofilm structures (17). If the
biofilm is highly compliant, the shape varies through the Turbulent boundary layers differ in that there are
growth cycle of the biofilm and also due to variations in several zones, including a laminar sublayer, a buffer
fluid shear stress (18). Changes in biofilm shape affect zone, and a turbulent core. As the distance along a flat
its porosity and density, therefore affecting the transfer plate increases, a transition region develops followed by
of solutes into and through the biofilm. Fluctuations in turbulence, as shown in Fig. 7. Estimating the turbulent
biofilm shape also affect the hydrodynamic drag that boundary layer thickness can be done from (21)
in turn influences the detachment rate and pressure 1/5
losses in a flowing system. In addition, it is thought ν
δm = 0.37x . (2)
that biofilm viscoelasticity may explain the large pressure ν∞ x
drops observed in biofilm-fouled pipes (19). However, very
few studies have been conducted on the material properties The laminar sublayer is quite thin but represents the
of intact biofilms, in part, due to the technical difficulty largest resistance to transport in the flow. However, the
of such testing. The small dimensions and pliability of resistance is much less for turbulent than for laminar flow
biofilms makes sample handling extremely difficult, and because the laminar sublayer is so thin and gradients are
removal of the biofilm from the substratum radically much steeper.
changes the integrity of the sample.
Boundary layers have a large role in biofilm formation, Microbiologically Induced Corrosion
so some discussion concerning them is instructive for the Microbial cells on a metal surface can cause microbiologi-
purposes of this section. In fluid mechanics, Prandtl (20) cally influenced corrosion (MIC) or biocorrosion. The forms
called the region where the viscous forces cannot be of corrosion caused by bacteria are not unique. Biocorro-
ignored the boundary layer. Prandtl arbitrarily suggested sion results in pitting, crevice corrosion, selective dealloy-
that it be considered the region where the x component of ing, stress corrosion cracking, and underdeposit corrosion.
the velocity is less that 99% of the free-stream velocity. The basic corrosion equations for the corrosion cell shown
This is an arbitrary division that does not correspond in Fig. 8 are
to any physically measurable boundary but corresponds
to an arbitrary mathematical definition. However, it is M −−−→ M2+ + 2e− (3)
a very useful concept, clarified numerous unexplained − −
phenomena, and provides a much better intellectual basis H2 O + 1
O
2 2
+ 2e −−−→ 2OH (4)
for discussing complicated flows (21).
An analogous concept exists for heat and mass trans- Nonuniform (patchy) colonies of biofilm result in the
fer. The momentum boundary layer represents the flow formation of differential aeration cells where areas under
regions dominated by viscous forces, and the thermal respiring colonies are depleted of oxygen relative to
boundary layer represents a region dominated by con- surrounding noncolonized areas. Having different oxygen
duction. Analogously, the mass boundary layer represents concentrations at two locations on a metal creates
a region dominated by diffusion. The dimensionless num- a difference in electrical potential and consequently
bers corresponding to them are the Reynolds (Re), Prandtl corrosion currents. Under aerobic conditions, the areas
(Pr), and the Schmidt (Sc) numbers, respectively. Figure 6 under the respiring colonies become anodic, and the
shows laminar boundary layers and profiles for momen- surrounding areas become cathodic.
tum, heat, and mass. In general, these will not be the same. Oxygen depletion at the surface of stainless steel can
The flat plate, boundary layer thickness for momentum, destroy the protective passive film. Stainless steels rely
heat, and mass are given elsewhere as are the complicated
profiles near the wall in turbulent flow (22).
Temperature Concentration Free stream flow

Velocity profile profile profile Turbulent
Momentum
boundary layer
Thermal Transition Laminar
boundary layer Laminar sublayer
Mass boundary
layer
Figure 6. Laminar boundary layers. Figure 7. Turbulent boundary layer.

on a stable oxide film to provide corrosion resistance. Iron-oxidizing bacteria, such as Gallionella, Sphaerotilus,
Corrosion occurs when the oxide film is damaged or oxygen Leptothrix, and Crenothrix, are aerobic and filamentous
is kept from the metal surface by microorganisms in a bacteria that oxidize iron from a soluble ferrous (Fe+2 ) form
biofilm. Oxygen depletion at the surface also provides a to an insoluble ferric (Fe+3 ) form. The dissolved ferrous
condition for anaerobic organisms such as sulfate-reducing iron could be from either the incoming water supply or the
bacteria (SRB) to grow. This group of bacteria is one of the metal surface. The ferric iron these bacteria produce can
most frequent causes for biocorrosion. They reduce sulfate attract chloride ions and produce ferric chloride deposits
to hydrogen sulfide that reacts with metals to produce that can attack austenitic stainless steel. The deposits
metal sulfides as corrosion products. Aerobic bacteria of iron bacteria on austenitic stainless steel are typically
near the outer surface of the biofilm consume oxygen brown or red-brown mounds.
and create a suitable habitat for the sulfate-reducing
bacteria at the metal surface. SRBs can grow in water TREATMENT METHODS
trapped in stagnant areas, such as dead legs of piping.
Symptoms of SRB-influenced corrosion are hydrogen Once the microorganisms have attached, they can with-
sulfide odor, blackening of waters, and black deposits. stand normal disinfection processes. Biofilm bacteria
The black deposit is primarily iron sulfide (5). One method display high resistance to biocides (23). Research demon-
of limiting SRB activity is to reduce the concentration strates that biofilm associated bacteria may be 150–3000
of their essential nutrients: phosphorus, nitrogen, and times more resistant to free chlorine and 2–100 times more
sulfate. Thus, purified (RO or DI) waters would have fewer resistant to monochloramine than free-floating bacteria.
problems with SRBs. Also, Any practices that minimize Research (24) suggests that Pseudomonas has a clever
biofilm thickness (flushing, sanitizing, eliminating dead- way of eluding its attackers. It secretes a sticky slime that
end crevices) minimize the anaerobic areas in a biofilm builds up on the pipe interior. A germicide flushed through
that SRB need (5). the water distribution system kills free-floating microbes,
Bacteria can produce aggressive metabolites, such as but it is less effective against bacteria embedded in the
organic or inorganic acids. For example, Thiobacillus slimy biofilm.
thiooxidans produces sulfuric acid and Clostridium When bacteria are in a film, they are very resistant
aceticum produces acetic acid. Acids produced by bacteria to biocides. They often produce more exopolymers after
accelerate corrosion by dissolving oxides (the passive film) biocide treatment to protect themselves. To destroy the
from the metal surface and accelerating the cathodic cell responsible for forming a biofilm, the disinfectant must
reaction rate. Many microorganisms produce hydrogen gas first react with the surrounding polysaccharide network.
as a product of carbohydrate fermentation. Hydrogen gas The cells themselves are not actually more resistant;
can diffuse into metals and cause hydrogen embrittlement. rather they have surrounded themselves with a protective
Aerated water flow
O2 O2 O2
Biofilm
Aerobic
O2 O2
Anoxic
Biofilm
Biofilm
O2 O2
Anaerobic
M+2 M+2
1
H 2O + O + 2e − → 2OH − M+2
2 2
M+2 M+2 M → M + 2 + 2e −
Cathode e− e−
e− e− e−
e− e−
e−
e−
Anode e−
Metal
Figure 8. Biofilm corrosion mechanism.

film. The disinfectant’s oxidizing power is used up before Table 2. Typical Biocide Dosage Levelsa
it can reach the cell. Dosage Level, Contact Time,
When cells are attached to a pipe wall, delivery of Biocide mg/L h
the disinfectant is limited by the rate of diffusion of
the compound across the boundary layer and through Chlorine 50–100 1–2
Ozone 10–50b <1
the film. It takes a higher concentration in a longer
Chlorine dioxide 50–100 1–2
contact time for the disinfectant to reach the bacteria
Hydrogen peroxide 10% (v/v) 2–3
cells in a biofilm compared to free-floating organisms. Iodine 100–200 1–2
Trace organics concentrate on surfaces. Extracellular Quaternary ammonium 300–1,000 2–3
polymers further concentrate trace nutrients from bulk compounds
water. Secondary colonizers use waste products from their Formaldehyde 1–2% (v/v) 2–3
neighbors. By pooling their biochemical resources, several Anionic and nonionic 300–500 3–4
species of bacteria, each that has different enzymes, can surfactants
break down food supplies that no single species could a
Reference 26.
digest alone. b
Ozone dosage is 10–50 mg/L, but the residual levels in water were
Traditional disinfectant testing has been done using 1–2 mg/L.
single-species free-floating laboratory cultures. The CT
constant (concentration × time) for a disinfectant required
to kill a particular bacteria should not be extrapolated to is particularly high; planktonic and biofilm bacteria are
bacteria in biofilms. This explains how bacterial counts killed, and chlorine also reacts with and destroys the
can be measured, even when water contains low levels polysaccharide web and its attachments to the surface. By
of chlorine. Typical chlorine levels in tap water are from destroying extracellular polymers, chlorine breaks up the
0.5–2.0 ppm. This amount of chlorine kills free-floating physical integrity of a biofilm. Characklis (27) recommends
bacteria but may not be enough to kill biofilm bacteria. improving a chlorine treatment program by taking specific
Chunks of sloughed off biofilm can contain viable bacteria additional measures.
which show up in plate counts. This is a particular problem In addition to their biocidal activity, quaternary ammo-
with Pseudomonas that is a great slime producer, and so nium compounds are effective surfactants/detergents,
is more chlorine resistant. which may be an important factor in their use for biofilm
The development of biocide resistance is not under- inactivation and removal from surfaces. Rinseability can
stood, but recent studies have used a variety of model be a problem because removal from a purified water system
systems to determine how and why biofilms are so resis- often requires exhaustive rinsing. Formaldehyde has been
tant to antimicrobial agents (25). As the importance of applied to pharmaceutical-grade systems. It is relatively
biofilms in water treatment has increased, much energy noncorrosive to stainless steel. Its effectiveness against
has been directed toward the study of the effects of antimi- biofilms is questionable, and it is a toxic carcinogen.
crobial agents on these surface-attached communities. Anionic and nonionic surface-active agents (surfactant
Biofilm resistance mechanisms include physical or chem- or detergent compounds) have limited biocidal activity
ical diffusion barriers to antimicrobial penetration into against the bacteria in purified water systems. Applica-
the biofilm, slow growth of the biofilm owing to nutrient tions may be found for these detergents in conjunction
limitation, activation of the general stress response, and with other biocides to improve biofilms and other particu-
the emergence of a biofilm-specific phenotype. late removal.
Biofilms can be removed and/or destroyed by chemical Pharmaceutical water-for-injection systems use recir-
and physical treatments. Chemical biocides can be divided culating hot water loops (hotter than 80 ◦ C) to kill
into two major groups: oxidizing and nonoxidizing. bacteria. When these systems are used continuously,
Any chemical that may result in residuals, attack ion planktonic bacteria are killed, and biofilm development is
exchange resins, or cause corrosion must not be used reduced (26). Biofilms are even found in hot water (80 ◦ C).
to control microorganisms. Physical treatments include Periodic hot water sanitization can also be used to destroy
mechanical scrubbing and hot water. An article by bacteria in a biofilm, but this requires a temperature of
Mittelman (26) has the most comprehensive information 95 ◦ C for a period in excess of 100 minutes (28).
on treatment of biofouling in purified water systems. Heavy biofilms cannot be removed from storage
Table 2 provides typical dosage levels and contact times tank walls by chemicals alone; mechanical scrubbing or
for various biocides. scraping, high-pressure spraying, or a combination is also
The effectiveness of oxidizing biocides in purified water required. Mechanical removal of biofilm from distribution
systems based on an equal milligram-per-liter dosage systems is impractical (26).
decreases in the following order: Unlike antibiotics used to fight bacteria associated with
human, animal, and plant diseases, bacteria do not develop
Ozone (O3 ) > chlorine dioxide (ClO2 ) > chlorine (Cl2 )
the same type of resistance to industrial biocides. The
> iodine (I2 ) > hydrogen peroxide (H2 O2 ). difference between antibiotics and industrial biocides is
that an antibiotic may have a small number of target
Chlorine is probably the most effective and least sites on or in a bacterial cell, but all oxidizing biocides
expensive of all oxidizing and nonoxidizing biocides (26). have a multitude of potential target sites. It is thought
The level of activity of chlorine against attached biofilms that chlorine, for example, has more than a hundred
potential target sites on or in microorganisms. It is Table 3. Maximum Ozone Solubility at

virtually impossible for microorganisms to develop general pO3 = 1.0 Atmosphere
resistance to such compounds (26). However, bacteria in T, ◦ F H, Atmosphere/x Solubility, mg/L (ppm)
a biofilm can resist biocides because they are shielded
in slime. 32 1940 1374.57
Bacteria associated with biofilms are much more dif- 41 2180 1223.24
50 2480 1075.27
ficult to kill and remove from surfaces than planktonic
59 2880 925.93
organisms. Numerous investigators and plant opera- 68 3760 709.22
tors have observed a rapid resumption of biofouling 77 4570 583.52
immediately following chlorine treatment (27). Incomplete 86 5980 445.93
removal of the biofilm allows it to return quickly to its
equilibrium state, causing a rebound in total plate counts
following sanitization. Initially, the bulk water bacteria
count in one study dropped to zero after sanitization, but On Ozone in
this was followed by a gradual increase in numbers to
levels at or below pretreatment levels. In this example,
regrowth started after 2 days and was back up to equilib- 4 3 2 1
rium levels after 20 days. Biofilms can also recover based 5m
Water Water
on various mechanisms (27). out in
As an oxidizer, ozone is approximately twice as powerful
as chlorine at the same concentrations. Like chlorine Figure 9. Diffusion contact chambers.
dioxide, ozone must be generated on-site because of its
high reactivity and relative instability. Systems must
be designed of appropriate ozone-resistant materials. traditional contact tank design with a compact self-
Ozone is usually dosed continuously at 1–2 mg/L. Success contained contacting system that is 98% efficient. Instead
in employing higher dosages noncontinuously has been of a 20,000–30,000 gallon contact tank for a 100,000-gallon
limited, possibly because of the limited solubility of pool, the new system uses a powered contacting/mixing/off-
ozone in purified water; it is difficult to produce high gas unit.
concentrations of ozone in solution (26). Although chlorine Ozone is an oxidative and reactive gas that is harmful
is not as powerful as ozone when you compare 1–2 mg/L to humans above certain concentrations. Ozone gas is
of each, chlorine can be used in higher sanitizing heavier than air; therefore, any undissolved ozone must be
concentrations with equal disinfecting strength. removed from the system and disposed of correctly. Several
Ozone is soluble in water only up to the partial pressure methods are available for ozone destruction, the simplest
above it; therefore, the concentration of ozone in the is by ozone adsorption and reaction with granulated
generator gas stream becomes very important. According activated carbon (GAC). Activated carbon adsorption is
to Henry’s law, the efficiency of absorbing a specific gas extensively used for small applications where air is the
into an aqueous phase is based on the partial pressure of ozonator feed gas. This is an adsorption process whereby
that particular gas in the total gas flow. Therefore, the the reaction consumes the carbon medium. The material
higher the partial pressure of ozone in the generator gas used is elemental carbon which has been steam activated
stream, the more complete is the concentration of ozone to provide a large internal surface area. Carbon is a strong
in the water. Table 3 shows the theoretical residuals of reducing agent; therefore, upon contact with ozone gas, the
ozone that can be achieved in water, based on an ozone carbon is oxidized to carbon monoxide and carbon dioxide,
gas partial pressure of 1.0 atmosphere and Henry’s law resulting in destruction of the ozone molecule. This
constants given in Perry (29). As would be expected, ozone reaction degrades or powderizes the GAC; therefore, it has
solubility decreases as water temperature increases. Also a finite life. To this end, the ozone consumes the carbon by
as a consequence of Henry’s law, the solubility of ozone slow-rate combustion. Due to the consumption of carbon,
increases as the partial pressure of ozone in the gas stream the medium must be replaced regularly. When the carbon
increases. In practical applications, ozone does not have is saturated with water and washed with sprays, the
sufficient contact time to achieve equilibrium conditions, reaction becomes partially catalytic and requires a larger
resulting in solubility levels lower than those shown in volume of GAC. For ozone installations where oxygen is
Table 3. Figure 9 shows a multiple chamber diffusion used as the feed gas, carbon adsorption destructors must
contact system. The ozonated water stream is led along a not be used, due to the dangers of combustion. The other
pipe located at the bottom of each contact tank. The pipe method is heat treatment that degrades the ozone rapidly
is perforated by small holes to allow fine bubbles to escape to oxygen.
and diffuse into solution. Hydrogen peroxide is frequently used as a biocide in
The latest ozone engineering principle involves using a microelectronic-grade purified water systems because it
self-contained ozone contacting/off-gassing system. This produces no by-products and rapidly degrades to water
system means that the large contact tanks found in and oxygen. A 10% by volume solution in purified
older system designs are no longer required. This water is effective in killing planktonic bacteria, but more
results in significant capital savings on a new pool or studies are needed on the effectiveness against attached
retrofit (typically 50 to 75%). This system replaces the biofilms (26). The use of hydrogen peroxide, though not
expected to be as effective as ozone, would be very simple Table 4. Comparison of Disinfectants Against
to implement. Food-Poisoning Bacteriaa,b
Peracetic acid, a derivative of hydrogen peroxide, Peracetic Active Benzalkonium
displays a very wide bandwidth of attack against microbes. Organism Acid Chlorine Chloride
Research has shown that peracetic acid will be used to an
ever-increasing degree in the field of human medicine At 20 ◦ C
Listeria monocytogenes 45 100 200
due to its bacterial, fungicidal, sporicidal, and antiviral
Staphylococcus aureus 90 860 500
action. Because of the wide spectrum of attack, peracetic ATCC 6538
acid is very suitable as a wide bandwidth disinfectant Enterococcus faecium 45 300 250
for ion exchange resins (results of work done by Degussa DSM 2918
Technical Applications Department in conjunction with At 5 ◦ C
Chemiewerk Homburg). Using a 0.2% peracetic acid Listeria monocytogenes 90 860 500
solution (in water, with a reaction time of 1 hour), a Staphylococcus aureus 90 1,100 750
slime concentration of 104–105/ mL, including mold, was ATCC 6538
reduced to almost zero. The short rinsing time after using Enterococcus faecium 90 450 500
peracetic acid is important (typically about 45 minutes DSM 2918
or 10–15BV). In addition to the excellent disinfection a
Lethality in 5 min.
b
action, peracetic acid (according to experiments) has a Concentrations of disinfectants given in ppm.
minimal effect on the ion exchange properties of cation or
anion resins.
Peracetic acid (peroxyacetic acid), C2 H4 O3 , the peroxide Peracetic acid has been accepted worldwide in the food
of acetic acid, is a disinfectant that has the desirable processing and beverage industries as an ideal for clean-
properties of hydrogen peroxide: broad-spectrum activity in-place systems (36); it does not require rinsing where
against microorganisms, lack of harmful decomposition the breakdown product, acetic acid, is not objectionable in
products, and infinite water solubility. high dilution. Peracetic acid is more toxic than hydrogen
Peracetic acid forms in an equilibrium reaction where peroxide and is a weak carcinogen but can be used
hydrogen peroxide and acetic acid react: with safety when diluted. Like all peroxides, it is a
powerful oxidizer and should be handled with proper
H O
O O H safety precautions. It is more corrosive to metals and
H O O (5)
O H + + H H plastics than hydrogen peroxide (36).
O O UV energy is found in the electromagnetic spectrum
between visible light and X rays and can best be described
Peracetic acid also has greater lipid solubility and is free as invisible radiation. The energy employed for UV
from deactivation by catalase and peroxidase enzymes. water treatment is further categorized into two primary
However, it is corrosive, and degradation products may levels measured as wavelengths—254 nm and 185 nm,
have to be rinsed from the surface of disinfected materials. where nm = 1/1000 of a micron. For disinfection and
Peracetic acid is a more powerful antimicrobial agent than ozone destruction, the 254-nm wavelength is used. All
hydrogen peroxide and most other disinfectants (30–32). living organisms contain DNA (deoxyribonucleic acid).
It has advantages for disinfection and sterilization not DNA provides the mechanism for all functions needed
found in any other agent. Against spores of Bacillus to sustain life.
thermoacidurans, it was reportedly the most active of UV light disinfection systems emit UV light that
23 germicides (33); against a range of bacteria it is penetrates the outer cell membrane of microorganisms,
lethal at 6–250 ppm, toward yeasts at 25–83 ppm, fungi passes through the cell body, reaches the DNA, and
at 50–500 ppm, bacterial spores at 100–500 ppm, and alters the genetic material. The microorganism is thereby
viruses at 15–2,000 ppm (34). The values obtained are destroyed nonchemically and cannot reproduce.
determined by the medium employed and the time Ultraviolet processing involves using radiation from
necessary for inactivation. the ultraviolet region of the electromagnetic spectrum
Table 4 gives a comparison of peracetic acid and two for disinfection (37). Typically, the wavelength for UV
other disinfectants against food-poisoning bacteria (35). processing ranges from 100 to 400 nm, as shown in Fig. 10.
Peracetic acid retains its activity better than many This range may be further subdivided into UVA (315 to
disinfectants at refrigeration temperatures and is more 400 nm) normally responsible for changes in human skin
effective at lower pH values (31). Aqueous solutions are that lead to tanning; UVB (280 to 315 nm) that can cause
comprised of the acid in combination with hydrogen skin burning and eventually lead to skin cancer; UVC
peroxide, acetic acid, sulfuric acid, water, and a stabilizing (200 to 280 nm), called the germicidal range, because
agent. All of these ingredients are necessary to keep it effectively inactivates bacteria and viruses, and the
it stable in storage; the concentration of the hydrogen vacuum UV range (100 to 200 nm) that can be absorbed
peroxide in some formulations may considerably exceed by almost all substances and thus can be transmitted only
that of the peracetic acid. Peracetic acid vapor, like that of in a vacuum.
hydrogen peroxide, is active against bacterial spores and The germicidal properties of UV irradiation are mainly
has been found most effective at 80% relative humidity, it due to DNA mutations induced through absorption of UV
has little activity at 20% relative humidity. light by DNA molecules. This mechanism of inactivation
Cosmic Gamma
X rays Ultraviolet Infrared Microwave Radio
rays rays
10−13m 10−9m 10−1m
l
Vacuum Shortwave Middlewave Longwave

UV UV (UV-C) UV (UV-B) UV (UV-A)
100 nm 200 nm 280 nm 315 nm 400 nm
254 nm Figure 10. UV light spectrum.
results in a sigmoidal curve of microbial population data suggest that the log reduction is related to the
reduction. To achieve microbial inactivation, the UV UV radiant exposure. The curve has a linear section
radiant exposure must be at least 400 J/m2 in all parts with a shoulder and tailing effects (38). All organisms
of the product. Critical factors include the transmissivity tested were reduced by four-log cycles when UV radiant
of the product; the geometric configuration of the reactor; exposure was less than 400 J/m237 . In some bacterial cells,
the power, wavelength and physical arrangement of the photoreactivation, a repair mechanism that is enhanced
UV source(s); the product flow profile; and the radiation by visible light in the blue spectral range, may occur.
path length. UV may be used in combination with other Photoreactivated cells show greater resistance to UV
alternative processing technologies, including powerful radiation than nonreactivated cells.
oxidizing agents such as ozone and hydrogen peroxide. The germicidal properties of ultraviolet irradiation are
Applications include disinfection of water supplies and due to DNA absorption of the UV light, causing cross-
food contact surfaces. Recently, interest has increased in linking between neighboring pyrimidine nucleoside bases
using UV to reduce microbial counts in juices. (thymine and cytosine) in the same DNA strand (39).
The shape of the curve for microbial inactivation by Due to the mutated base, formation of hydrogen bonds
UV light is sigmoidal. Figure 11 is an idealized depiction to purine bases on the opposite strand is impaired.
of a sigmoidal curve. The initial plateau is due to an DNA transcription and replication is thereby blocked,
injury phase of the microorganism in response to UV compromising cellular functions and eventually leading
exposure. After the initial plateau, the maximum amount to cell death. The amount of cross-linking is proportional
of injury has been surpassed; thus, minimal additional UV to the amount of UV exposure. The level of mutations that
exposure would be lethal for microorganisms, and survivor can be reversed depends on the UV repair system in the
numbers rapidly decline. The end of the curve has a tailing target microorganism. Once the threshold of cross-linking
phase due to UV resistance of the microorganisms and to is exceeded, the number of cross-links is beyond repair,
experimental components, such as suspended solids, that and cell death occurs (39). This phenomenon is reflected in
may block the UV irradiation. the shape of the inactivation curve described before. The
Much of the prior literature has focused on UV cross-linking threshold corresponds to the point of rapid
disinfection of water supplies. The literature is insufficient decline after the initial plateau phase on the sigmoidal
to develop comprehensive microbial inactivation reaction survival plot of UV exposure.
kinetics data or models. There are, however, studies To disinfect water, it is essential that all parts (each
relative to the UV radiant exposure required to obtain volume element) of the product receive UV radiant
a four-log reduction of various microorganisms. These exposure of at least 400 J/m2 (at 254 nm) to reduce human
pathogens and viruses by at least four-log cycles (40).
Thus, the homogeneity of the flow pattern and the
Sigmoidal deactivation radiation field may have critical effects on disinfection.
0 An additional critical factor is the transmissivity of
−0.5 the material being disinfected. If the material is highly
transparent to UV light, disinfection may be more
N/N0 log deactivation
−1
effective; turbid materials attenuate and scatter UV
−1.5
radiation, resulting in less microbial inactivation. The
−2 thickness of the radiation path through a material is also
−2.5 important because attenuation increases with the length
−3 of passage; thus, the geometric configuration of process
−3.5 systems is critical. Another critical factor to consider
−4
is the UV wavelength used because it affects microbial
inactivation.
−4.5 0 100 200 300 400 500 600 700 800
2 The growth of organisms increases as temperature
Power, J/m
increases. The effect of temperature on the reaction
Figure 11. Idealized microorganism deactivation. rate of a biological process is usually expressed in the
following form (41): The reduction of light may reduce the growth rate
of some microorganisms. Microbes may be classified
rT = r20 θ (T−20) (6) according to their energy and carbon requirements (42).
Growth from light is expected for some organisms as a
This is similar to the Arrhenius equation used in result of photosynthesis. For example, algae use carbon
chemistry; an approximate doubling of reaction rate for dioxide in photosynthetic activity to produce new cells,
each 10 ◦ C temperature rise. The range is limited because oxygen, and water.
there is little biological activity in ice or boiling water. The criteria for chemical addition and other micro-
Figure 12 illustrates this and shows that a decrease from biological control for a typical nuclear fuel storage
80 to 60 ◦ F has a significant impact on the growth rate. The pool include
growth rate can be reduced, but the temperature changes
that are practical in pools do not kill the organisms. • minimal corrosion
Increasing temperature also increases the kill rate • no damage occurs to other parts and/or systems
(decreases kill time). The effect of temperature on the • no residual remains that can adsorb onto ion
kill rate of microorganisms is well represented by a form exchange resins
of the Van’t Hoff–Arrhenius relationship (41). In terms
• personnel safety.
of the kill time (t in the equation) required for a given
percentage kill, the relationship is
This severely limits the treatment chemicals that can
t1 E(T2 − T1 ) be used, for example, chlorine cannot be used. Although
ln = (7) there may be beneficial affects from controlling and/or
t2 RT1 T2
manipulating light and temperature, the focus is on
Using T2 = 20 ◦ C and chlorine at pH = 7.0, the effects treatment to remove microorganisms and keep them
of temperature on kill rate are illustrated in Fig. 13. minimized. Also, as previously discussed, the chemicals
Figure 13 shows that kill time can be significantly reduced focus on those that will not leave residuals or cause
by modest increases in temperature. corrosion. Therefore, the focus is on ozone, peracetic acid,
and hydrogen peroxide. The International Atomic Energy
Agency has studied this in some detail (1). They provided
a list of potential methods for removing microorganisms
Temperature effects on growth
from spent fuel pools that should be considered in a
5
final study or evaluation. Ion exchange columns must
4.5
be bypassed when ozone is at a high concentration in the
4
water because ozone attacks and degrades the resins (43).
3.5
It is believed that ozone is effective in long residence
r (T )/r (20)
3
times and for sustained residuals. This expectation is
2.5
partly based on experience from vendors using ozone in
2
biofilm-fouled swimming pools (44).
1.5
The use of chemical agents must be demonstrated
1
for personnel safety. The maximum possible dissolved
0.5
ozone in the pools that transfers to the atmosphere
0
would be related to Henry’s law. At 86 ◦ F, H = 5980
0 20 40 60 80 100 120
atmospheres/mole fraction, and the residual is 1 mg/L.
T, °F The mole fraction (x) is then,
Figure 12. Temperature effects on biological growth.
1 mg L 18 g mole g
x= × × × × 3 = 4×10−7
L 1, 000 g mole 48 g 10 mg
Temperature effects on kill time
The partial pressure (maximum) in equilibrium with the
3
pool surface is based on Henry’s law constant (H) in
2.5 Table 3:
2
pi = Hx = 5980 × 4 × 10−7
t1/t2
1.5 = 2 × 10−3 atmospheres (2, 000 ppm)

1
The STEL/Ceiling/TWA is 0.1 ppm, so this is significantly
0.5 higher. A material balance is used to determine the
0 effective vapor phase concentration. Figure 14, material
0 20 40 60 80 100 120 140 160 balance shows the ozone transferring from the water
T, °F
surface into the ventilation air. The material balance
is thus:
Figure 13. Temperature effects on kill time. Qozone = (Qvent + Qozone ) yozone (8)
average (TWA) is 0.1 ppm. The estimated concentration

is 1.27 ppm that exceeds the limit. Therefore, the
Q vent
liquid concentration would need to be controlled at less
than 0.1 mg/L to ensure personnel protection. However,
Q ozone an ozone system that intermittently supplies high-
concentration ozone was effective in preventing biofilm
Pool surface formation using a 1-mg/L ozone dose for 10 minutes (47).
Asea Brown Boveri (ABB) carried out tests with ozone as a
Figure 14. Material balance [SCA1][nlh2]diagram. biocide on the water of a small industrial cooling tower in
Switzerland (48). The test results showed that ozone is an
excellent biocide. In 1988, an ozonation plant was installed
A dissolved gas has two resistances, gas-phase and liquid- at the side stream cooling water system of a heating power
phase. The mass transfer (F) flux is station in Germany (49). The operation showed that ozone
works well at 0.1 mg/L for 2–3 hours contacting time per
F = KL (CB − C∗ ) = KG (p∗ − pB ) (9) day. Ozone destroys and reacts with pollutants in the air.
If this is considered, the ozone concentration in air in pool
The flux is also equal to the individual driving forces as areas will be much lower than the worse case calculation
(Table 5).
F = kG (pI − pB ) = kL (CB − CI ) (10) The concentration above the pools using the 10-minute
treatment is then
By combining these and using Henry’s law, the following
are determined for the overall mass transfer coefficients, 10 min
and either one can be used: C10 min = 1.27 × = 0.00882
24 h × 60 min/h
1 This result is well below the TWA of 0.1 ppm.
KL = (11)
1 1
+
HkG kL
NOMENCLATURE
1
KG = (12)
1 H A Area
+
kG kL C Concentration
CI Concentration at interface
According to Thibodeaux (45), the gas-phase and liquid- CB Concentration in bulk solution
phase coefficients for water and CO2 are 3000 cm/h and C∗ Fictitious concentration in bulk gas
20 cm/h, respectively. The ozone value can be directly used CT Concentration × time
as 20 because the molecular weight falls in the range for E Activation energy, J/g mole
direct substitution. However, the value of the gas-phase F Mass transfer flux
coefficient is determined from the ratio of the cube roots of H Henry’s law constant
molecular weights (46): kG Local gas mass transfer coefficient
1/3 kL Local liquid mass transfer coefficient
18 KG Overall mass transfer coefficient, based on gas
kG−O3 = kG−H2 O = 2163
48 KL Overall mass transfer coefficient, based on liquid
M Molecular weight
The overall coefficient is then p Partial pressure, atmospheres
1 pI Partial pressure at interface, atmospheres
KL = = 20
1 1
+
5, 980 × 2, 163 20 Table 5. Calculation of
Ozone Above Pools
Thus it is seen that the transfer is totally controlled by the
liquid phase. The material balance then becomes Parameter Value
p MO3 , g/mole 48.00
B
pB MO3 K L A CB − Mair , g/mole 29.00
= H
(13)
pB PT , atm 0.87
PT Mair K L A CB − + Qvent Qvent , scfm 28,100
H
Qvent , g/h 6.2E+07
For small pB , this can be simply solved as CB , mg/L 1.00
KL , cm/h 20.00
KL ACB Mair KL , m/h 0.20
pB = PT (14) A, m2 648.14
KL ACB + Qvent MO3
F × A, g/h 129.63
Calculated p, atm 1.10E−06
The estimated partial pressure of ozone was based
Calculated O3 , ppm 1.27
on the values in Table 3. The NIOSH time weighted
pB Partial pressure in bulk, atmospheres systems to stepwise nutrient supplementation. Ultrapure

p∗ Fictitious pressure in bulk liquid Water 11(6): 43–50.
PT Total pressure, atmospheres 16. Bott, T.R. (1998). Techniques for reducing the amount of
Q Gas mass flow rate biocide necessary to counteract the effects of biofilm growth
R Gas constant in cooling water systems. Appl. Thermal Eng. 18(11):
Re Reynolds number 1059–1066.
rT Reaction rate at T ◦ C 17. Stoodley, P., Lewandowski, Z., Boyle, J.D., and Lappin-
r20 Reaction rate at 20 ◦ C Scott, H.M. (1999). Structural deformation of bacterial
T Temperature biofilms caused by short-term fluctuations in fluid shear: An
t Time in situ investigation of biofilm rheology. Biotechnol. Bioeng.
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v Velocity
x Mole fraction 18. Boyle, J.D., Dodds, I., Stoodley, P., and Lappin-Scott, H.M.
(1997). Stress management in biofilms. In: Biofilms:
y Vapor mass fraction
Community Interactions and Control. J.W.T. Wimpenny,
δ Boundary layer thickness
P.S. Handley, P. Gilbert, H.M. Lappin-Scott, and M. Jones
κ Conductivity
(Eds.). BioLine, Cardiff, UK, pp. 15–22.
ν Kinematic viscosity
19. Picologlou, B.F., Zelver, N., and Characklis, W.G. (1980).
θ Temperature-activity coefficient
Biofilm growth and hydraulic performance. J. Hydraul. Div.
Am. Soc. Civ. Eng. 106(HY5): 733–746.
BIBLIOGRAPHY 20. Prandtl, L. (1904). Ueber Fluessigkeitbewegung mit Kleiner
Reibung (Concerning Fluid Movements with Small Friction),
Verhandl. III Int. Math.-Kong., Heidelberg; also reprinted in
1. International Atomic Energy Agency. (1988). Durability of Vier Abhandlungen zur Hydrodynamik. Goettingen, 1927.
Spent Nuclear Fuels and Facility Components in Wet Storage.
21. De Nevers, N. (1970). Fluid Mechanics. Addison-Wesley,
IAEA-TECDOC-1012, Vienna, Austria.
Reading, MA.
2. Edstrom. (2002). Available: http://www.edstrom.com/
Resources.cfm?doc id=23. 22. Bird, R.B., Stewart, W.E., and Lightfoot, E.N. (1960). Trans-
port Phenomena. John Wiley & Sons, New York.
3. Mittelman, M.W. (1985). Biological fouling of purified-
water systems: Part 1, Bacterial growth and replication. 23. LeChevallier, M.W., Cawthon, C.D., and Lee, R.G. (1988).
Microcontamination 3(10): 51–55, 70. Inactivation of biofilm bacteria. Appl. Environ. Microbiol.
54(10): 2492–2499.
4. Mayette, D.C. (1992). The existence and significance of
biofilms in water. Water Rev. Water Quality Research Council, 24. Anderson, R.L. et al. (1990). Effect of disinfectants on
Lisle, IL, pp. 1–3. Pseudomonas colonized on the interior surface of PVC pipes.
5. Geesey, G.G., Lewandowski, Z., and Flemming, H.-C. (Eds.). AJPH. 17–21.
(1994). Biofouling and Biocorrosion in Industrial Water 25. Mah, T.C. and O’Toole, G.A. (2001). Mechanisms of biofilm
Systems. Lewis, Ann Arbor, MI. resistance to antimicrobial agents. Trends Microbiol. 9(1):
6. Coghlan, A. (1996). Slime city. New Sci. 15(2045): 32–36. 34–39.
7. VanHaecke, E. et al. (1990). Kinetics of Pseudomonas aerug- 26. Mittelman, M.W. (1986). Biological fouling of purified-water
inosa adhesion to 304 and 316-L stainless steel: Role of systems: Part 3, Treatment. Microcontamination 4(1): 30–40,
cell surface hydrophobicity. Appl. Environ. Microbiol. 56(3): 70.
788–795. 27. Characklis, W.G. and Marshall, K.C. (Eds.). (1990). Biofilms.
8. Stanley, P.M. (1983). Factors affecting the irreversible John Wiley & Sons, New York.
attachment of Pseudomonas aeruginosa to stainless steel. 28. Collentro, W.C. (1995). Microbial control in purified water
Can. J. Microbiol. 29(11): 1493–1499. systems—case histories. Ultrapure Water 12(3): 30–38.
9. Costerton, J.W. et al. (1995). Microbial biofilms. Annu. Rev. 29. Perry, R.H. and Green, D.W. (1979). Perry’s Chemical Engi-
Microbiol. 49: 711–745. neers’ Handbook, 6th Edn. McGraw-Hill, New York.
10. Hamilton, N.F. (1988). Antimicrobial controls effects of 30. Eggensberger, H. (1979). Zentralbl. Bakteriol. Mikrobiol.
bioslime. Modern Plast. 166–168. Hyg. [B] 168: 517–524.
11. Flemming, H.C. and Geesey, G.G. (Eds.). (1991). Biofouling 31. Baldry, M.G.C. (1983). J. Appl. Bacteriol. 54: 417–423.
and Biocorrosion in Industrial Water Systems. Springer-
32. Krzywicka, H. et al. (1975). Resistance of Microorganisms to
Verlag, New York.
Disinfectants. W.B. Kedzia (Ed.). Polish Acad. of Sciences,
12. Meltzer, T.H. (1993). High-Purity Water Preparation for the Warsaw.
Semiconductor, Pharmaceutical, and Power Industries. Tall
33. Hutchins et al. (1949).
Oaks, Littleton, CO.
34. Block, S.S. (1991). Disinfection, Sterilization, and Preser-
13. Patterson, M.K., Husted, G.R., Rutkowski, A., and Mayette,
vation, 4th Edn. Lea and Febiger, Philadelphia, PA,
D.C. (1991). Isolation, identification, and microscopic prop-
erties of biofilms in high-purity water distribution systems. pp. 167–181.
Ultrapure Water 8(4): 18–24. 35. Orth, R. and Mrozeck, H. (1989). Fleischwirtsch 69: 1575–
14. Pittner, G.A. and Bertler, G. (1988). Point-of-use contam- 1576.
ination control of high purity water through continuous 36. Dychdala, G.R. (1988). Proc. 4th Conf. Prog. Chem. Disinfec-
ozonation. Ultrapure Water 5(4): 16–22. tion. Binghamton, NY, pp. 315–342.
15. Husted, G.R., Rutkowski, A.A., and Couture, A. (1994). 37. FDA. (2000). Available: http://vm.cfsan.fda.gov/∼comm/ift-
Response of oligotrophic biofilm bacteria in high-purity water uv.html.
INDUSTRIAL MINE USE: MINE WASTE 609
38. Hoyer, O. (1998). Testing performance and monitoring of UV include tailings excess decant (rainwater or process
systems for drinking water disinfection. Water Supply 16(1/2): water running off tailings impoundments), process acid
419–442. streams, and mine drainage waters. Drainage from
39. Miller, R., Jeffrey, W., Mitchell, D., and Elasri, M. (1999). tailings impoundments is often circumneutral in pH and
Bacterial responses to ultraviolet light. Am. Soc. Microbiol. contains low concentrations (<20 mg/L) of total dissolved
65(8): 535–541.
metals (10). Process acid stream effluents originate from
40. Bernhardt, H. (1994). Desinfektion Aufbereiteter Ober- the use or generation of acids during metallurgical
flachenwasser mit UV-Strahlen. Wasser-Abwasser. 135(12):
processes and can contain very high levels of dissolved
677–689.
solids and toxic metals. Mine drainage waters are
41. Tchobanoglous, G. and Burton, F.L. (1991). Wastewater
commonly of three main types: (1) saline formation waters;
Engineering; Treatment, Disposal, and Reuse, 3rd Edn.
(2) acidic, heavy-metal- and sulfate-containing waters
Metcalf & Eddy, McGraw-Hill, New York.
formed during biologically mediated and abiotic oxidation
42. Frobisher, M., Hinsdill, R.D., Crabtree, K.T., and Good-
of sulfides (so-called acid mine drainage or AMD); and
heart, C.R. (1994). Fundamentals of Microbiology. Saunders,
Philadelphia, PA. (3) alkaline, hydrogen-sulfide-containing, heavy-metal-
43. Purolite. (2002). Personal conversation, Sam Ashworth with
poor waters resulting from buffering reactions (usually
Francis Boodoo, The Purolite Company, Bala Cynwyd, PA. carbonate) and sulfate reduction within AMD (11,12).
44. Finney, A. (2002). Personal communication, Sam Ashworth
AMD surfaces as discharge from adits and abandoned
with Allan Finney (email), Envron Inc., Regina, Sk., Canada. workings of sulfidic mines or as drainage from sulfide-rich
45. Thibodeaux, L.J. (1979). Chemodynamics: Environmental
overburden material or spoil heaps (13).
Movement of Chemicals in Air, Water, and Soil. Wiley-
Interscience, New York.
ACID MINE DRAINAGE GENERATION
46. Crowl, D.A. and Louvar, J.F. (1990). Chemical Process Safety
Fundamentals with Applications. Prentice-Hall, Englewood
Acidity generation due to sulfide oxidation occurs by two
Cliffs, NJ.
processes: proton acidity and metal acidity. The former
47. Nakayama, S. et al. (1985). Anti-biofouling ozone system for
occurs during the oxidation of sulfides, and the latter is
cooling water circuits. II. An application of seawater. Ozone:
Sci. Eng. 7(1): 31–46.
from the hydrolysis of metal species in solution (15). Each
is discussed here in more detail.
48. Wellauer, R. (1990). Cooling water treatment with ozone.
Ozone: Sci. Eng. 12(3): 243–253. Iron pyrite, the most common mineral leading to AMD,
reacts with oxygen and water according to the following
49. Liechti, P.A. et al. (1992). One year full-scale study of ozone
cooling water treatment at a German electric power station. reaction (16):
Ozone: Sci. Eng. 14(6): 531–544.
2FeS2 + 7O2 + 2H2 O ↔ 2Fe2+ + 4SO4 2− + 4H+ (1)
INDUSTRIAL MINE USE: MINE WASTE This reaction often occurs in underground workings or
deep within spoil heaps and overburden, resulting in
CONSTANTIN VON DER HEYDEN the removal of oxygen and the discharge of an anaerobic
School of Geography and the effluent. Accordingly, oxygen is a limiting substrate within
Environment the deeper workings or lower levels of the spoil heap
Oxford, United Kingdom where anaerobic conditions prevail throughout the year.
Younger (17) differentiates the production of AMD from
flooded workings into ‘‘juvenile’’ and ‘‘vestigial’’ acidity:
INTRODUCTION the former is the dissolution of weathering salts formed on
sulfides when the water table within the workings rises
Intensive industrial development and particularly the pro- following cessation of dewatering activities; the latter
duction of effluents from mining operations has led to is the continuing oxidation of sulfides in the seasonally
worldwide concern for environmental and health impacts flooded zone of the workings as the water table rises and
following decades of contaminated effluent discharge drops within the annual hydrologic cycle.
into natural waterways (1). Developing economies often
depend heavily on extractive or primary industry, and
many third-world governments face the difficult task of Table 1. Typical Mine Drainage Compositiona
reconciling economic development with environmental and
Cu–Pb–Zn Mixed EPA Statutory
social protection. Concern arising from the discharge of
Coal Mines Sulfide Mines Limits
polluted effluent from the mining industry was recorded as
early as 1556 (2), and the legacy of unsustainable develop- pH 2.6–6.3 2.0–7.9 mg/L 6–9
ment is clearly chronicled in sediments worldwide (3–6). Al 1–58
as the discharge of mining and industrial effluents has Cu 0.005–76 0.05
led to a substantial increase in riverine, estuarine, and Fe 1–473 8.5–3200 3.5
marine sediment metal concentrations (7–9). Mn 1–130 0.4 2
Pb 0.02 0.2
Several types of acid and toxic effluents are produced
Zn 0.04–1600 0.2–0.5
by mining and metallurgical processes during operations
and following site decommission (Table 1). These effluents a
Reference 14.
610 INDUSTRIAL MINE USE: MINE WASTE
On contact with the atmosphere, which often com- Active or conventional treatment processes for effluent
mences only at the site of effluent discharge from flooded remediation usually involve expensive technology and
workings or spoil heaps, the oxidation of ferrous to ferric infrastructure and high process costs. Kuyucak (10) lists
iron and the precipitation of ferric oxyhydroxides gener- some of the common active, physicochemical processes:
ates further acidity:
1. active neutralization systems
Fe2+ + O2 + 4H+ ↔ Fe3+ + 2H2 O (2) 2. ion exchange materials, such as resins and zeo-
Fe3+ + 3H2 O ↔ Fe(OH)3 + 3H+ (3) lites (21)
3. membrane processes, such as reverse osmosis,
As noted, Equations 1 and 2 are dependent on an aerobic ultrafiltration/microfiltration
environment. However, once ferric iron has been formed, 4. solvent extraction
Fe3+ acts as the oxidizing agent and the oxidation of pyrite
5. electrochemical treatment (22)
can proceed in an anaerobic environment:
6. bioremediation through controlled sulfate reduc-
FeS2 + 14Fe3+ + 8H2 O ↔ 15Fe2+ + 2SO4 2− + 16H+ (4) tion (23,24)
The reaction kinetics in Equations 1 and 3 are signifi- Passive treatment technology, which as the name
cantly higher than those of Equation 2, and accordingly implies has significantly lower capital and maintenance
the oxidation of ferrous iron is the rate-limiting step in this costs, commonly includes (13)
series (11). However, numerous iron oxidizing bacteria can
markedly increase the oxidation of ferrous to ferric iron. 1. aerobic, surface-flow wetlands (reed beds)
Of these, Thiobacillus ferrooxidans and Leptospirilium fer- 2. subsurface flow systems, such as reducing and
rooxidans are likely to be the most important organisms, alkalinity producing systems—RAPS (25,26)
increasing the rate of reaction by six orders of magnitude 3. combination wetlands, such as compost wet-
(106 ) (11). These organisms function optimally below pH lands (27)
3, thus requiring a degree of pyrite oxidation and ferric
4. anoxic and oxic limestone drains (28,29)
hydrolysis to lower the solution pH to optimal levels (18).
Johnson and Hallberg (19) and Hallberg and Johnson (20) 5. biosorbents (30–32)
show that a host of other organisms known as moderate
acidophils, which include sulfur-oxidizing bacteria and Active neutralization facilities are still most widely
archaea, heterotrophic microorganisms, and some lower used to treat mine waters but vary greatly in the
eukaryotic life-forms, function optimally at pH 3–5.5 and degree of sophistication, depending on the geography
may be involved in the initial sulfide oxidation and proton and local specifications of the site, the nature of the
acidity generation. effluent, and various other environmental, technical, and
Other members of the pyrite family, such as arsenopy- financial constraints. As such, the facilities can range
rite (FeAsS) and chalcopyrite (CuFeS2 ), also generate from the simple addition of neutralizing agents to the
proton acidity upon oxidation, releasing As or Cu into effluent stream, to complex chemical plants consisting
solution in addition to Fe. Monosulfide minerals, such as of reactors, clarifiers, and sludge dewatering technology.
chalcocite (Cu2 S), sphalerite (ZnS), and galena (PbS), are Lime as CaO or Ca(OH)2 is the most common neutralizing
also often encountered in sulfidic deposits. Although the agent used for treating low pH effluent, owing to the
oxidation of these minerals does not generate proton acid- widespread availability, low cost, and high reactivity of
ity (see Equation 5), subsequent hydrolysis of the metal the material. However, lime neutralization results in poor
ions generates metal acidity as in Equation 3: quality effluent and the need to dispose of large volumes
of sludge; accordingly, certain situations require using
ZnS + 2O2 ↔ Zn2+ + SO4 2− (5) other neutralizing reagents, such as Mg(OH)2 , Na2 S, NH3 ,
Na(OH) and CaCO3 (10).
The current state-of-the-art active lime neutralization
TYPES OF MINE EFFLUENT REMEDIATION FACILITIES process is called the high density sludge process (HDS),
where more than one reactor is used to perform the
Mine effluent discharge is almost always a point source,
neutralization, and a mixture of sludge, recycled from
so mine-water problems may be addressed by isolating
the clarifier, and lime is used as the neutralizing agent in
the contaminant source and either treating the discharge
the first reactor (Fig. 1). Polymers are added to improve
in situ (i.e., within the working or the spoil heap by
flocculation, and a clarifier is used to enhance solid/liquid
suppressing the reactions releasing contaminants) or by
separation, decreasing the volume and increasing the
active or passive water treatment following discharge.
stability of the disposal sludge.
Innovative in situ treatment techniques such as galvanic
suppression, application of bactericides, and introduction
of neutralizing or reducing agents are receiving increasing PROCESS IN MINE EFFLUENT REMEDIATION
attention and represent real potential. However, such
techniques have not yet achieved widespread application The activity of hydrogen ions in solution (the pH of the
and require further applied and fundamental research on solution) is the key determinant in the composition of mine
both field and laboratory scales. waters and of their toxicity (16). Metal mineral solubility
Lime Air Polymer
AMD water
Mix tank Clarifier
Overflow
Neutralization reactors 1 & 2
Sludge/lime Sludge to
Lime
tank disposal
Figure 1. The high density sludge process (10).
increases markedly at low pH, and the precipitation The complexation of metal cations with hydroxide ions
of the dissolved metal cation as an insoluble species results in the formation of insoluble metal hydroxide
is low. Moreover, adsorption, which is often a primary (Equation 6), oxide, and oxyhydroxide precipitates (33,41).
process of metal removal from anthopogenically polluted Hydrolysis and oxidative hydrolysis are the most common
systems (7,9), is also often strongly pH dependent (33). processes of metal precipitate formation in aerobic
Adsorption approaches zero as the pH decreases below the surface waters (13,42). However, hydroxide precipitation
adsorption edge of the metal, which for common metals decreases the pH of the water due to the production
such as Cu, Co, Ni, Pb, and Zn is around pH 4–5 (34). of hydrogen ions: the metal acidity discussed above
Anions, for example SO4 , demonstrate the converse; a (Equation 6). As such, oxidation of effluent with high metal
pH decrease leads to greater anion adsorption (34,35). concentrations [e.g., Wheal Jane, see (43)] can rapidly
The free aquo ion is the most bioavailable, so the pH lower the pH of the water and hence affect the mobility
of the solution also affects its toxicity, directly through and solubility of other metals (15,44).
pH-mediated effects on organisms and indirectly as a
result of its effect on the concentration of anions (e.g., M2+(or)3+ + H2 O ↔ M(OH)2(or)3 ↓ +2(or)3H+ (6)
oxyanions of Cr and As) and toxic metals such as Cu,
Pb, and Zn (36–38). As such, correcting the pH is the Reduction Reactions
most important and first consideration in mine effluent Reduction processes are used in active bioreactors and
remediation (13). in RAPS, and numerous researchers identify bacterially
Assuming that effluent pH has been regulated within mediated sulfate reduction as the most effective way
an acceptable range (pH 5–9), Hammer (39) and Dunbabin to decrease sulfate and heavy metal concentrations in
and Bowmer (40) list the most common chemical and contaminated mine drainage (23,45,46). The reduction of
biological processes by which mine effluent quality sulfate and the production of hydrogen sulfide lead to an
is improved: increase in alkalinity and the precipitation of insoluble
metal sulfides (Equations 7 and 8):
1. oxidation and hydrolysis
2. reduction reactions SO4 + Cx Hy Oz ↔ H2 S + wHCO3 (7)
3. adsorption of pollutant complexes to organic and M2+ + H2 S ↔ MS ↓ +2H+ (8)
inorganic surfaces
4. uptake of pollutants by plants Adsorption by Organic and Inorganic Surfaces
5. physical filtering of suspended solids by plants Adsorption and surface complexation commonly occurs
and substrate on sediments, suspended or colloidal matter, and plant
6. Neutralization and precipitation by the formation of surfaces (47). Within contaminated drainage, transport of
ammonium (NH4 + ) and carbon dioxide (CO2 ) pollutants is often facilitated by adsorption on a variety of
suspended and colloidal solid surfaces. Colloidal aggregate
Oxidation and Hydrolysis formation and settling and the settling of suspended solids
are common processes whereby such contaminants are
The change in valence state following oxidation of incorporated into sediments.
certain metals can dramatically influence their solubility: Adsorption is highly pH-dependent (33,41), for example,
oxidation of Fe2+ and Mn2+ , both highly soluble in the SO4 adsorption onto Fe(OH)3 approaches 100% below pH
reduced state, to Fe3+ and Mn4+ results in rapid metal 3, whereas metal cations dominate the adsorption sur-
precipitation as oxide and (oxy)hydroxides. face above pH 4.5 (34). The most important and widely
612 INDUSTRIAL MINE USE: MINE WASTE
studied adsorption surfaces in mine effluent impacted the microbiology of acid mine waters. The processes that
systems are (oxy)hydroxide precipitates of iron and man- use or depend on, microbial action have been described
ganese (35,48–51). The order of metal affinity for MnO2 above. Hence, listed here are the most common examples
binding sites is Co > Ni ≥ Zn > Cu (52), and that for of microbial involvement in processes of mine effluent
FeOOH sites is Pb > Zn ≥ Co ≥ Ni > Cu (34). remediation:
Metals are also complexed with a range of organic
material such as algae, bacterial cells, detritus, and • oxidation of Mn (71,72)
organic coatings on mineral surfaces (40,47,53,54). The • oxidation and hydrolysis of Fe (73,74)
organic adsorption affinity of metals decreases in the • oxidation of sulfides (11)
order Cu = Fe Zn Mn (55,56). Adsorption and sur-
• sulfate reduction
face complexation are rapid processes producing pollutant
attenuation from the water column but are transitory due • products of organic decay (CO2 , NH4 + , and
to marked pH dependency (33,41). Ions immobilized as organic acids)
surface complexes are rapidly released during changes in • surfaces for adsorption
effluent pH conditions.
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J.A. (2003). Optimization of metal sulphide precipitation abandoned Cleveland Ironstone field, north-east England. 7th
in fluidized-bed treatment of acidic wastewater. Water Res. Natl. Hydrol. Symp. British Hydrological Society, Newcastle
37(2): 255–266. Upon Tyne, September 6–8, 2002.
25. Sikora, F.J., Behrends, L.L., Brodie, G.A., and Taylor, H.N. 45. Cloete, E. (2000). Biological sulphate reduction in artificial
(2000). Design criteria and required chemistry for removing acid mine drainage using different carbon sources. WISA-
manganese in acid mine drainage using subsurface flow Minewater Drainage Technol. Conf. Rhodes University,
wetlands. Water Environ. Res. 72(5): 536–544. Grahamstown, January 23–28, 2000.
26. Stephenson, B., Harris, T.M., and Rosche, W.A. (2001). Treat- 46. Hedin, R.S., Hammack, R., and Hyman, D. (1990). Potential
ment of mine drainage with subsurface flow wetlands. Abs. importance of sulphate reduction processes in wetlands
Papers Am. Chem. Soc. 221: 506. constructed to treat mine drainage. In: Constructed Wetlands
for Wastewater Treatment. D.A. Hammer (Ed.). Lewis, Ann
27. Wieder, R.K. (1993). Ion input/output budgets for 5 wetlands
Arbor, MI, pp. 508–514.
constructed for acid coal-mine drainage treatment. Water Air
47. Drever, J.I. (1997). The Geochemistry of Natural Waters.
Soil Pollut. 71(3–4): 231–270.
Prentice-Hall, Englewood Cliffs, NJ.
28. Cravotta, C.A. and Trahan, M.K. (1999). Limestone drains to
48. Kay, J.T., Conklin, M.H., Fuller, C.C., and O’Day, P.A.
increase pH and remove dissolved metals from acidic mine
(2001). Processes of nickel and cobalt uptake by a man-
drainage. Appl. Geochem. 14(5): 581–606.
ganese oxide forming sediment in Pinal Creek, Globe Mining
29. Cravotta, C.A. (2004). Size and performance of anoxic District, Arizona. Environ. Sci. Technol. 35(24): 4719–4725.
limestone drains to neutralize acidic mine drainage. J.
49. Kim, J.-Y. and Chon, H.-T. (2001). Pollution of a watercourse
Environ. Qual. 33(3): 1164–1164.
impacted by acid mine drainage in Imgok Creek of the
30. Xie, J.Z., Chang, H.L., and Kilbane, J.J. (1996). Removal and Gangreung coal field, Korea. Appl. Geochem. 16: 1387–1396.
recovery of metal ions from wastewater using biosorbents and
50. Schemel, L.E., Kimball, B.A., and Bencala, K.E. (2000).
chemically modified biosorbents. Bioresource Technol. 57(2):
Colloid formation and metal transport through two mixing
127–136.
zones affected by acid mine drainage near Silverton, Colorado.
31. Kratochvil, D. and Volesky, B. (1998). Biosorption of Cu from Appl. Geochem. 15: 1003–1018.
ferruginous wastewater by algal biomass. Water Res. 32(9):
51. Yu, J.-Y. and Heo, B. (2001). Dilution and removal of
2760–2768. dissolved metals from acid mine drainage along Imgok Creek,
32. Utgikar, V., Chen, B.Y., Tabak, H.H., Bishop, D.F., and Korea. Appl. Geochem. 16: 1041–1053. .
Govind, R. (2000). Treatment of acid mine drainage: I. 52. Suarez, D.L. and Langmuir, D. (1976). Heavy metal relation-
Equilibrium biosorption of zinc and copper on nonviable ships in Pennsylvania soil. Geochim. Cosmochim. Acta 40:
activated sludge. Int. Biodeterioration Biodegradation 46(1): 589–598.
19–28.
53. Noller, B.N., Woods, P.H., and Ross, B.J. (1994). Case studies
33. Langmuir, D. (1997). Aqueous Environmental Geochemistry. of wetland filtration of mine waste water in constructed and
Prentice-Hall, Englewood Cliffs, NJ. naturally occurring systems in Northern Australia. Water
34. Dzombak, D.A. and Morel, F.M. (1990). Surface Complexation Sci. Technol. 29(4): 257–265.
Modelling: Hydrous Ferric Oxide. John Wiley & Sons, New 54. Stevens, S.E., Dionis, K., and Stark, L.R. (1990). Manganese
York. and iron encrustation on green algae living in acid
35. Rose, S. and Elliott, W.C. (2000). The effects of pH upon the mine drainage. In: Constructed Wetlands for Wastewater
release of sulphate from ferric precipitates formed in acid Treatment. D.A. Hammer (Ed.). Lewis, Ann Arbor, MI,
mine drainage. Appl. Geochem. 15(1): 27–34. pp. 765–773.
614 SUGARCANE INDUSTRY WASTEWATERS TREATMENT
55. Cohen, R.H. (2000). Conjunction of geochemical modelling 73. Burke, S.P. and Banwart, S.A. (2002). A geochemical model
and pilot scale experiments for testing bioreactor removal of for removal of iron (II) (aq) from mine water discharges. Appl.
arsenic and chromium. WISA-Minewater Drainage Technol. Geochem. 17(4): 431–443.
Conf. Rhodes University, Grahamstown, January 23–28, 74. Zhang, C.L. et al. (1997). Physiochemical, mineralogical, and
2000. isotopic characterization of magnetite-rich iron oxides formed
56. Tipping, E. and Hurley, M.A. (1992). A unifying model of by thermophilic iron-reducing bacteria. Geochim. Cosmochim.
cation binding by humic substances. Geochim. Cosmochim. Acta 61(21): 4621–4632.
Acta 56: 3627–3641.
57. Jain, S.K., Vasudevan, P., and Jha, N.K. (1989). Removal of
some heavy metals from polluted water by aquatic plants: SUGARCANE INDUSTRY WASTEWATERS
Studies on duckweed and water velvet. Biological Wastes 28: TREATMENT
115–126.
58. Zayed, A., Gowthaman, S., and Terry, N. (1998). Phytoaccu- MARÍA-DEL-CARMEN
mulation of trace metals by wetland plants: Duckweed. J.
DURÁN-DE-BAZÚA
Environ. Qual. 27: 715–721.
UNAM, National Autonomous
59. Zhu, Y.L., Zayed, A.M., Qian, J.-H., de Sousa, M., and University of Mexico
Terry, N. (1999). Phytoaccumulation of trace metals by wet- México D.F., México
land plants: Water hyacinth. J. Environ. Qual. 28: 339–344.
60. Cohen, R.H. and Staub, M.W. (1992). Technical Manual for
the Design and Operation of a Passive Mine Drainage
Sugar (sucrose) is a sweet, crystalline, white or colorless
Treatment System. Report to the U.S. Bureau of Land
Reclamation. Colorado School of Mines, Golden, CO.
substance, derived from the juice of several plants. World
sugar production amounts approximately to 120 million
61. Hedin, R.S., Nairn, R.W., and Kleinmann, R.L.P. (1994).
Passive Treatment of Polluted Coal Mine Drainage, Bureau of
tonnes, of which two-thirds come from sugarcane and
Mines Information Circular 9389. United States Department one third from sugarbeet. Sugarcane is a perennial grass
of the Interior, Washington, DC. that grows between the tropics (30◦ latitude north and
62. Shutes, R.B., Ellis, J.B., Revitt, D.M., and Zhang, T.T. (1993). 30◦ latitude south) in more than 100 countries. It is the
The use of Typha latifolia for heavy metal pollution control in most efficient earth grass plant for storing solar energy as
urban wetlands. In: Constructed Wetlands for Water Quality biomass and reaches field yields up to 150 ton/ha. A variety
Improvement. G.A. Moshiri (Ed.). Lewis, Ann Arbor, MI. of products are obtained from this versatile plant (Fig. 1).
63. Hansel, C.M. and Fendorf, S. (2001). Characterisation of Many studies on sugarcane are published in journals and
Fe plaque and associated metals on the roots of mine- books. Sugarcane processing to produce sugar represents
waste impacted aquatic plants. Environ. Sci. Technol. 35(19): one of the oldest ‘‘industries’’ in modern times. In America,
3863–3868. the first sugarcane processing plants were located in the
64. Batchelor, A. (2000). Some perspectives on the use of wetlands New Spain territories as well as in the Caribbean islands
for the amelioration of mine drainage. WISA-Minewater since the sixteenth century. In Mexico, for example, the
Drainage Technol. Conf. Rhodes University, Grahamstown, first sugarcane mill was established in Veracruz on the
January 23–28, 2000. Gulf of Mexico in 1525 (1,2).
65. Pulles, W. (2000). Development of passive mine water The power for sugarcane mills originally came from
treatment technology. WISA-Minewater Drainage Technol. water sources (rivers) and from cane bagasse burning.
Conf. Rhodes University, Grahamstown, January 23–28,
Considering that up to the first half of the twentieth
2000.
century, industry was a synonym for smoke, wastewater,
66. Costley, S.C. and Wallis, F.M. (2001). Bioremediation of
and wastes in general, the sugarcane industry was no
heavy metals in a synthetic wastewater using a rotating
exception. Therefore, considering modern sustainability
biological contactor. Water Res. 35(15): 3715–3723.
concepts, the more than 2000 sugar processing plants still
67. Glombitza, F. (2001). Treatment of acid lignite mine flooding
operate around the world with relatively poor technologies
water by means of microbial sulphate reduction. Waste
Manage. 21(2): 197–203. from an environmentally friendly point of view. Figure 2
shows a schematic diagram of a sugarcane factory,
68. Pagnanelli, F., Toro, L., and Veglio, F. (2002). Olive mill solid
residues as heavy metal sorbent material: A preliminary including the wastes generated.
study. Waste Manage. 22(8): 901–907. Roughly, one metric tonne of sugarcane renders the
69. Podda, F., Zuddas, P., Minacci, A., Pepi, M., and Baldi, F. following products:
(2000). Heavy metal coprecipitation with hydrozincite
[Zn-5 (CO3 )2 (OH)6 ] from mine waters caused by photosyn- 350 kg wet bagasse 35%
thetic micro-organisms. Appl. Environ. Microbiol. 66(11): 100 kg sugar 10%
5092–5098. 60 kg straw and leaves 6%
70. Nordstrom, D.K. (2000). Advances in the hydrogeochemistry 40 kg final syrup, molasses 4%
and microbiology of acid mine waters. Int. Geol. Rev. 42(6): 40 kg cachasses 4%
499–515. 100 kg cane heads 10%
71. Chapnick, S.D., Moore, W.S., and Nealson, K.H. (1982). 310 kg evaporated water 31%
Microbially mediated manganese oxidation in a fresh-water 1000 kg sugarcane 100%
lake. Limnol. Oceanogr. 27(6): 1004–1014.
72. Thornton, F.C. (1995). Manganese removal from water using After sugar, the by-product with more added value
limestone filled tanks. Ecological Eng. 4: 11–18. is the final syrup, known as molasses. Molasses is a
SUGARCANE INDUSTRY WASTEWATERS TREATMENT 615
Soil amendment,
animal feed, etc.
Xylitol, ethanol,
and other chemicals
Miscellaneous
Furfural and
derivatives
Cellulose and
products
Electricity
Bagasse Charcoal and

Recycling
activated carbon
Methane-rich
biogas
Pulp and paper

Boiler cinders
Paper and fiber
Fibrous products boards
Particle and moled

Cane tops and
boards
leaves
Sugarcane Sugar
Flue gases
Direct utilization Animal feed,
Fertilizer fertilizer, etc.
(soil improver)
Rum, ethanol,
Animal feed Filter muds derivatives
(cachasse) Distilling
industries Spirits, anhydrous
Raw wax ethanol
Vinegar, other food
Molasses organic acids
Other
biotechnological Acetone, butanol,
products glycerol
Single cell protein
Aconitic acid,
itaconic acid
Monosodium
Miscellaneous glutamate
Dextran, xanthan
gum, L-Lysine
Figure 1. Versatile sugarcane use.
very inexpensive carbon source for many biotechnological wastes, and many processes have been devised to reduce
products, including vaccines and antibiotics (Table 1). Of their polluting impact and to gain some added value
course, fermented and distilled beverages, such as rum, from treating them (5). Tables 2 and 3 show the average
are more widely known biotechnological products. composition of some of these wastewaters, and Table 4
In Figs. 3 and 4, diagrams for sugar and ethyl alcohol presents the regulatory limits that Mexico established in
production are presented. In Fig. 3, the example is the the 1990s for this agro-based industry.
production of raw sugar. The two other most popular It is clear from Table 3 that liquid effluents from a
sugar commercial products are the so-called plantation distillery in the sugarcane mill have a very important
white sugar or mill white sugar (in Mexico, it is known as impact on the overall composition of its wastewaters.
‘‘standard’’ sugar) and refined sugar. Literature presents Also, to comply with the regulations for both sugar
block diagrams for the production of these different production and distilled products, namely ethanol (ethyl
types of sugar (1). Wastewaters are the most conspicuous alcohol), a removal efficiency of more than 95 and
616 SUGARCANE INDUSTRY WASTEWATERS TREATMENT
Flue gas
Boiler house
Cinders
Cane Wastewaters
Bagasse
Water
Cane sugar “Bagacillo”

Power
factory
Molasses Ethyl alcohol

Chemicals
Filter cake
Grease and To cane fields
(cachasse)
fats
Sugar
Gaseous
emissions
Raw materials By-Products / Residues Final products
Figure 2. Raw materials, products, and by-products of the sugarcane industry.
99.8% must be reached for general wastewaters and anaerobic systems are chosen for treating those process
vinasses, respectively. Most of these vinasses, to date, are streams that contain biodegradable compounds because
discharged to receiving bodies (soil, surface water sources) methane-rich biogas can be a plus from the bioconversion.
without any treatment or with a partial depuration To improve the biotreatment and reuse the water
because of the notion that these wastewaters improve soil. in the process, aerobic polishing and sometimes a
However, this is true only when soils are very poor. For physicochemical treatment are added. From the aerobic
good agricultural soils, they have a negative effect (9–11). treatment, the biomass produced can be used in feedlots,
To reduce costs, biological systems are preferred to particularly for fish (12). Leftover treated water can be
physicochemical processes. For that reason, in general, used for irrigating cane fields. In tropical countries, it
is very common to ‘‘cultivate’’ river shrimp (Cammarus
montezumae), known in Mexico as ‘‘acociles’’ (from
Table 1. Molasses Compositiona
the Nahuatl or Aztec language, atl = water, cuitzilli =
Parameter % weight Parameter % weight bent, that bends in the water). Then, an interesting
biological cycle is rendered. Aerobic biomass together with
Water 20 K2 O 3.5
Sucrose 32 CaO 1.5 carotenoproteins from cephalothorax and exoskeleton from
Glucose 14 P2 O5 0.2 river shrimp (the unedible portion), are pelleted for fish
Fructose 14 Carbonates, CO3 2− 1.6 feedlots, and the unedible residues from fish are ground
Nitrogen compounds 10 Sulfate ions 0.4 and used for shrimp cultivation. Figure 3 shows a complete
and other nature-like cycle process instead of the typical man-made
Organic products Other inorganics 0.8 linear polluting processes (Fig. 2).
Density, g m/L 1.42
When wastewaters contain mainly high concentrations
a
Reference 3. of inorganic compound and they are highly soluble, as
Aerobic
biomass for
Washing Aerobic Water
Water Sugarcane feedlots
wastewater treatment recycling
Resins to other
Ion-exchange resins Regeneration uses
and regeneration Water wastewaters and
solutions softening spent resins To solar drying and
solids to other uses
Milling
Cane cutting Bagasse Fly ash, boiler Return to
Oil and grease Cane shredding Boiler house blowdown,purges bagasse burners
Cane crushing Steam
Water to cane
Cane pressing Floor wash, Grease trap
fields
Cane inbibition bearing cooling and solids
separation Grease and solids
water
to bagasse burners
Lime Ca(OH)2 Lime addition
and heating
Bagacillo Cachasse Cachasse cake

Mixed juice
filtration to cane fields
Biogas to Water to
Clarification further use cane fields
Juice recycling
To solar drying Aerobic

HCl + NaOH Multiple stage Acid-caustic
wastewaters and solids to treatment
washing solutions evaporation
other uses
Condensates and To cooling Water

excess condensates lagoons recycling Anaerobic
and condenser water
treatment
Vacuum
boiling Vinasses
Seed magma Molasses or
Centrifugation final syrup
tank
Yeast and Ethanol
nutrients production
Massecuit Massecuit
receiver receiver
Cool water for Syrup Vacuum

Centrifugation recrystallization boiling Sugar dust
crystals washing
Sugar crystals Raw sugar

Dry hot air rotary drying crystals
Biomass
pelleting
Protein Fish
complexes cultivation
Carotenoid Fish by-

pigments products
Chitin River
(chitosan) shrimps
Figure 3. Example of water use, wastewater generation, and treatment proposals for raw sugar.
happens with boilers purges and acid-caustic solutions the caustic and acid products used as raw materials in
used to clean heat transfer surfaces in evaporators the sugarcane mill, reducing the environmental impact of
and vacuum boiler pans, the most suitable process both enterprises (2).
is to eliminate water by evaporation (preferably solar Figures 5 and 6 present schemes of an aerobic plant
evaporation, taking advantage of climatic conditions in for treating wastewaters generated in a plantation sugar
tropical areas). The resulting impure salts, collected as production plant (14). This plant wastewater treatment
dry solids, may be recycled by the companies that sell system had a different approach. The wastewater
(a) Tank 1
15,000 L cane molasses, diluted to 8°Brix at pH 4.5
Mixing – Dilution
10 L H2SO4
18,000 L
5 kg urea
Tank 2
15 kg (bioactivator)
Pasteurization
Penicillin (for bacilli, short and long, cocci, fungi)
Yeast /proliferation, consumes molasses sugars, addition of

Tank 3
more molasses (duplicating the volume of preparation).
Yeast preparation
It is first to 10°Brix till reaching 16ºBrix. To avoid
ethanol formation, the mixture is aerated. When mixture
reaches 6ºBrix, the next step comes
10,000 L yeasts developed at 6°Brix

Tank 4
40,000 L diluted molasses and 30 L H2SO4
Mixing
Aeration
When 15 –16°Brix is reached, molasses are added and
fermentation starts (anaerobic ethanol production)
(b) Water (NH4)2SO4 y (NH4)3PO4 Heads

Sulfuric acid
Yeast Yeast
Molasses
1 2 3 4 5 Filter Ethanol
Air 95 – 96°
6 7 8
Tails
Steam
Fussel oil
Vinasses
Figure 4. (a) Sequential steps for ethanol production in a typical Mexican sugarcane mill using
the final syrup or molasses as a carbon source (4). (b) Ethanol production flow in a typical
Mexican sugarcane mill using the final syrup or molasses as a carbon source (4).
1/2″ Biogas to H2S and CO2

stripping and burning 5
1
2 6
1.5 m Window
“Bell”
biogas Angle 3″ × 1/4
collector
Effluent to 3
primary settler 2″
4
Siphon 0.80 m
Biogas stripper
Profile PTR 3″
3.20 m
0.80 m 1 Biogas
Manhole 2 Reagent addition
3 Water level pipe
1.64 m
4 Purge
Feed 2.1/2″
5 Biogas volume
Climber 1 m Sampler measuring pipe
1 m 25% 6 Secondary settler
feeding pipe
Concrete Sludge purge
Figure 5. Upflow anaerobic sludge bed reactor (UASB) and biogas absorber tower (13).
618
Table 2. Liquid Effluent Characteristics of Some Cane Sugar Processing Plants in the World
Puerto
Parameter Ricoa Hawaiia Philippinesa Louisianaa Indiaa Mexicob
pH 5.3–8.8 n.r.d 5.3–7.9 n.r. 6.8–8.4 6–10

Biochemical oxygen demand (BOD5 ), mg/L 112–225 115–699 130–1220 81–562 67–660 20–36,700c
Chemical oxygen demand (COD), mg/L 385–978 942–2340 50–1880 720–1430 890–2236 47–176,635c
Total suspended solids, mg/L 500–1400 3040–4500 n.r. 409 792–2043 20–46,190
Total nitrogen, mg/L n.r. n.r. n.r. n.r. n.r. 0.2–1260
Total phosphorus, mg/L n.r. n.r. n.r. n.r. n.r. 0.2–2000
Grease and oil, mg/L n.r. n.r. n.r. n.r. n.r. 0–570
a
Reference 6.
b
Reference 7.
c
When vinasses are considered.
d
n.r.: not reported.
composition is similar to those of other countries that Table 3. Average Vinasse Compositionsa
do not contain vinasses (Table 2), so once the suspended Parameter Parameter
matter is eliminated in a primary settler, an aerobic
reactor is adequate for removing most of the dissolved pH 4.8–4.9 Total volatile 76–83
biodegradable pollutants. Here, the feasibility of using an solids, g/L
anaerobic reactor to ‘‘digest’’ the aerobic biomass when Biochemical oxygen 90,000 Total fixed solids, 21–23
demand, mg/L g/L
it is not used for feedlots is shown (13). This reactor
Chemical oxygen 106,000 Dissolved volatile 69–76
gives the added value of methane-rich biogas production, demand, mg/L solids, g/L
once the gas is stripped in a column using the treated Organic nitrogen, 446 Dissolved fixed 18–22
water to dissolve H2 S leaving the methane-rich gas free mg/L solids, g/L
of this corrosive compound and ‘‘enriching’’ the treated Total nitrogen, mg/L 730
wastewater in sulfur compounds before sending it to cane Ammonium ion, mg/L 310 Phosphorus, mg/L 150
fields as irrigation water. Grease and oil, mg/L 2 Calcium, mg/L 2,960
Settleable solids, 27 Magnesium, mg/L 1,370
mL/L
BIBLIOGRAPHY Total solids, g/L 97–106 Sodium, mg/L 310
Total suspended 8–10 Potassium, mg/L 2,550
1. Chaux, D., Durán-de-Bazúa, C., and Cordovés, M. (1991). solids, g/L
Towards a Cleaner and More Profitable Sugar Industry. Total dissolved solids, 87–97 Sulfate ions, mg/L 10,500
UNIDO, Vienna, Austria. g/L
2. Durán-de-Bazúa, C., Cordovés, M., and Zedillo, L.E. (1994). a
Reference 3.
Demonstration of Cleaner Production Techniques for the
Sugar Cane Agroindustry. Final Draft, Consultancy Report
1994. United Nations Industrial Development Office. Project
US/INT/91/217/15-01-2. UNIDO/UNDP, Mexico City, Mexico. Informe técnico de proyecto VIN-01-95. GEPLACEA, CNIIAA,
3. Jiménez, R., Martı́nez, M., Espinoza, A., Noyola, A., and PIQAYQA-FQ-UNAM. Facultad de Quı́mica, UNAM, México
Durán-de-Bazúa, C. (1995). La Caña de Azúcar, su Entorno D.F., México.
Ambiental. Parte II. Tratamiento de vinazas en una planta 4. Castro-González, A., Bernal-González, M., and Durán-de-
piloto en México en un reactor anaerobio de lecho de lodos. Bazúa, C. (2004). Tratamiento de vinazas de plantas
Table 4. Regulatory Limits Established in Mexico for Cane Sugar and Ethanol Production Plant Liquid Effluentsa
Cane Sugar Distilling Industry
Daily Average Instantaneous Daily Average Instantaneous
Parameter Value Value Value Value
pH 6–9 6–9 6–9 6–9

BOD5 , mg/L 60 72 200 240
COD, mg/L n.r.b n.r. 260 360
Total suspended solids, mg/L n.r. n.r. 200 240
Settleable solids, mg/L 1.0 1.2 1.0 2.0
Total nitrogen, mg/L n.r. n.r. 10 12
Total phosphorus, mg/L n.r. n.r. 5 6
Grease and oils, mg/L 15 20 10 20
Phenols, mg/L 0.5 0.75 n.r. n.r.
a
Reference 8.
b
n.r. not reported
620 ESTIMATED USE OF WATER IN THE UNITED STATES IN 1990 INDUSTRIAL WATER USE
Sludge Influent
purge Purge Purge
Sludge
Primary aerobic Aeration tank Secondary
settler treatment settler
cat-walk Sludge
Sludge
aerobic Aeration tank
treatment
Feed
UASB tank
Chlorine addition Secondary settler
Purge Purge effluent
Sludge purge General effluent

Figure 6. Complete sugarcane mill wastewater treatment plant, including a primary settling
tank, an anaerobic feed tank, a UASB reactor, and a biogas absorption tank (biogas stripping)
(14).
destiladoras de alcohol usando consorcios microbianos disposal of excess biological sludge generated in a wastewater
anaerobios. Bebidas Mexicanas 13(3): 12–14, 16–20, 22–25. treatment plant. Anaerobe (Biotechnology) 7: 143–149.
5. Durán-de-Bazúa, C. (2004). Tratamiento Biológico de Aguas 14. Castro-González, A., Durán-de-Bazúa, M.C., Enrı́quez-
Residuales Industriales. PIQAyQA-Facultad de Quı́mica, Poy, M., and Pliego-Bravo, Y. (1998). Consideraciones en un
UNAM, 5th Edn. (1994). México, D.F. Mexico. 6th Edn., in ingenio azucarero para minimizar las descargas lı́quidas
press. y mejorar las condiciones de operación de su planta de
6. Bao-Guo-Yu and Chen-Shi-Zhi. (1990). Treatment and tratamiento de aguas residuales. Ingenio (México) 3(34): 2–7.
Utilization of Pollution Effluents of Cane Sugar Factories in
China. UNIDO. Workshop on pollution control and low waste
technologies in agro-based industries. Shanghai, China. ESTIMATED USE OF WATER IN THE UNITED
7. Anonymous. (1976). Uso del Agua y Manejo Del Agua Residual STATES IN 1990 INDUSTRIAL WATER USE
en la Industria. Vol. 8. Azúcar. Secretarı́a de Recursos
Hidráulicos. México, D.F. Mexico.
8. DOF. (1993, 1995). Normas Oficiales Mexicanas en Materia U.S. Geological Survey
de Protección Ambiental. NOM-002-ECOL-1993, Proy. NOM-
064- ECOL-1995. Diario Oficial de la Federación, Secretarı́a
de Desarrollo Social (Sedesol), Mexico City, Mexico.
Industrial water use includes water for such purposes as
9. Bautista-Zúñiga, F., Reina-Trujillo, T. de J., Villers-Ruiz, L.,
processing, washing, and cooling in facilities that man-
and Durán-de-Bazúa, C. (2000). Mejoramiento de Suelos
Agrı́colas Usando Aguas Residuales Agroindustriales. Caso:
ufacture products. Major water-using industries include,
Vinazas crudas y tratadas. Serie: Quı́mica Ambiental del but are not limited to, steel, chemical and allied products,
Suelo. Vol. 1. PIQAyQA-FQ, UNAM. México D.F., México. paper and allied products, and petroleum refining.
10. Bautista-Zúñiga, F., Durán-de-Bazúa, C., Reyna-Trujillo, T., Many States have developed permit programs that
and Villers-Ruiz, L. (2000). Agroindustrial organic residues: require reporting of industrial withdrawals and return
Handling options in cane sugar processing plants. Part I and flows. Estimates for 1990 are improved over those
Part II. Sugar y Azúcar 95(9): 32–45; 95(10): 23–37. of previous years because of the availability of more
11. Villatoro-Reséndiz, J. (1998). Estudio de la Transformación comprehensive inventories of industrial facilities and more
de la Materia Orgánica Biodegradable de la Vinaza Cruda y complete water-use records. Information on deliveries
Tratada en Los Suelos Acrisol y Vertisol, Del Municipio Miguel from public suppliers to industrial users were estimated
Alemán en el Estado de Veracruz, México. Tesis profesional from a variety of methods if not available directly from
(Biologı́a). UNAM, Facultad de Ciencias, México D.F., México. public suppliers. Consumptive-use estimates generally
12. Durán-Domı́nguez, M.C., Pedroza-Islas, R., Rosas- were based on coefficients ranging from 3 to 80 percent
Vázquez, C., Luna-Pabello, V.M., Sánchez-Zamora, A., (depending on the type of industry) of withdrawals
Capilla-Rivera, A., Paredes-Gómez, L., Valderrama-
and deliveries.
Herrera, S.B., and Vázquez-Cedeño, I. (1991). Producción
de alimentos para peces: Utilización de subproductos del
Industrial water use (freshwater withdrawals, public-
tratamiento de aguas residuales. In: Premio Nacional Serfı́n supply deliveries, saline water withdrawals) during
El Medio Ambiente. J.J. De Olloqui (Ed.). Futura Eds., Méx., 1990 was an estimated 19,300 Mgal/d of self-supplied
México, pp. 79–106.
13. Castro-González, A., Enrı́quez-Poy, M., and Durán-de-
Bazúa, C. (2001). Design, construction, and starting-up of This article is a US Government work and, as such, is in the
an anaerobic reactor for the stabilisation, handling, and public domain in the United States of America.
Table 1. Industrial Water Use By Water-Resources Regions [Figures May Not Add to Totals Because of Independent
Rounding. All values in Million Gallons Per Day]
Self-Supplied Withdrawals
By Source and Type
Ground water Surface water Total Reclaimed

Waste
Region Fresh Saline Fresh Saline Fresh Saline Total Water
New England 96 0.0 382 68 479 68 547

Mid Atlantic 361 .2 1,370 1,470 1,730 1,470 3,200 6
South Atlantic-Gulf 896 0 1,920 94 2,810 94 2,910
Great Lakes 235 3.7 3,950 0 4,190 3.7 4,190
Ohio 532 0 1,840 0 2,370 0 2,370
Tennessee 23 0 1,170 0 1,190 0 1,190
Upper Mississippi 349 0 618 0 967 0 967
Lower Mississippi 501 .6 2,120 67 2,620 67 2,690
Souris-Red-Rainy 1.3 0 47 0 49 0 49
Missouri Basin 114 0 57 0 171 0 171
Arkansas-White-Red 67 0 301 0 368 0 368
Texas-Gulf 141 1.1 600 1,460 741 1,460 2,200 2
Rio Grande 11 0 1.0 0 12 0 12
Upper Colorado 2.9 0 2.5 0 5.4 0 5.4
Lower Colorado 49 0 124 0 174 0 174
Great Basin 77 2.3 29 0 106 2.3 108
Pacific Northwest 336 0 691 36 1,030 36 1,060
California 126 0 4.8 25 130 25 156
Alaska 5.2 0 106 0 111 0 111
Hawaii 20 .6 23 0 43 .6 44
Caribbean 11 1.2 0 50 11 51 62
Total 3,950 9.7 15,400 3,260 19,300 3,270 22,600 9
Table 2. Industrial Water Use By States [Figures May Not Add to Totals Because of Independent Rounding. All values in
Million Gallons Per Day]
By Source and Type

Waste
State Fresh Saline Fresh Saline Fresh Saline Total Water
Alabama 31 0.0 753 0.0 784 0.0 784 0.0

Alaska 5.2 0 106 0 111 0 111 0
Arizona 39 0 124 0 163 0 163 2.3
Arkansas 99 0 78 0 177 0 177 0
California 125 0 3.4 25 129 25 154 .8
Colorado 33 0 85 0 118 0 118 0
Connecticut 19 0 61 68 80 68 148 0
Delaware 18 0 47 6.0 65 6.0 71 0
D.C. .5 0 0 0 .5 0 .5 0
Florida 282 0 121 56 403 56 459 0
Georgia 346 0 311 33 657 33 689 .5
Hawaii 20 .6 23 0 43 .6 44 0
Idaho 170 0 26 0 196 0 196 0
Illinois 155 0 309 0 464 0 464 0
Indiana 129 0 2,350 0 2,480 0 2,480 0
Iowa 71 0 148 0 219 0 219 0
Kansas 50 0 3.8 0 53 0 53 .5
Kentucky 93 0 220 0 313 0 313 0
Louisiana 289 .6 2,070 67 2,360 67 2,430 0
Maine 9.8 0 244 0 254 0 254 0
621
622 ESTIMATED USE OF WATER IN THE UNITED STATES IN 1990 INDUSTRIAL WATER USE
Table 2. (continued)
By Source and Type

Waste
State Fresh Saline Fresh Saline Fresh Saline Total Water
Maryland 21 0 49 379 70 379 450 63

Massachusetts 65 0 22 0 87 0 87 0
Michigan 175 3.7 1,510 0 1,680 3.7 1,690 0
Minnesota 65 0 89 0 154 0 154 0
Mississippi 144 0 126 0 269 0 269 0
Missouri 53 0 32 0 85 0 85 0
Montana 30 0 27 0 57 0 57 0
Nebraska 39 0 2.4 0 41 0 41 0
Nevada 9.4 0 .8 0 10 0 10 0
New Hampshire .3 0 37 0 37 0 37 0
New Jersey 53 .2 273 1,020 326 1,020 1,340 0
New Mexico 4.6 0 1.7 0 6.3 0 6.3 0
New York 85 0 189 0 274 0 274 0
North Carolina 63 0 328 5.5 390 5.5 396 0
North Dakota 2. 0 6.6 0 8.8 0 8.8 0
Ohio 123 0 230 0 354 0 354 0
Oklahoma 3.3 0 32 0 35 0 35 0
Oregon 31 0 254 0 284 0 284 1.6
Pennsylvania 180 0 1,690 0 1,870 0 1,870 0
Rhode Island 2.5 0 9.1 0 12 0 12 0
South Carolina 47 0 585 0 632 0 632 0
South Dakota 5.0 0 10 0 15 0 15 0
Tennessee 69 0 813 0 882 0 882 0
Texas 143 1.1 741 1,460 884 1,460 2,340 22
Utah 77 2.3 29 0 106 2.3 108 0
Vermont 1.0 0 43 0 44 0 44 0
Virginia 195 0 300 66 495 66 561 0
Washington 104 0 397 36 501 36 536 0
West Virginia 106 0 26 0 132 0 132 0
Wisconsin 58 0 409 0 468 0 468 0
Wyoming 6.0 0 9.9 0 16 0 16 0
Puerto Rico 11 0 0 0 11 0 11 0
Virgin Islands .1 1.2 0 50 .1 51 51 0
Total 3,950 9.7 15,400 3,260 19,300 3,270 22,600 90
freshwater, 5,190 Mgal/d of public-supplied freshwater, 3,330 Mgal/d, or 14 percent of freshwater withdrawals
and an additional 3,270 Mgal/d of saline water. (See and deliveries; saline consumptive use was 913 Mgal/d,
Table 1: water-resources regions and Table 2: States.) or about 28 percent of saline water withdrawals.
Industrial freshwater use during 1990 was 13 percent In 1990, the Great Lakes and Mid Atlantic water-
less than during 1985 and represents 7 percent of total resources regions had the largest withdrawals for indus-
freshwater use for all offstream categories. Surface water trial purposes as shown in figure 20 (GIF file), or
was the source for about 82 percent of self-supplied (PostScript file (620 Kb)). Indiana, Louisiana, Texas,
industrial withdrawals; ground water, 18 percent; and Pennsylvania, and Michigan reported the largest state
reclaimed wastewater, only a fraction of 1 percent. Public- withdrawals for industries as shown in figure 21 (GIF
supplied deliveries to industries accounted for 13 percent file) or (PostScript file (508 Kb)). Indiana, Louisiana,
of public-supply withdrawals. Pennsylvania, and Michigan reported the largest
The source and disposition of water for industrial freshwater use (figure 22 (GIF file)), or (PostScript
purposes are shown in the pie charts below (or as a file (508 Kb)), and Maryland and Texas reported
GIF file or PostScript file (94 Kb)). The consumptive use the largest quantities of reclaimed wastewater used
of freshwater for industrial purposes during 1990 was by industries.

586 Bonding of Toxic Metal Ions

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586 BONDING OF TOXIC METAL IONS

0.5 g/L zeolite CA 150

Low contaminated Bonding agents Purified water

Figure 1. (a) Removal of zinc (50 mg/L, pH 6) by

60 Cr(VI) - new synthesis

Development programme of the European Union is gratefully

Effects of aqueous Al, Cd, Cu, Fe(II), Ni, and Zn on Pb

(a) Loaded bonding agent

BPM CEM BPM

Recycled bonding agent Heavy metal as

(b) Loaded bonding agent

Figure 4. (a) Regeneration of water-soluble

Figure 1. (a) PP membranes of 0.1 µm pore

Figure 2. Process scheme of a bench-scale MF plant.

Filtration at 0,5 bar with cross-flow 30 min (BF 30 sec; FF 20 sec)

Transmembrane pressure, mbar

(3) 80 Lm−2h−1, with back-flush

Heat UV unit destructor

Figure 1. Typical spent fuel storage schematic.

MICROBIOLOGICAL MECHANISMS Desorption

TREATMENT RATIONALE Turbidity versus sediment

material. The nephelometer, also called a turbidimeter,

Temperature Concentration Free stream flow

Figure 6. Laminar boundary layers. Figure 7. Turbulent boundary layer.

Aerated water flow

Figure 8. Biofilm corrosion mechanism.

potential target sites on or in microorganisms. It is Table 3. Maximum Ozone Solubility at

Vacuum Shortwave Middlewave Longwave

100 nm 200 nm 280 nm 315 nm 400 nm

254 nm Figure 10. UV light spectrum.

1.5 = 2 × 10−3 atmospheres (2, 000 ppm)

average (TWA) is 0.1 ppm. The estimated concentration

pB Partial pressure in bulk, atmospheres systems to stepwise nutrient supplementation. Ultrapure

Lime Air Polymer

Mix tank Clarifier

Neutralization reactors 1 & 2

Figure 1. The high density sludge process (10).

Bagasse Charcoal and

Pulp and paper

Particle and moled

Single cell protein

Figure 1. Versatile sugarcane use.

Cane sugar “Bagacillo”

Molasses Ethyl alcohol

Raw materials By-Products / Residues Final products

Figure 2. Raw materials, products, and by-products of the sugarcane industry.

Bagacillo Cachasse Cachasse cake

To solar drying Aerobic

Condensates and To cooling Water

Cool water for Syrup Vacuum

Sugar crystals Raw sugar

Carotenoid Fish by-

Yeast /proliferation, consumes molasses sugars, addition of

10,000 L yeasts developed at 6°Brix

(b) Water (NH4)2SO4 y (NH4)3PO4 Heads

1/2″ Biogas to H2S and CO2

pH 5.3–8.8 n.r.d 5.3–7.9 n.r. 6.8–8.4 6–10

pH 6–9 6–9 6–9 6–9

Sludge purge General effluent

By Source and Type

Ground water Surface water Total Reclaimed

New England 96 0.0 382 68 479 68 547