Scott and Ollis

Integration of Chemical and Biological Oxidation
Processes for Water Treatment: Review and

Recommendations
Jon P. Scott and David F. Ollis
Chemical Engineering Department, North Carolina State University,
Raleigh, NC 27695
The literature of studies which used a combination of chemical and biological

degradation ( usually oxidative) of organic contaminants in water is reviewed.
Beneficial efects of such two-step treatments are commonly reported; these results,
primarily f i o m laboratory studies, suggest potential advantages for water treatment
via process integration rather than single technology processing.
Four wastewater contaminant types are identified which can benefit from
combined processes: 1.) recalcitrant compounds 2.) biodegradable wastes with
small amounts of recalcitrant compounds 3.1 inhibitory compounds and
4.) intermediate dead-end products. The design key for such two-step systems lies
in choosingprocesses that complement each other and lead to a synergistic effect.
Predicting this perJormance outcome requires knowledge of the physical, chemical
and biological properties of the major reaction intermediates and their
susceptibility to degradation by each process.
Economic, physical and technological limitations of the indiuidual
processes should be recognized for design of more effective and economical
integrated processes. The ultimate treatment goal, whether specific pollutant
removal or reduction of a global parameter such as TOC, must be known so that
appropriate and complementary processes can be utilized. More work is needed
concerning the degradation kinetics within the combined process,
from initial attack of the primary compound through dynamics of
intermediates and on to total mineralization.
INTRODUCTION fectiveness and cost. Physical processes such as precipitation,

adsorption or air stripping, for example, transfer pollutants
The devclopmcnt of “priority pollutant” lists and the in- from the aqueous to a second phase, but the pollutant is not
creased continuing liability from wastewater effluents sent destroyed. Chemical oxidation may be slow to moderate in
off-site have raised interest in destructive and oxidative pro- rate and selective, or rapid but non-selective, thus generating
cesses for contaminant removal. Among the variety of physi- appreciable reactor or oxidant costs. Aerobic biological oxi-
cal, chemical and biological processes developed for water dation is limited when the feed is either recalcitrant to
treatment, each has inherent limitations in applicability, ef- biodegradation, o r inhibitory o r toxic to the bioculture. Other
88 May, 1995 Environmental Progress (Vol. 14, No. 2)

conversion processes may be limited by economics, oxidative cling of biological and chemical schemes [7, 81 while others
potential, effluent Characteristics or tendency to form harm- examined concurrent oxidative treatments [ 9 , 10, 11, 121.
ful by-products. Effective treatment of a particular wastewa- The four types of wastewaters follow:
ter, given these limitations, may require a combination of
available processes in such a way as to exploit their individual
strengths and thus attain the desired water characteristics Type I. Recalcitrant Compounds
within reasonable economic constraints. Domestic wastewa-
ter treatment plants have long employed a wide range of Large macromolecules such as soluble polymers may not
physical, chemical and biological processes positioned to take
be easily biodegradable due to their size or lack of reactive
advantage of each unit operation strength, exemplifying this
sites. Chemical oxidation can break these compounds into
approach. smaller, biodegradable fragments. Ultraviolet light photolysis
Integration of destructive processes for recalcitrant or in- [ I 3 1 ozone [14, 1.51 photocatalysis [ 1 6 ]and ozone followed by
hibitory contaminant conversion is advantageous conceptu- hydrogen perioxide [I71 have been used for this purpose.
ally. Wastewater that is toxic, inhibitory or refractory to bio- Biological degradation of the untreated contaminant was
logical cultures can be chemically pretreated to produce bio-
negligible for these examples. Chemical oxidation led to
genic intermediates. Conversely, biological pretreatment can smaller chain lengths, increased biological activity and even-
initially remove the biodegradable fraction of wastewater tually greater degradation of the compounds. Suzuki et a/.
containing a mixture of refractory and biogenic compounds, [I71found that polyethylene glycol needed to be broken down
and thereby conserve subsequent use of expensive chemical to a molecular weight of at most 300 before a bioculture
oxidant for the small remaining refractory fraction. could utilize it. Narkis and Schneider-Rotel [I81 used ozone
Despite extensive water treatment experience, surprisingly to degrade the surfactant nonyl phenol ethyoxylatc into
little basic engineering research has addressed the combining smaller and more biodegradable compounds.
of chemical and biological processes and how this combina- Other synthetic compounds are also recalcitrant and re-
tion affects the global contaminant removal efficiency. Such quire chemical oxidation before significant biological activity
information can be useful for optimizing pollutant removal can occur. Steber and Wierich [19] found that l-hydroxy-
and minimizing economic cost. Several studies have noted ethane-1 ,l-diphosphonic acid (HEDP) could not be biode-
the change in biodegradability of a waste stream subjected to graded without pretreatment with sunlight in the presence of
prior chemical oxidation [ 1, 2, 3, 4, 5, 61. The approximately photosensitizers. Kiwi et al. [ 2 0 ] found that treatment of
fifty studies of chemical and biological degradation processes recalcitrant anthraquinone-2-sulfonic acid sodium salt with
in series have appeared only within the last twenty years, Fenton’s reagent (H,O, with iron salts) led to a significant
with much of the research activity occurring only very re- enhancement in biological activity. Kearney et al. studied the
cently. We review this prior literature below. The increase in degradation of pesticides [21, 22, 231, herbicides [24] and
pollutant destruction that often accompanies such two-step recalcitrant munitions [ 251 by combined chemical and biolog-
process combination will be evaluated and key engineering ical oxidation processes. Yocum et al. [ 2 6 ]ozonated indus-
elements and needs discussed. trial wastewaters from toluene diisocyanate, ethylene glycol,
styrene monomer and ethylene dichloride production pro-
cesses and found increased biodegradability due to the chem-
PRIOR LITERATURE ical pre-oxidation step. A d a m and Spitzer [ 271 found that
treatment of a number of finish oils and emulsifying agents
Previous studies using some form of combined chemical (with the exception of ethyoxylated alkylphenol) benefitted
oxidation and biological process to treat difficult contami- from ozone/hydrogen peroxide pretreatment.
nants in wastewaters appear in Table 1. This survey spans Stable natural organic matter such as humic acids have
treatment problems ranging from contaminated groundwater also been subjected to combined processes [ 28, 291. Chemical
to highly specialized industrial wastewater. The treatment oxidation caused these macromolecules to release or frag-
objective varies with each study, as shown by the number of ment into smaller biodegradable compounds. Much of the
methods used to measure the biodegradability of the waste earlier literature considering chemical oxidation followed by
and eventually the removal effectiveness of the combined biodegradation was concerned with this effect in the detri-
system. The chemical processes utilized include hydroxyl rad- mental sense that drinking water disinfected with ozone pro-
ical-mediated advanced oxidation processes, as well as ozone, moted subsequent biological growth in water distribution sys-
hydrogen peroxide, permanganate and natural sunlight, tem [30, 311. Currently, biological/sand filters following
among others. Biological processes include both aerobic and ozonation are routinely used to remove such biodegradable
anaerobic pure and mixed cultures. The final column of Table oxidation products [ 321. Research with ozone followed by
1 provides a qualitativc measure of how the process combina- biologically active granular activated carbon (BAC) demon-
tion influenced the effectiveness of the overall system com- strated that the combination can significantly influence water
pared to controls. This measure follows the conventions in quality, with examples of either negative or positive results
Table 2. Combination of oxidative processes generally leads [33, 34, 351.
to increased degradation of the target compound(s1 with some
exceptions: Nine cases noted a dramatic increasc ( + + 1 and
all others reported a modest increase ( + > for at least one Type ZI. Largely Biodegradable but Requiring Subsequent
pollutant. Chemical Polish
Domestic and some industrial wastewaters contain large

Wastewaters Amenable to Combined Processes amounts of biodegradable organics in addition to relatively
small concentrations of recalcitrant compounds. These latter,
Four types of wastewater are identified below that show persistent compounds may lead to noncompliance in dis-
potential for increased degradation by combined processes. charge effluent if not specifically removed. Combination of
The wastewater characteristics dictate the types below and biological followed by chemical processes may prove useful in
often indicate the order in which the chemical and biological this situation. Biological treatment mineralizes the large
processes are applied. Most studies in Table 1 follow the biodegradable portion, effectively reducing the residual
expected sequential treatment order as described for each chemical oxygen demand of the water. A chemical polishing
wastewater type, however two reports found success with cy- treatment is then applied to degrade the persistent com-
Environmental Progress pol. 14, No. 2) May, 1995 89

Table I Studies Utilizing Chemical and Biological Degradation of Organic Compounds
Authors Chemicals Degraded Biological Degradation Measure of Biodeeradabiiitv , Order of
-
Grade*
Scheme
~ ~~
Adarns et al. 1993 (37) 1,4-diaxane, .3 x 10 -3 M UV/Ozone Anaerobic pretreatment in

- +
2-meth yl-l,3-dioxolane some cases and aerobic post-
treatment
~. -
Adams et al, 1994 (36) 1,4-dioxane, l.2 2.6 x 10 -3 M
- Ozone/ Hydrogen Anaerobic pretreatment in +
2-methyl-1,3-dioxolane, ,20mg/L Peroxide some cases and aerobic post-
1,3-dioxolane 20 mg/L treatment
~ ~
Adams and Spitzer Finish GIs, 000 mg/L Ozone/Hydmgen Activated Sludge culture Removal of TOC C -> B +/%
1994 (27) Emulsifying Agents Peroxide
~
I
Amador et al. 1989 (29) Glycine-humic acid complexes 0pg/ml Artificial Sunlight Soil Microorganisms Evolution of 14-COz 1 C->B +
Irradiation
I
.
Anagiotou et al. 1993 Domestic Landfill Leachate Fenton's Reagent Activated Sludge BODS, COD, measure of I -> C -> B +
(8) 1 ndC->B
Barton and Drake Methanol, 1950-5400 mg / L Fenton's Reagent Activated Sludge culture in Dissolved oxygen C -> B +/O
1994 (66) Reduced sulfur compounds, )ODs to chemical flow-through reactors concentration, mixed liquor
Turpenes eactar settleability and soluble
(Blow heat condensates) liluted to 308 mg/L BOD5
5ODs to bioreactor
Baxter and 2,4-dichlorobiphenyl 1.1-1mg/W ml Artificial Sunlight Pseudomoms isolated from B -> C +
Sutherland 1984 (43) iacterial suspension Irradiation Activated Sludge
G r g e e t al. 1994 (39) Pulp and paper wastewater 8 mg/L AOX Electron beam Activated Sludge culture Removal of DOC and AOX C -> B +/O
with and without Oxygen uptake
oxygen and
hydrogen peroxide
Bowers et al. 1989 (62) 2,44ichlorophenol, '58 mg/L COD Fenton's Reagent Acclimated and non- Maximum specifk substrate C -> B +/O
Dinitro-o-cresol, 135 mg/L COD acclimated Activated Sludge utilization rate
Industrial Wastewaters 277 and 6365 mg/L
:OD
Ehwers et al. 1991 (56) 1) rrolidine, Sulfanilic Acid, 1 x 10 -3 M Fenton's Reagent, Activated Sludge culture Removal percentage of COD 1 C -> B
rJyaphthalene, Phthalic Acid, Potassium Measurement of toxicity
Diphen lamine, Skatole, Permanganate or
Benzal&hyde, Indole, Catechol, Ozone
Resorcinol, Hydroquinone,
Vanillin, Pyrogallol, Salicylic
Acid, Coumarin
Brunet et al. 1982 (33) Surface Water cjot explicitly given Ozone Biologically active granular Oxygen uptake C -> B +
activated carbon Measurement of ATP and
dehydrogenase activity
~~
~ ~~ ~.
Zarberry and Beneing Toluene, 4.7 x 10 -4 M Fenton's Reagent Microbial cultures derived Michaelis-Menten rate C -> B + /o
1991 (65) Trichloroethylene, 5.5 x 10 -4 M from contaminated soil constants
Pen tachlorophenol 1.0 x 10 -4 M
Zozzens and Adanis 2,4-dinitrophenol, 30mg/L and Ozone or Activated Sludge culture Removal of COD C -> B +/-
1994 (74) 4-nitro henol, 200 mg/L Ozone/Hydrogen
2,4-dicglorop henol, Peroxide
4chlorophenol,
4-aminophenol,
2,4-diaminophenol,
2-amino-4-nitrophenol,
2-amino-4-chlorophenol
Eckstein 1994 (59) Naphthalene, 59 pM Ozone/ Hydrogen Specific d e raders or Evolution of 14-COb C -> B + /-
Phenanthrene, Peroxide Activated dudge cultures Measurement of toxicity
Pen tachlorophenol 435
49 PbM
Gilbert 1987 (42) Substituted Aromatics (28 1 x 10 -3 M Ozone Biological Oxygen Demand Ratio of BOD5/DOC as a C -> B +
compounds) function of percent COD
reduction
-
Gilbert 1984 (69) Aromatic Industrial 1730-5300 m / L COD Fenton's Reagent Activated Sludge Ratio of BODs/COD and C -> B +t
Wastewater, BOD20/COD
EDTA-contamina ted f ! f i r mmg/L COD)
/ L &TA
wastewater
Cuillet et al. 1974 (13) Polystyrene Not explicitly given UV-light Soil microorganisms or Evolution of 14-CO2 C -> B +t
Activated Sludge
microorganisms
Hao et al. 1994 (73) Dinitrotoluene Sulfonates (Red 665 mg/l COD Wet Air Activated Sludge culture, Removal of COD C -> B +/O
Water) Oxidation Acinetobacter or Increase in biomass and
Nitrosomonas nitrite production for the
respective cultures
Hapeman et al. 1994 A trazine Not explicitly given Ozone C -> B ++
(44)
~~
Heinzle et al. 1992 (7) Chlorine bleaching effluents = (1-2 g/L) COD Ozone Biofilm culture Removal of TOC, COD, AOX C -> B, +
B -> C and
CyClhg
Hu and Yu 1994 (63) 2-chlorophenol, 500 mg/L Acclimated and non- Removal of COD C -> B +/-
3chlorophenol, acclimated Activated Sludge
$<hlOrO henol,
2,4-dich/&ophenol,
2.4.5-trichloro~henol
Hwang et a]. 1986 (11) 4-Chloropheno1, 25 pg/L Photo1 sis with Natural microbial Evolution of 14-C@ C+ B +
2,4-Dichlorophenol, Phenol, naturaYsunlight population
2,4,5-Trichlorophenol,
Pen tachlorophenol
(Continued on following page)
IJanssens et al. 1984 1 Water Treatment filtrate 12.0-3.7
mg/L
- TOC C->B 1 +
carbon filtration
I
Jones et al. 1985 (54) Oil shale wastewater 1500-1800mg/l DOC Removal of Dissolved
(Previously subjected to Organic Carbon (DOC)
biooxidation)
C-’B I
Katayama and PCB, TNT, TCB, TCDD, DDT 1 pg/mL UV-light UV resistant White rot fungi Evolution of 14-CO2
Matsumura 1991 (‘4 and others ( P . chrysosporium BKM F-
1767) T
+
1IC;rney et al. 1986 Coumaphos 1500 mg/L UV/Ozone Flavobacterium sp. ATCC Evolution of 14-CO2
27551 suspension and also Degradation of parent
soil columns 1mm-d ~~ ~
1IC;rney et al. 1988 Atrazine 33 mg/L Ozone (pH 6.5,8 Soil Microorganisms or soil Evolution of 14-CO2
100 mg/L 10) microorganisms with
Pseudomonas sp. strain A
IKtarney et al. 1983 Trinitrotoluene (TNT) 1 or 10 mg/L UV/Ozone Soil Microorganisms and Evolution of 14-CO2
Pseudomonas Putida in
biometer flasks
iwi et al. 1993 (20) Anthraquinone Sulfonate Photo-assisted Incubation with sewage Zahn-Wellens
. Fenton‘s Reagent sludge
~ ~~
IK’ I I
Kong and Sayler 1983 4-chlorobiphenyl /0.7mg/~ Artificial Sunlight Incubation by mixed culture Evolution of 14-CO2
I lrradia tion Iobtained from river sediment
Koyama et al. 1994 Chlorobenzoates, 53 - 3876 pM Fenton’s Reagent Methanogenic Digester Removal of TOC
(64) monochlorophenols, Sludge Evolution of methane
dichlorophenols,
p-dichlorobiphenyl
Langlais et al. 1989 Paranitroaniline, 7.2x 10 -4 M Ozone Activated Sludge Carbon elimination flux C->B I ++/O
(14) P.E.C. (M.W. moo), 3.05 x 10 -4 M microorganisms on biodisks Ratio of BODs/TOC I
Anthraquinone-2-sulfonic acid 1.25 x 10 -5 M I
Lee and Carberry Pentachlorophenol 1 xlO-3M Fenton’s Reagent Selected Microbial Oxygen uptake to determine
1992 (53) x Hydrogen Consortium (Pseudomonas kinetic rate constants,
Peroxide putida and Pseudomonas Degradation of primary C-’B I
I aeru inosa) and Activated
SludpRe
compound
Removal of COD
I +
IManilal et al. 1992 Activated Sludge Respiration rates compared
to nontoxic controls to
determine inhibition
3zone Ratio of BOD2o/TOC and c->B
nonacclimated seeds BOD2o/COD
I I
Miller et al. 1988 (61) Benzo [a] pyrene 100 mg/L UV light or Incubation with Activated Evolution of 14-Cq C->B +
natural sunli ht Sludge or soil test system
with and wigout
1 I I
100 pg/mL UV light with and Incubation with Activated Evolution of 14-Ca
without Hydrogen Sludge or soil test system
Peroxide
= 40 mg/L Ozone Incubation for 20 days with Removal of COD and TOC C -> B +
Rotel 1980 (18) sewa e sludge ( M d f i e d Ratio of COD/CODo and
OEC%method) TOC/TOCo
Narkis and Schneider- Municipal Waste, Z4160 mg/L COD Ozone Activated Sludge BOqo and Ratio of C -> B +
Rotel 1980 (67) Municipal + Industrial Waste miamrganisms COD/CODo and
TOC/TOCo
Ravikumar and Gum1 Pentachlorophenol LM Fenton's Reagent Mixed culture in soil Heterotrophic plate counts C+B +
1991 (10) columns
~
Sierka and Bryant E-stage wastewater 1000 mg/L TOC Ti@/Sunlight Activated Sludge culture Removal of COD, TOC,AOX C -> B +
1994 (40) (with and without and color
ozone) and Measurement of toxicity
ultrafiltration
Somich et al. 1990 (23) Metolachlor, Atrazine, L- 100 mg/L range Ozone/Hydrogen Soil metabolism Evolution of 14-C@ C->B ++/+
Cyanazine Peroxide
Somich et al. 1988 (24 Alachlor Soil metabolism Evolution of leC& C -> B *
Precursors of trihalomethanes !.3-3.3 mg/L TOC Ozone Biofilm Removal of TOC and C->B +/0
and haloacetic acids TTHMFP
Total trihalomethane
o
! rmation potential )
and Wierich I-Hydroxyethane 1,l-
- Anaerobic incubation by Evolution of 14-C@ C -> B *
diphosphc acid (HEDP) sewage sludge and also
green algae
I
Stowell et al. 1992 (70) Zchlorophenol 1.43 x 10 -3 M Ozone Pseudomonas Putida , . Heterotrophic late counts C -> B +
Degradatton o&rimary
compound and mtennediates
Removal of TOC
Suzuki et al. 1976 (17) Polyethylene Glycol (MW SOOO) !% solution Ozone( H 12) Pseudomonas Aeruginosa Oxygen uptake by Warburg C -> B +
followec! by= PEG-K manometer
Peroxi
H Y Y *e Growth measurements
~~~ ~ ~~
r
S d et al. 1978 (1s) 1.4% for chemical Ozone at pH = 12 Incubation with natural Removal of TOC,
,tudy, 0.1% (parent bioculture Molecular weight
ompound) and 02% distribution
reaction mixture) for
>iologicalstudy I
(Continued on following page)
~~
1.44 x 10 -3 M Ozone Biological Oxygen Demand Ratio of BOD5/TOC C->B +/-

(71)
Tanaka and Ichikawa SDS, ABS, TBC, NPE 100 mg/L Ti02/UV-light Anaerobic digestion Ratio of COD methane
1993 (16) produced to initial COD I c->B I
van der Koij et al. Drinking Water Not explicitly given Ozone (0-4 mg/L) Biofiltration Removal of Assimilable C->B +/-
+
1989 (35)
Wang et al. 1994 (n) Bleaching Plant Effluent 1408 mg/L COD y-ray ~ ~ ~ ~ Biological
I d i ~Oxygen
t i Demand
~ ~ I C->B I + I
IRatio of COD/BODs
Wang 1992 (57) o-cresol, 200-600 mg/L Ozone, Fenton’s Anaerobic cultures Biochemical Methane
2,4-dinitrophenol 100 mg/L Reagent or Potential
Permanganate Anaerobic Toxicity Assay
Wang et al. 1989 (58) 2,5-dichlorophenol 6.13 x 10 4 M Ozone at pH 3 and Anaerobic batch cultures Biochemical Methane I C->B 1 +/O 1
3.68 x 10 -3 M 9 I Potential
I
Watt et al. 1985 (2) Effluent of Activated Sludge Not explicitly given Ozone Mixed culture in 50-day Removal of Doc B->C +/0
metabolizing mixed feed aerobic incubation
Wilhelmi and Ely Acrylonitrile Waste 42000 mg/ L COD Wet Air Conventional industrial Ratio of BOD5/COD C -> B +
1976 (76) Oxidation waste treatment Removal of COD
L
I I
Yamazaki et al. 1983 Humic Acid (MW > 2000) 960 mg/L COD Removal percentages of COD
(2.9) I and TOC I C->B I + I
Yacum et al. 1978 (26) Toluene Diisacyanate Waste, 3360mg/L TOC Ozone Acclimated seed culture BOD5 and removal of TOC C -> B +
Polyol Waste, 830mg/L TOC
St ene Waste, 90rng/L TOC
E Xylene Dichloride Waste 4 0 0 m d L TOC
Table 2 Indicators of Effectiveness for Combined Oxidation Studies
~~ ~
Indicator Effect of Combination on Overall Effectiveness

++ Dramatic increase
+ Modest increase
0 Negligible increase
- Decrease or adverse effect
pound. The primary biological step reduces the number and biodegradable and biological treatment is generally more cost
concentration of compounds that may compete for the chem- cffective than chemical treatment. The lower substrate uti-
ical oxidant, thus increasing overall removal efficiency and lization rate, high maintenance, and greater susceptibility to
lowcring treatment costs. system upset, however, could potentially increase the
A d a m ef al. [ 3 6 ]examined biologically pretreated indus- biotreatment cost. Consequently, it cannot be stated in gen-
trial wastewater containing 1,4-dioxane. This compound is eral whether a two-step chemical and biological treatment
recalcitrant to biodegradation but susceptible to chemical ox- can be economically justified compared to a single step bio-
idation, especially by hydroxyl radical attack. Anaerobic pre- logical treatment.
treatment was used initially in some studies and resulted in Manila1 et al. [41] degraded the inhibitory compounds
the formation of metabolic by-products such as formate, ac- methyl vinyl ketone (MVK), 2,4-dichlorophenol (2,4-DCP)
etate and propionate. Comparison between ozone/hydrogen and pentachlorophenol (PCP) by photocatalysis (UV-light
peroxide treatment of the anaerobic effluent and a fresh with titanium dioxide catalyst). This chemical oxidation of
dioxane solution suggested that the presence of metabolic MVK resulted in a decrease and eventual removal of biologi-
by-products did not significantly retard dioxane degradation. cal inhibition as measured by the oxygen uptake activity of an
This work also utilized an aerobic biological treatment fol- activated sludge culture. Intermediate oxidation times of PCP
lowing the chemical treatment, in order to further mineralize and 2,4-DCP resulted in increased inhibition due to the early
the reaction by-products. Similar results were found with 2- formation of more toxic intermediates, but further oxidation
methyl-1,3-dioxolane [371. eventually removed the inhibitory character.
Heinzle et al. [ 7 ] compared a variety of oxidation schemes Gilbert [ 421 ozonated twenty-eight substituted aromatic
for degrading pulp bleach plant effluents and in particular, compounds and found that continued ozonation generally led
reducing the level of adsorbable organic halogens (AOX) in to an increase in the biodegradability of the reaction mixture,
these waters. Aerobic pretreatment followed by either (1) although some compounds were much more reactive than
ozonation then biotreatment or (2) cyclic ozonation/biotreat- others. The authors determined that 50-70% removal o f the
ment were deemed the preferable treatment options. The C O D was needed before the mixture was considered
authors determined that a combination of treatment schemes biodegradable. Reaction intermediates of aniline and 4-amino
reduced the usage of ozone for a given water quality goal. benzoic acid oxidation were less biodegradable than the par-
Haberl et al. [38] also showed that initial biological treat- ent compound, leading to a drop in the biodegradability of
ment of pulp bleaching effluent was preferable to initial the reaction mixture. Further oxidation reestablished thc
chemical oxidation, since 50% of the original effluent was trend of increasing biodegradability with increased extent of
biodegradable. Subsequent chemical oxidation by ozone or oxidation.
ozonc/gamma-irradiation led to a considerably higher overall
DOC (dissolved organic carbon) and AOX elimination than
did chemical pretreatment followed by biologically activated Type N.Intermediate Dead-end Products
sludgc treatment, due to wastage of oxidant and energy o n
biogenic compounds. Other combined studies of pulp and Combincd processes may also be effective in the degrada-
paper wastewater treatment include Berge et al. [ 391 utilizing tion of specific metabolic products, which may otherwise ac-
electron beam and Sierka and Bryant [40] utilizing a combi- cumulate in the reaction medium and inhibit the microorgan-
nation of heterogeneous photocatalysis (with and without isms. This behavior has a higher potential of occurrence in
ozone) and ultrafiltration. defined biological (e.g., pure) cultures, wherc the enzymes
necessary for total contaminant degradation, eithcr through
metabolism or cometabolism, are not present and thus a
Type III. Inhibitory Compounds complete pathway to mineralization is not available.
Kearney et al. [ 211 found that the insecticide coumaphos
Industrial waste streams often contain biodegradable com- was initially destroyed more effectively by the microorganism
pounds that possess some degree of either toxicity or activity Flavobacterium sp. ATCC 27551 S2 than by a simultaneous
inhibition to the bioculture. These compounds can be de- combination of ultraviolet light and ozone. Howcvcr, a
graded through cometabolic activity or through the presence metabolic intermediate, chlorferon, was formed which could
of specific degrader species in the microbial population. The not be degraded further. The authors used UV/ozone or
bioculture that treats a toxic o r inhibitory effluent is often ozone on this metabolic intermediate to rapidly convert it
less robust and more susceptible to a system upset. Chemical into more biodegradable fragments, which were sent in turn
preoxidation has the potential to partially degrade these to a soil column for further biological metabolism.
compounds into less toxic and more biodegradable interme- Baxter and Sutherland [43] utilized artificial sunlight to
diates, leading to a wastewater more amenable to biotreat- destroy metabolic intermediates of 2,4’-dichlorobiphenyI
ment and a more robust and efficient biological process oper- biodegradation by a Pseudomonas isolate. Although the in-
ation. tcrmediates could be degraded biologically, the addition of
Practical use of combined treatments for Type 111 waste- light opened a second degradation pathway which led to more
waters presents an economic dilemma. The feed stream is thorough destruction.
Environmental Progress (Vol. 14, No. 2) May, 1995 95

Dead-end intermediates may also be formed during chemi- Jones et al. [54] found significant differences between
cal oxidation. Hapeman et al. [44] found that ozonation of ozone, ultraviolet light, and an advanced oxidation process
atrazine led to the formation of 2-chloro-4,6-diamino-s-tri- (UV/ozone) during the degradation of oil shale wastewater.
azine (CAAT) which could not be degraded further. Isolation UV photolysis failcd to significantly decrease the dissolved
of a specialized degrader species, Klebsiella tewagena, was organic carbon concentrations or to enhance subsequent
required to destroy the CAAT contaminant. biooxidation. Ozonation mineralized 8% of the carbon and
the conversion reached 26% after biooxidation. UV/ozone
treatment converted nonpolar materials to more biodegrad-
able polar compounds and provided the greatest overall effi-
DISCUSSION ciency, with 59% carbon mineralized after the combined
treatment, rising to 87% if the bioculture was acclimated to
This section considers how individual process characteris- the chemical oxidant effluent rather than the initial com-
tics were utilized to enhance contaminant destruction, the pound.
order and relative intensity in which the oxidants were uscd, Kearney et al. [ 221 ozonated atrazine at p H values of 6.5, 8
and the methods and parameters utilized for ascertaining the and 10. Atrazine reacted slowly with ozone, but the rate
efficiency in each process. increased with p H and resulted in more polar reaction inter-
mediates. Subsequent bacterial metabolism was higher with
the waste subjected to chemical oxidation at high pH values.
Choice of Chemical Oxidant
The chemical oxidant used in integrated chemical-biologi- Potential for Toxic By-products
cal treatment schemes will determine the oxidation interme-
diates and thus both the subsequent biodegradability of the The chemical oxidant can also play a role in the formation
reaction products and the overall effectiveness of the system. of toxic by-products. Chlorine can react to form halogenated
Different intermediates may result due to the oxidizing po- organics that may be toxic to the subsequent biological cul-
tentials, selectivity or reaction mechanism with each oxidant. ture [55]. Bowers et al. I561 determined that although toxic-
For example, many studies found increased compound de- ity is generally decreased with chemical preoxidation, toxicity
struction and eventual mineralization through advanced oxi- can increase for some compounds such as benzaldehydc, re-
dation processes. These processes involve the in situ forma- sorcinol, and salicylic acid, depending on the chemical oxi-
tion of hydroxyl radicals (OH.), which react quickly and dant used. Wang [ S 7 ] found that potassium permanganate
non-selectively with a wide range of organic compounds [45]; did not decrease the toxicity of 2,4-dinitrophenol to an anaer-
such processes include UV’hydrogen peroxide, UV/ozone, obic culture, although ozone and Fenton’s Reagent treatment
hydrogen peroxide/ozone and photocatalysis 146, 471. did.
Conversely, molecular ozone [ 481 and permanganate [ 491, Wang et af. [S8] found that ozonation of 2,s-dichlorophe-
among others, react through alternative pathways and with no1 at a pH of 3 led to increased dissolved organic carbon
varying oxidative strengths, which often leads to different removal but higher toxicity values than ozonation at a p H of
reaction products. These pathway dependent behaviors are 9. The authors attributed the increased toxicity to an unde-
evident with ozonation under various p H and water condi- termined reaction product.
tions, because ozone can react with organics either directly,
or indirectly through decomposition and formation of hy-
droxyl radicals (OH.) [ 501. This decomposition is accelerated Effect on Fate
at high p H values or in the presence of hydrogen peroxide,
UV light, or other promoters [51]. Molecular ozone will react Oxidants can affect the fate of chemicals found in the
selectively whereas hydroxyl radical is highly nonselective in environment. Organics that are sparingly soluble in aqueous
its attack of organic compounds [52], thus different reaction medium will become more soluble as chemical oxidation leads
products are often expected. The following section provides to hydroxylated intermediates. Likewise, some volatile organ-
examples of how the choice of chemical oxidant affects the ics may also remain in aqueous solution more readily upon
destruction of the primary compounds, the formation of toxic oxidation. Eckstein [ 591 found that ozone/hydrogen peroxide
intermediates, and the biological uptake and ultimate fate of treatment of naphthalene and phenanthrene led to less
the remaining organics. volatile and less adsorbable reaction intermediates respec-
tively. Thus, the organics had higher bioavailability due to
pretreatment, although these particular examples did not re-
Oxidizing Ability sult in higher biodegradation.
Miller et al. [60] found that addition of hydrogen peroxide
Lee and Carberry [53] determined that the oxidation rate accelerated the degrading effect of UV light considerably
of pentachlorophenol by hydrogen peroxide was negligible and led to better biological mineralization of 2,4-di- and
compared to oxidation with Fenton’s Reagent (hydrogen per- 2,4,S-trichlorophenoI. (79% and 59% mineralization of DCP
oxide catalyzed with ferrous ion), which produces hydroxyl and TCP respectively during a 4-day incubation after irradia-
radicals. Pretreatment with Fenton’s Reagent also led to tion in the presence of 0.1 M H,O,, versus 7.7% and 5.9%
faster and more extensive subsequent destruction of PCP in after irradiation only.) U V light in the presence of hydrogen
the biological system (either activated sludge or selected mi- peroxide led to a greater fraction of polar intermediatcs and
crobial culture) than did pretreatment with hydrogen perox- mineralization, whereas U V photolysis alone yielded reaction
ide alone. products exhibiting significant binding to soil. Similar results
Somich et al. [24] found that U V photolysis led to rapid were found for the combined degradation of benzo[a]pyrene
removal of the chlorine substituent from the herbicide [61], although mineralization was considerably lower.
alachlor. Incubation of the reaction mixture with soil mi-
croorganisms led to 60% mineralization of the compound.
Ozone reaction in alachlor solution was slower than photoly- Choice of Biological Agent
sis, but resulted in a more thorough destruction of the com-
pound (through cleavage of the aromatic ring) and greater The biological systems used in these combined studies are
mineralization (80% at thc same radiolabelled position) after more varied than the numerous chemical oxidation pro-
incubation. cesses. As with the choice of chemical oxidant, the appropri-
96 May, 1995 Environmental Progress Wol. 14, No. 2)

ate biological scheme is dependent on the characteristics of effective at degrading wastewaters, especially when the water
the wastewater and the goal of the treatment. Wastewater contained only 2,4-dichlorophenol and not a mixed industrial
with multiple biodegradable organics may be more efficiently waste. As the chemical reaction time was extended, however,
treated with a robust activated sludge community. Con- the substrate uptake by the unacclimated culture (measured
versely, specialized bacterial species or highly acclimated cul- in terms of T O C and COD) increased and in some instances
tures may be appropriate for individual, bioresistant pollu- exceeded that of the acclimated culture. This result suggests
tants. This section will outline and compare different micro- that acclimation of a more diverse culture to reaction inter-
bial culturcs utilized by these combined studies. mediates may be more efficient than acclimation to the origi-
nal waste stream.
Hu and Yu [63]also found that unacclimated cultures gen-
Comparison between Different Cultures erally biodegraded ozonation by-products of chlorophenols
better than untreated chlorophenols. The authors attributed
Some combined studies have used several biological sys- this to either the destruction of the parent compound or the
tems to receive the reaction products from chemical pro- formation of more biodegradable intermediates. Pretreat-
cesses [19, 60, 611. Guillet et a/. [13] found that radiolabelled ment had an adverse effect, however, on some of the biologi-
carbon dioxide evolution rates during biodegradation of a cal cultures that were acclimated to the parent compounds:
photodegraded styrene reaction mixture were similar for a reduction of COD by acclimated cultures was better for some
garden soil culture and activated sludge. The percentage of of the untreated samples than for samples ozonated for a
labelled carbon recovered was approximately 25%, however, short time (6 to 10 minutes).
and required addition of fresh sludge cultures to attain ap- Jones [54] determined that the combination of UV/ozone
preciable mineralization ( > 70%). followed by biological treatment with a culture acclimated to
Other studies considered addition of specific degrader wastewater from an oil shale process led to an overall de-
species to a bioculture in order to accelerate biodegradation struction of 59% DOC. A culture directly acclimated to the
of specific compounds [ 251. Kearney et al. [ 221 added a Pseu- UV/ozone reaction products, however, provided 87% overall
domonas strain to soil microorganisms; soil amended with the reduction in DOC. Stable microbial cultures could not be
Pseudomonad increased mineralization of formulated atra- developed for reaction products from either ozone or UV
zine rapidly and attained higher I4CO, recovery ( = 60%) light pretreatment.
than did unamended soil columns ( = 40%). Eckstein [ 5 9 ]found that after thirty minutes of ozone/hy-
Lee and Carberry [53]compared activated sludge to a se- drogen peroxide treatment, the reaction products of pen-
lected microbial consortium, developed specifically to de- tachlorophenol oxidation were mineralized to the same ex-
grade PCP. Biodegradation of untreated PCP was slow for tent by a generic mixed culture as a culture composed of
both cultures. Once the PCP was chemically pretreated, how- specific degraders of PCP.
ever, the microbial consortium degraded PCP and produced
chloride ion more effectively than did the activated sludge
culture. This result will not hold for all compounds and treat- Pure Cultures
ment systems, as described below.
Pure microbial cultures have been cultivated and geneti-
Comparison between Acclimated and Nonacclimated cally engineered to degrade chemical compounds that are
Cultures generally resistant to biodegradation by conventional treat-
ment. This approach can be effective for highly defined wastes
or wastes which are highly toxic to other microorganisms.
An interesting aspect of the biological processes used in Treatment with pure cultures may be effective only if the
combined treatment is the effect of acclimation on the degra- objective is to reduce the concentration of the target com-
dation ability. Acclimation of microorganisms to the sub- pound. Complete mineralization may not be achieved, result-
strate of interest is widely used to maximize the removal ing in the accumulation of end products and requiring either
efficiency of specific compounds which are difficult to biode- the addition of a second process (as seen with Type IV
grade. This is accomplished by increasing the feed concentra- wastewater) or a more robust microbial community.
tion of the compound of interest over a period of time to
allow for the growth of microorganisms which can utilize the
compound as a carbon or nutrient source. In a combined Anaerobic Cultures
chemical and biological treatment, however, the substrate de-
graded by the bioculture may not be the original compound
to which it was acclimated, but one or more reaction inter- Anaerobic treatment has also been used in combined stud-
mediates. Degradation of these intermediates will depend on ies, both after [16, 57, 58, 641 and before [36]chemical treat-
whether the specific microorganisms or others present in the ment. As found with some Type I1 wastewaters, anaerobic
microbial community have the necessary enzymes (chemical pretreatment can be effective at degrading compounds while
oxidation intermediates may or may not be the same as producing a reduced reaction by-products load.
metabolic intermediates) and ability to successfully biode-
grade them. In some cases, the acclimated cultures may have
an advantage in degrading the intermediates due to their Practical Aspects of Combining Processes
specialized metabolic pathways. Likewise, a culture not strin-
gently acclimated may have a larger number of species which Combining chemical and biological processes poses inter-
are more adaptable in degrading the intermediate. Thus, a esting challenges in conducting research and operating a
question arises concerning the usefulness of strongly accli- full-scale plant efficiently. It may be important that the
mating mixed cultures versus utilizing more robust unaccli- chemical oxidant and bioculture do not mix. Ozone, for ex-
mated cultures in these situations. Also, if acclimation is used, ample, is used as a disinfectant and would be detrimental to
should the culture be acclimated to the original compound or the biological culture if toxic residual amounts remained from
to one or more of the primary intermediates? pretreatment. High concentrations of hydrogen peroxide can
Using reaction products arising from Fenton’s Reagent also prove detrimental to the bioculture although relatively
pretreatment of phenolic waste, Bowers [ 621 compared the low concentrations do not pose a serious problem for mi-
biodegradation by acclimated and unacclimated activated croorganisms. Carberry and Benzing [ 651 found that increas-
sludge cultures. The acclimated culture was initially more ing the hydrogen peroxide concentration relative to TCE or
Environmental Progress (Vol. 14, No. 2) May,1995 97

PCP increased biodegradability up to a point, but at an initial compounds. This phenomenon was also found during ozona-
molar ratio of 6:l (H,O,:pollutant) (4.7 X - 3.3 X tion of conventional biological treatment effluent [ 671 and
M), the high residual levels of peroxide adversely affected the UV/ozone treatment of oil shale wastewater [ 541. Takahashi
bioculture. Barton and Drake [66] found increased toxicity in et al. [71]also found an optimum oxidation time for ozona-
samples of blow heat condensates, which were pretreated tion of nitrophenols and two synthetic dyes (Congo Red and
with high levels of hydrogen peroxide (8.8 X l o p 2 MI, despite Orange 11). Ozonation led to more biodegradable mixtures
taking steps to quench the residual peroxide (2.9 X l o p 2 M). but further oxidation after a dose of 2.3-3.8 mg ozone/mg
Heinzle et al. [ 7 ]experienced a pump failure that led to a T O C nitrophenols or 1.3-1.7 mg ozone/mg TOC synthetic
high ozone level in the biological system, and subsequent dyes led to a decrease in the BOD,/TOC ratio of the reac-
deactivation of the bioculture. Kearney et ul. [21]made position mixtures. Speitel et al. [72]found that ozonation of one
tive use of the cell-killing abilities of chemical oxidation. lake water at high ozone concentrations (5 mg O,/mg TOC)
UV/ozone, applied after biological oxidation by a specialized led to destruction of trihalomethane precursors, but this dose
bacterial species, not only destroyed chemical intermediates was not preferable since the oxidant was wastcd on
but also killed the organism and prevented its viable release biodegradable organics. Significant amounts of bromide were
into the environment. also oxidized to bromate at the higher ozone concentrations.
Special steps were taken by some researchers to prevent Janssens et al. [34]found that small ozone doses (2 mg/L)
the introduction of chemical oxidants into subsequent biolog- increase biological activity in downstream activated carbon
ical processes. These included holding the chemical reaction filters, and thus extend the filter lifetime and removal effi-
mixture for a day to dissipate residual ozone [54, 671, adding ciency. Increased ozonation did not significantly enhance this
catalase [56, 62, 661 o r sodium sulfite [ 3 6 ]to solutions with positive effect but did cause higher production levels of as-
residual hydrogen peroxide or adding sodium sulfate to re- similable organic carbon (AOC). This increased AOC load
duce the potassium permanganate residual [ 561. was less adsorbable on the carbon and resulted in a faster
The chemical reaction conditions also require steps to pre- breakthrough of the filter, although T O C removal was higher
pare the reaction mixture for biodegradation. The use of at the high ozone concentrations.
Fenton’s Reagent is most effective at low pH values ( 3 - 5 )
[68],thus adjustment to higher p H levels may be necessary
prior to biodegradation [53, 651. Removal of iron hydroxide Formation of Toxic By-products
precipitate may also be required after using Fenton’s Reagent,
however Gilbert [69] noted that an activated sludge unit Short chemical oxidation times may prove detrimental due
worked well despite the presence of such a precipitate. to the formation of toxic intermediates. Manila1 et 01. [41]
Potassium permanganate forms a MnO? precipitate that must found that an intermediate product of the photocatalytic oxi-
be removed [56, 571, and photocatalysis requires removal of dation of PCP and 2,4-dichlorophenol led to inhibition of an
the metal oxide catalyst [ 16, 411 before subsequent biodegra- activated sludge culture. This effect was removed, however,
dation. with further chemical oxidation. Bowers [62] found slightly
higher toxicity values for 2,4-dichlorophenol solutions after
partial oxidation, and subsequently decreased toxicity as the
Effect of Reaction Time oxidation time was cxtended. This behavior has also been
reported with wet air oxidation of 2-chlorophenol [ I ] or trini-
trotolucne wastewaters [73],and ozonation of aniline [ 5 , 421
Decreased EfJiciency or amino-substituted phenols [74].
The reaction time in the chemical oxidation process is im-
portant in a combined process. Longer oxidation times lead Measure of Biodegradability
to a greater degree of oxidation and higher removal when
chemical oxidation is the sole treatment. Higher overall re-
moval does not necessarily occur at the long chemical oxida- Gross Parameters
tion times in a combined system, however. When a biological
process is receiving the chemically pretreated effluent, exces- Methods for reporting biodegradability in these systcms
sive chemical oxidation may result in highly oxidized products vary considerably. Gross estimators of water quality include
possessing little metabolic value for the microorganisms. biological oxygen demand (BOD), chemical oxygen demand
Large oxidant doses could be wasted on easily biodegradable (COD), total organic carbon (TOC) and dissolved organic
reaction intermediates resulting in decreased system effi- carbon (DOC). A measure of oxidation state of the wastewa-
ciency. ter can be estimated from the formula [75],
Stowell et al. [70]studied the degradation of 2-chlorophe-
no1 by ozone. Two major reaction intermediates, chlorosuc- 4(TOC - COD)
cinic acid and oxalic acid, appeared sequentially during Average Oxidation State = (1)
TOC
ozonation. Biological growth rate studies using Pseudomonas
Putida on the solutions of the individual intermediates indi- where TOC is in mg Carbon/liter and C O D is mg
cated that the greatest biological degradation occurred with Oxygen/liter. Other common methods report the ratio of
the chlorosuccinic acid intermediate, while the oxalic acid either BOC/COD [42, 69, 76, 771 or BOD/TOC [14, 71, 781.
was not utilized. These parameters may be used to compare the biodegrad-
Adams et ul. [ 3 6 ]found that the key to an effective process ability of the wastewater as a function of chemical oxidation
was complete removal of the parent compound, 1,4-dioxane. time. Yamazaki et al. [ 281 noted, however, that an increasing
The point of disappearance of this compound corresponded ratio with oxidation time may not necessarily indicate in-
to the highest BOD level of the effluent during chemical creasing biodegradability but only a reduction in the T O C or
oxidation. Further chemical oxidation only served to decrease COD. Reductions in BOD, C O D and TOC are also used to
the residual biological oxygen demand. report the destruction of organics during chemical and bio-
Gilbert [69]determined that partial oxidation of aromatic logical oxidation. These measures, however, give little insight
and EDTA-containing industrial wastewater with Fenton’s into the biological system mechanisms.
Reagent led to a highly biodegradable effluent, but further Other biodegradability measures include substrate destruc-
oxidation led to lower BOD,,,:COD ratios. This latter result tion, oxygen uptake, EC,, toxicity measurements, cell growth
suggests wastage of the chemical oxidant on biodegradable counts, intracellular ATP levels and evolution of carbon-14

labelled CO,. Eckenfelder [791 suggested utilizing a fed batch step may not be adequate in all cases. For example, 95% of a
reactor to measure oxygen uptake and to assess biodegrad- reaction mixture may be mineralized in the second biological
ability and toxicity of wastewaters. process whereas without pretreatment, mineralization may
be negligible. Chemical pretreatment plays a large role in
achieving the high global mineralization value although sub-
Kinetic Measurements stantial mineralization did not occur in that step. A scenario
such as this demonstrates the need for measuring the individ-
A few studies have reported biodegradability in a kinetic ual efficiencies while requiring attainment of the overall
rate form. This information is more quantitative than the treatment goal.
previous measures and can be used in the design of biological The simplest method compares the effectiveness of each
reactors and prediction of process performance. These stud- successive process by computing a ratio of the percentage of
ies characteristically report substrate removal rate as follow- the treatment goal attained in a single process to the total
ing Monod kinetics, potential efficiency.
% of Treatment Goal Attained in Chemical Step

X= (4)
100% Attainment of Treatment Goal
% of Treatment Goal Attained in Biological Step
Y= (5)
where qmakis the maximum specific substrate removal rate, 100% Attainment of Treatment Goal
K , the half velocity constant, S the substrate concentration
and X the biomass concentration. Lee and Carberry [53] Z=X+Y (6)
measured the specific substrate uptake rate, S U R = where Z is the total efficiency of the combined process. The
( d S / d t ) ( l / X ) , and used a curve fitting program to determine major criterion is that the desired Z value is attained. Fur-
the qmrXand K , values. Carberry and Benzing [65] also used ther analysis can then be done concerning the amount of
this method in terms of C O D for the removal of TCE, PCP
treatment accomplished in the respective processes, i.e., ra-
and toluene. Both studies utilized electrolytic respirometry to tios of X/Z and Y/Z. Variables, such as process time or
obtain oxygen uptake data. oxidant strength, can be changed to measure their impact on
Bowers et al. [62] determined instantaneous qmaxvalues these ratios.
from fed-batch data by measuring Yamazaki et al. [28] performed this type of analysis in the
treatment of humic acid solutions by a combination of
gamma-irradiation and activated sludge. Efficiencies in terms
(3) of C O D and T O C reduction were calculated for each oxida-
tion step and at different time intervals during the biological
where S,,= substrate input rate and S, = substrate response oxidation. The authors compared the relative efficiencies of
within the fed-batch reactor. These values of biodegradability the chemical and biological treatments by determining ratios
were used to compare the results from different chemical of X/Z and Y/Z. High Y/Z ratios were considered optimal
oxidation times and biological cultures, (assuming that high Z values could also be attained) because
Stover et al. [SO] measured the specific substrate uptake these imply that a large amount of C O D and T O C destruc-
ratc during the degradation of acrylonitrile, 2,4-dinitrophenol tion occurred in the biological system, which the authors con-
o r 1,Zdichloropropane and their ozonation products. Narkis sidered economically favorable. Intermediate oxidation doses
and Schneider-Rotel [ 671 reported first order biodegradation led to the preferred efficiency ratios, although the BOD/COD
rate constants for the destruction of TOC and COD in mu- and BOD/TOC ratios continued to increase with increased
nicipal and industrial wastewater treatment effluent. chemical oxidation. Higher chemical doses tended to reduce
the positive effect on the biological culture found with intcr-
mediate doses.
Measurement of Efficiency in Process A second method considers the ratio of efficiency of the
combined process to the efficiency that would bc accom-
Goal for E’ciency plished if either of the individual processes were used solely,
(assuming equal reaction time, oxidant dose, economic cost,
The measure of effectiveness depends on the treatment or other factor deemed important.) This ratio provides a
goal. The degree of mineralization of all organics may be the measure of the synergism obtained when combining pro-
measure of effectiveness if high purity water or specified cesses and allows for comparison of this measure as a func-
T O C effluent limits need to be attained. Other treatments tion of system variables such that optimal reaction conditions
may consider the primary goal as total reduction of toxicity o r may be identified. Many studies listed in Table 1 have re-
the specific removal of the primary compound. Determining ported their results in comparison to those attained by utiliz-
a goal is an essential step in combined studies because it ing one of the individual processes, although rarely both. The
helps to define process efficiencies and provides a basis for synergism found with respect to each individual process may
comparison and eventually optimization within the process. be extremely valuable, especially when Type I1 or 111 wastew-
aters are degraded, since theoretically, either the chemical or
biological process could be used for complete mineralization
of the waste.
Comparisons between Individual Eficiencies
The global efficiency for the combined processes consid- Constraints on System
ered in this paper consists of a chemical and a biological
component. How these individual process efficiencies are Measures of efficiency will only be important within the
computed and compared is important, because these values constraints imposed on the particular treatment system. Thcse
may be the basis of discovering optimal reaction conditions constraints may appear as economic and physical limitations
for the integrated system. As seen in this review, the initial that are traits of the particular waste treatment facility, such
process step strongly influences the effectiveness of the sec- as reactor volumes, volumetric flow rate or treatment time.
ond process and hence the global efficiency. Simply compar- With no limitations, the most effective treatment would sim-
ing the percentage of the treatment goal attained in each ply allow an indefinite reaction time until the treatment goals
Environmental Progress p o l . 14, No. 2) May, 1995 99

are satisfied. Only in the presence of limitations can an effi- type will affect these results substantially. A model analysis
ciency be defined and compared under different reaction of chemical oxidation followed by an activated sludge process
times and conditions. The particular limitations that restrict or fixed column bioreactor considers these additional cases
a treatment plant's operation may also create and shift re- 1821.
gions of optimal operation due to the synergy within the
integrated system.
Esplugas and Ollis [81] constrained a hypothetical two-
stage process using chemical oxidation followed by biological RECOMMENDATIONS FOR FUTURE STUDIES
treatment. Degradation of a recalcitrant compound and its
assumed sole intermediate followed first-order degradation Recent studies are reporting in greater dctail information
rates in the chemical process while the intermediate followed that better elucidates the positive effect found by applying
Monod kinetics (equation 2 ) in the biological system. The chemical and biological processes in series. Identification of
constraint of a fixed overall reactor time was set and the intermediates and determination of their toxic or inhibitory
individual residence times were varied to determine the ef- properties and their susceptibility to further chemical or bio-
fect on substrate degradation and system efficiency. In this logical degradation is important in expanding this under-
study, the respective efficiencies of the chemical and biologi- standing. There is a great need, however, for a more rigorous
cal system were, approach to reporting efficiencies and modeling the overall
degradation. Such information could assist in the design and
determination of optimal operating conditions of integrated
(7) processes. Below are some suggestions for future studies.
Biological Studies Beyond Biodegradability
where S,,, is the concentration of recalcitrant compound A Numerous studies have reported improvement in bio-
entering the chemical reactor (mg/L), S,, is the concentra- degradability, after chemical oxidation or physical process
tion of intermediate compound(s1 S leaving the chemical re- treatment, by measuring biological oxygen demand or assess-
actor (mg/L), S,, is the concentration of intermediate com- ing toxicity by measuring an EC,, value. These gross param-
pound(s) S leaving the biological reactor (mg/L) and S,, is eters provide little information about the conversion path-
the concentration of compound A remaining after chemical ways and ultimate fate of a parcnt compound, its reaction
oxidation. The overall system efficiency was the sum of chem- intermediates and the final effluent quality in the bioreactor.
ical and biological efficiencies, To better study the effects of one process on the other and
to predict behavior in actual process streams, biological stud-
ies that receive pretreated waste need to be run in systems
(9) which mimic an actual process. Information concerning the
rate of substrate degradation, extent of mineralization and
ultimate fate of all compounds can be determined from these
The authors found that a maximum efficiency was present systems. The extent of conditioning of the microbial culture
and that efficiency goals could be achieved under a variety of to the parent compound, reaction intermediates, or synthetic
reaction times (see Figure 1). More importantly, the chemical mixtures also needs to be reported. As cited above, acclima-
and biological processes accomplished different percentages tion of the biomass to a particular substrate may accelerate
of the total degradation at these different conditions. Given its biodegradation but hinder thc biodegradation of other
trcatment goals could bc attained under a variety of operat- substrates.
ing conditions and oxidant usage, and an economic optimum
could be sought while holding the treatment objective con-
stant. For the example in Figure 1, an 83% efficiency can be Intermediates and their Properties
achieved by 7.2 hours in a (photo) chemical reactor alone, or
by 3 hours in the (photo) chemical reactor and 7 hours in a The reaction intermediates formed in combined processes
biological reactor. If the total fixed and operating costs of the are often the key to the efficiency of the system. If chemical
bioreactor are less than about 4/7 of the chemical reactor oxidation is followed by biological treatment, the resistance
(on a volume basis), as is often the case, then the combined to further chemical oxidation, the biodegradability and the
system would be less expensive. Changes in relative reactivity toxicity of these intermediates all directly influence the effec-
of the primary contaminant and intermediate in both the tiveness of each treatment step and determine when it would
chemical reactor and bioreactor or in reactor operation and be optimal to switch processes. Future studies should recog-
nize this element and report the individual intermediates
formed. A better rationalization of the kinetic phenomena
that occur and of process synergy can be gained through such
information.
Kinetic Models (both chemical and biological)

- Photoreactor Efficiency
----e Biological
Reactor Efficiency
-0- Total Efficiency
Kone of the studies listed in Table 1 presented an overall
kinetic model for the combined process. Such a model would
be required for the design of combined processes and the
determination of optimal operating regions in terms of effi-
ciency or economic cost. The effect of changing such system
variables as flow rates, reactor volumes, organic load etc. on
0 2 4 6 8 10 the total efficiency of the system is important and could con-
Photoreactor Time (hours)
veniently be predicted with an overall engineering model.
FIGURE 1. Efficiency as function of photoreactor resi- The work by Esplugas and Ollis 1811 and Scott and Ollis [82]
dence time (Esplugas and Ollis [Sll). is a step in this direction.

Biological Kinetics with Multiple Substrates and/or ates and any economic or physical limitation imposed on the
Inhibition system.
Only a few studies have utilized kinetic models to rcpre-
The few kinetic models’ to date often ignore the kinetic sent substrate degradation, with a majority of the biological
competition that occurs in both processes as multiple reac- studies relying on gross parameters. More work needs to be
tion intermediates are formed. For example, in the chemical done on kinetic and reactor modeling of both processes with
reactor, competition for the oxidant will occur in systems that respect to the intermediate species. Competition for chemi-
contain a mixture of the parent compound and primary inter- cal oxidant by the compounds and multiple substrate kinetics
mediates. Oxidant competition may also occur when biotreat- for biological mixed cultures are two examples for further
ment is followed by chemical oxidation [ 3 6 ] ,as the recalci- study.
trant targct compound competes with metabolic by-products The global efficiency of the combined process is a key
o r with biogenic materials that were not completely removed. performance measure of these systems. The treatment objec-
Effluents from chemical pretreatment processes will in- tive can indicate what data is to be measured and the manner
clude multiple solutes with different biodegradabilities. Stud- in which efficiencies are computed and compared. More work
ies to datc which have adopted biological kinetic models have needs to be done on how characteristics of the system en-
not considered multiple substrates. Also, models have not hance or limit the individual and global efficiencies and even-
been extended to circumstances where a fraction of the com- tually the overall treatment cost.
pounds present may inhibit biodegradation at high concen-
trations. This is an important kinetic case (Type 111 wastewa-
ter) because application of combined processes is potentially ACKNOWLEDGEMENT
beneficial for this type of wastewater.
We are pleased to thank the Hoechst-Celanese Corpora-
tion Kenan Program in Environmental Science and Technol-
Comparisons of Relative Efficiency in Each Process ogy for both provision of research support and a fellowship to
Step Jon Scott during this study.
The final recommendation for combined studies is to ana-

lyze and present data in terms of global and individual pro- LITERATURE CITED
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Ozonation,” J . Water Pollut. Control Fed., 57(2), pp.
157-166 (1985).
3. Schmitt, M., and D. C. Hempel, “Improvement of Biolog-
CONCLUSIONS ical Catabolism by Preliminary Treatment with Ozone,”
Fourth World Congress of Chemical Engineering (Pre-
Combination of chemical and biological processes leads to prints), Karlsruhee, Germany (June 1991).
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Pretreatment usually enhances the second process. Initial Kraft Process Pulp Mill Effluent,” Ozone Science & En-
chemical oxidation can destroy compounds that would other- grg., 14, pp. 461-485 (1992).
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Integration of Chemical and Biological Oxidation

Processes for Water Treatment: Review and

The literature of studies which used a combination of chemical and biological

INTRODUCTION fectiveness and cost. Physical processes such as precipitation,

88 May, 1995 Environmental Progress (Vol. 14, No. 2)

Domestic and some industrial wastewaters contain large

Environmental Progress pol. 14, No. 2) May, 1995 89

Adarns et al. 1993 (37) 1,4-diaxane, .3 x 10 -3 M UV/Ozone Anaerobic pretreatment in

1.44 x 10 -3 M Ozone Biological Oxygen Demand Ratio of BOD5/TOC C->B +/-

Indicator Effect of Combination on Overall Effectiveness

Environmental Progress (Vol. 14, No. 2) May, 1995 95

96 May, 1995 Environmental Progress Wol. 14, No. 2)

Environmental Progress (Vol. 14, No. 2) May,1995 97

98 May, 1995 Environmental Progress (Vol. 14, No. 2)

% of Treatment Goal Attained in Chemical Step

Environmental Progress p o l . 14, No. 2) May, 1995 99

Biological Studies Beyond Biodegradability

Kinetic Models (both chemical and biological)

100 May, 1995 Environmental Progress (Vol. 14, No. 2)

The final recommendation for combined studies is to ana-

Environmental Progress (Vol. 14, No. 2) May, 1995 101

102 May,1995 Environmental Progress (Vol. 14, No. 2)

Environmental Progress (Vol. 14, No. 2) May, 1995 103

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