Removing dissolved organic

contaminants from water

Second of a sir-part series on
water treatment processes

Walter J. Weber, Jr. pesticides (I). More than 700

Fklward H.Smith specific compounds,
Universiry of Michigan many of them
proven or
AM Arbor. Mich. 48109
potentially
hazardous,
The scope of contamination of the M- have been
c
tion's water resources by dissolved or- identified in treatment, particularly
ganic substances is r e f l d in the &- sources of drink- 7 by halogenation. It is
velopment strategy for the Revised ing water in the unlikely, even with im-
Primary Drinking Water Regulations. united states (2). proved practices for
Three of the five phases of the regula- Of parallel Concern is 7 wastewater treatment
tions focus on establishing maximum the broad range of natu- 7 and disposal, that the
contamination levels for volatile or- rally occurring compounds that extent of dissolved or-
ganic compounds (VOCs), synthetic or- can be transformed into potentiauy 1 ganic contamination
ganic Compounds (SOCs), and organo- hazardous substances in the course of will abate, given the

FIGURE 1
ProcessRow for QzOnatlon and GAC adsotpth

Preomnation

Sedimentation Treated
Pastozonation water

970 Envimn. Sci.Technol.,Vol. 20, No. 10, 1980 W13936W86109200970$01.5WO @ 1986 American Chemical Sociely
likelihood of continued and perhaps ex- ration process, carbon adsorption and on the basis of fundamental mass conti-
panded use of synthetic chemicals and ion exchange adsorption; and two nuity relationships, or material bal-
the inherent difficulties of rigorous membrane separation processes, re- unces, for the phases under consider-
source control. The situation is exacer- verse osmosis and ultrafdtration. Fig- ation. The general form of the material
bated in the case of groundwater by the ures 1 and 2 illustrate typical applica- balance relationship for substance i in a
lengthy times associated with the mi- tions of these processes for water completely mixed reactor (CMR) ele-
gration and subsequent appearance of supply and wastewater treatment (4,s). ment is as it is shown in the equation
pollutants after initial entry to the sub- The discussion of each process is below.
surface (3). complementedby a diagram and an ex- An important aspect of developing
Extension and refmment of water ample of a typical application. Associ- process-specific design models from a
and wastewater treatment technologies ated design considerations and features general material balance relationship is
have intensified in the wake of the con- the accurate representation of process
are presented in sidebars, each of mechanisms in the reaction-reactor
tamination problems of the past decade, which presents a set of equations that terms that describe mass flux and con-
and more rigorous approaches to the comprise a mathematical description, version rates. Accurate determination
design and operation of such technolo- or model, of the process in question. of the application-specific coefficients
gies have evolved. This paper reviews The integration of process-modeling associated with each reaction-reactor
several of these technologies; it dis- principles into the design and operation term is also essential to the successful
cusses the major classes of physico- of treatment systems, especially physi- use of models for purposes of design
chemical processes for removing dis- cochemical systems, is perhaps one of and operation. A basic understanding
solved organic compounds from water the most significant technological ad- of process energetics and dynamics fa-
(The term wafer is used in a generic vances to have occurred in the field of cilitates the structuring of descriptive
sense; it includes surface and subsur- water and wastewater treatment over equations and the identification and
face supplies intended for municipal or the past decade; sufficiently so, in the quantification of important system
industrial use as well as wastewaters opinion of the authors, to warrant em- components.
requiring treatment prior to discharge phasis and discussion in setting the The design bases established by such
or reuse.) A brief description is given stage for considerationof specific proc- models can first be refined and cali-
for each unit process, along with a sum- esses and unit operations. brated using bench scale data and then
mary of the limitations and further de- used to devise appropriate pilot p m
Design philmphy grams for model verification. This is a
velopment needs associated with each.
The review is not exhaustive, but A process model constitutes both a departure from more traditional a p
basis and a means for incorporating proaches that use pilot tests for prelii-
rather it focuses on four processes that into the design of a process those varia- nary information gathering, an expen-
appear to offer the greatest potential for bles that are significant for its operation sive and time-consuming process. Once
general application in the water supply and performance. A model should c a p verified on a pilot scale, a model,
and wastewater treatment industries. ture the physics of the process it repre- rather than more tests, can be used to
These processes are chemical oxida- sents and must of course adhere to the examine the effects of changing process
tion, a transformation process; air principles of continuity. In most envi- variables and to project a system’s re-
stripping, a liquid-gas separation proc- ronmental engineering systems, appli- sponses to a variety of circumstances
ess; two variants of a liquid-solid sepa- cations models are developed primarily that may be anticipated in practice but

FIGURE 2
Wastewater treatment and water reclamation by air stripping, GAC adsorption, and RO
Chlorination

Recarbonation Finration

Sedimentation v

Environ. Sci. Technol.. Yol. 20, No. 10. 1980 971

that are not reproducible in a pilot pro- dation. tered applications (14). Relatively
gram. In addition to allowing savings in Ozonation has enjoyed wide applica- lower capital costs and ease of opera-
time and expense, this approach per- tion for potable water treatment in Eu- tion make the use of chlorine dioxide
mits more ready extrapolation of find- rope. Its acceptance in the United States and chloramines an attractive alterna-
ings from site to site. It also renders has been slow, however, because of the tive to ozonation for preoxidation proc-
process design and operation more ef- associated capital and operating costs, esses in water treatment. There is some
fective because it provides increased the logistics of retrofitting ozonation concern, however, regarding chlora-
flexibility in analysis and response. operations to existing water treatment mine reaction products and their associ-
The philosophical stage for the de- facilities, uncertainties regarding its ef- ated health effects (15).
sign and operation of physicochemical fectiveness in treating refractory or- Although partial or intermediate or-
processes for water and wastewater ganic micropollutants, and the lack of ganic oxidation byproducts often are
treatment applications having been set, residual distribution system protection more biodegradable or otherwise more
it is appropriate to consider major cate- provided when ozone alone is used. or less amenable to removal by certain
gories of such processes, prominent ex- Ozone has demonstrated significant treatments than were their parent com-
amples of their application, and models potential for partial oxidation of natu- pounds, they are not necessarily less
typically used for their design. rally occurring organics (including hu- toxic (7). For this reason, applications
mic substances) that may serve as triha- of chemical oxidation should be accom-
Chemical oxidation lomethane (THM) precursors. It is panied by analyses of the nature and
Chemical oxidation is a process dur- useful for the destruction of THMs and fate of intermediate products.
ing which electrons are removed from a synthetic organic contaminants and for Similarly, because chemical oxida-
substance to increase its oxidation state. the modification of natural and anthro- tion is seldom a self-contained process,
In most cases organic oxidation in wa- pogenic substances for more effective the interactions among and effects of
ter and wastewater, although thermo- removal by complementary technolo- oxidation intermediates and oxidant re-
dynamically favorable, exhibits low gies (7-9). It is likely that there will be siduals on subsequent treatment opera-
rates of reaction; so low, in fact, that an increase in the use of ozonation as a tions (flocculation or activated carbon
complete oxidation is generally imprac- pretreatment for other primary separa- adsorption) warrant careful consider-
tical from an engineering or economic tion or transformation processes in wa- ation. The potential for use of less con-
viewpoint. It is useful in such applica- ter and wastewater treatment in the ventional oxidants, such as hydrogen
tions to define oxidation as a selective years ahead (6, 10). peroxide and ferrates, and of catalyzed
transformation of undesirable sub- Permanganate oxidation processes oxidation processes-particularly those
stances into presumably less harmful or have had limited application in U. S . that involve combinations of ozone, ul-
otherwise less objectionable species. A water and wastewater treatment; they traviolet irradiation, and hydrogen per-
qualitative guide to the reactivity or are used primarily for taste and odor oxide-invites more detailed investiga-
amenability of selected organic com- control in the treatment of drinking wa- tion (7, 16-18).
pounds to oxidation is as follows (6): ter. In this application, the permanga- Finally, as an alternative to current
High reactivity-phenols, alde- nate is normally introduced as early as system- or compound-specific ap-
hydes, aromatic amines, certain or- possible to allow maximum contact proaches to applications of oxidative
ganic sulfur compounds (thioalco- time and subsequent removal of precip- processes, a more systematic, princi-
hols, thioethers) itated MnOz formed as a result of the ple-oriented methodology that allows
Medium reactivity-alcohols, alkyl- reduction of Mn(VII) to Mn(1V). Al- the identification of those factors that
substituted aromatics, nitro-substi- though permanganate is not an eco- govern system performance should be
tuted aromatics, unsaturated alkyl nomical oxidant for direct removal of pursued. This will facilitate the struc-
groups, carbohydrates, aliphatic ke- THMs or most other potentially toxic turing of models for predicting the re-
tones, acids, esters, and amines or carcinogenic organic pollutants (7, sponses of whole classes of organic
Low reactivity-halogenated hydro- it has been shown to reduce the produc- compounds to various oxidative proc-
carbons, saturated aliphatic com- tion of THMs in waters containing esses in the context of comprehensive
pounds, and benzene monomeric precursors such as phenols, treatment schemes. Figure 3 shows a
Because oxidation processes tend to anilines, and quinones-provided that process that uses ozone to oxidize or-
be energy intensive and therefore the raw water does not also contain pro- ganic contaminants (19).
costly, their breadth of application in portionally high levels of humic mate-
water and wastewater treatment is lim- rial (11).The effectiveness of perman- Air stripping
ited (7). This is particularly the case for ganate has been enhanced in certain More than a half century ago, simple
wastewater treatment. Because oxida- applications with small dosages of pow- aeration systems were used routinely to
tion processes are fundamentally stoi- dered activated carbon (12). strip water of organic taste- and odor-
chiometric, much higher levels of oxi- Chlorine dioxide, too, has gained its producing compounds (20).This prac-
dant are required for high levels of broadest application in the water and tice fell into disuse as more effective
organic concentration. wastewater industry as a disinfectant chemical oxidation and carbon adsorp-
Growing experience with ozone, per- and reagent for removing of taste- and tion processes were developed and re-
manganate, and chlorine compounds in odor-producing organic matter from fined. Interest has been rekindled,
water treatment, however, has demon- municipal water supplies. It has been however, by the increasing numbers
strated that appropriate integration of used for treatment of contaminated and concentrations of VOCs appearing
oxidation reactions with other unit groundwater and for oxidation of raw in raw water supplies.
processes often can enhance overall or- surface influents (7.A particularly ap- Removal of organic substances from
ganic removal efficiency at modest pealing feature of chlorine dioxide is water by air stripping involves their
cost. An example of this is found in the that it provides the dual benefits of pro- transfer from the liquid (water) phase to
coupling of chemical oxidation and bio- ducing minimal THMs and of provid- the gas (air) phase. The air-water inter-
logical treatment, a process in which ing an active residual disinfectant in face is thus of primary concern in strip-
biologically resistant compounds can, distribution systems (13). per system design. Aeration basins and
by partial transformation, be rendered Chloramines have demonstrated par- packed columns are the two most com-
more amenable to subsequent biodegra- tial benefits of similar nature in scat- mon reactor configurations employed.

972 Environ. Sci. Technol., Vol. 20,No. 10, 1986

 FIGURE 3
Ozone p- using oxygmenriched air and countermmnt flowthrough contactor
I Ozone generation 1 Ozone contacting -

unit

Aeration in stripping basins is accom-

I Design and application features for ozonation plished either by introducing air
through diffusers (bubble aeration) or
Typical application by mechanical agitation (surface aera-
Preozonation of a water supply for reduction of THMs and THM r ~ ...~ tion). Although bubble aeration is gen-
erally more efficient, surface aeration
Primary design considerations and approach is usually easier to retrofit and has been
Preliminaryconsiderations demonstrated to be effective for the
Influent: nature and concentration of components; impacts on ozone stripping of many Phase I VOCs,Phase
dncnmnnnitinn
-.....-.
....... II SOCs, and Phase lV volatile chlorin-
Ozone source gases: air; oxygen-enricheda;r; high-purity oxygen ation byproducts (21,22).
Generators: Otto plate; tuoe type; Lowther plate As their name implies, packedcol-
Key oesiqn parameters: feed gas flow rate; temperature and pressure;
generator voltage and frequency umn strippers use a deep bed or tower
Diffuser-agitation equipment: optimum design based on hydrodynamic ard reactor to provide sufficient contact
mass transfer considerations time and packing material withim the
Reactor systems reactor to ensure a large contact surface
Options: completely mixed flow (CMFR) or plug flow (PFR); cocurrent or for phase transfer. Principal design pa-
countercurrent ozone flow rameters for packed-column strippers
CMFR design equations: include water temperature, depth and
Ozone mass transfer (absorption) into the liquid phase: type of packing, surface loading rate,
(d[Od/df)abs = KLa ([0& - 1031) and volumetric air-to-water ratio (23).
KLais the volumetric mass transfer coefficient across area, a; IO,]and [O& Packed-column aerators generally are
are molar temporal and saturation concentrations. operated i n a countercurrent flow
mode, with slowly falling films of wa-
Liauid-Dhasemass balance for flow 0 and volume V ter meeting risiig air to promote effi-
cient phase transfer. Flooding-a condi-
tion in which the downward stream of
water is so impededby the upward flow
s-phase mass balance for flow Qg and volume Vg: of air that the void spaces of the pack-
(MWo,IRT) (Vg) (dPoJd0 ing are saturated and mass transfer
ceases-is the most frequent opera-
= (MWoJRT) i(Qg.irPos.in - Qg,ouPo,ouJ
tional problem for countercurrent
- (dPo,Idt)abs V g - (dPo,ldt)midecmpvg~ packed columns.
R is the universal gas constant; Tis absolute temperature; MWo, and po, Henry’s law and appropriate phase
are molecular weight and partial pressure of ozone, respectively and interface (fh) mass transport ex-
Source: Reference 19. Adapted with permission from Wasfewale, Disintect;oan. Manual of Preclj- pressions that incorporate interphase
No. 4 0 1986, Water Pollution Control Federation concentration gradients an be coupled
to describe, respectively, the thermody-

Environ. Sci. Technol., Vol. m,NO.10, 1986 973

 FIGURE 4
Air-sbipping tower with concentration profilesfor countercurrent Row

T
Air -
e,
.,,,
Y.
1
water

namics and kinetics of stripping proc- In-well aeration may be suitable in phase. to the surface of a solid phase,
esses. Mathematical models are now cases that require emergency treatment where it accumulates for subsequent
being r e f i and verified for the inClu- or where lower efficiency is acceptable extraction or destruction. Activated
sion of appropriate system design pa- because of its relatively low cost and carbon is the most common solid
rameters for stripping basins and ease of implementation (28). In certain phase, or adsorbent, used in water and
packedcolumns. cases of large-scale surface water sup wastewater treatment, although ion ex-
Aeration basin design has the advan- ply and wastewater treatment, it may be change adsorption normally uses a syn-
taze of b e i i able to draw on a substan- feasible to adaot existine treatment ba- thetic polymer resin as an adsorbent or
tial t m ~ yof experience with oxygen sins for remobl of V&s by surface exchanger matrix (6).
transfer processes in natural systems aeration (21, 29). The air-stripping The use of activated carbon adsorp-
and other treahnent operations. Me- process has been shown to be particu- tion in the water industry has evolved
chanical surface aerator systems are in larly effective for removal of THMs, from applications for taste and odor
most cases easier and less expensive to affording total THM reductions of control to a spearurn of uses for re-
construct and operate than are column more than 90% in appropriately de- moval of specific organics, such a?,
or packed-bed systems. Energy re- signed systems (23,30,31). chloroOrganiccompounds and aliphatic
quirements, a major cost factor, are In summary, air stripping offers p and aromatic hydrocarbons; for reduc-
about the same for mechanical aerators tential for the relatively effective and tion of total organic carbon m); for
and countercurrent packed-column economical treatment of waters con- removal of THM precumm, such as
strippers (24). Packed columns enjoy taminated primarily by VOCs. For cer- humic substances; for use as a support
the advantages of requiring smaller tain applications, it should be consid- medium for attached growth for biolog-
amounts of land and of offering better ered as an augmentation to other i d l y aided removal of organics; and
opportunity for containment and treat- processes rather than as an independent for dechlorination (34). Some water
ment of related off gases. operation. Further inquiry, including treatment plants replace sand or other
Although much of the development comparative economic assessment, is fdter media with GAC. In other in-
work in air-stripping technology for required to determine optimum air-wa- stances, the use of posttidter GAC col-
wastewater and large-scale surface wa- ter contacting modes. The utility of ex- umns that provide greater carbon
ter applications is still in the laboratory isting mass transfer models must be depths and contact times is necessBIy to
and pilot plant stages, there have been verified under conditions more closely obtain the required removal of undesi-
several field installations of air-strip approximating field circumstances. able organic substances.
ping systems for removal of halogena- More precise analysis of the MNE, ex- The carbon adsorption process is
ted VOCs from contaminated ground- tent, and potential health effects of air- widely used to treat industrial wastes
water. In a few cases the &pping borne emissions resulting from aeration for reduction of overall organic con-
process has been used in conjunction processes and, for problematic cases, tent, specific compound removal, by-
with granular activated carbon (GAC) the design of cost-effective off gas con- product recovery, and toxicity rednc-
adsorption to achieve overall organic trols should be a priority for research tion (35-38). Adsorption technology
contaminant reduction (25). If VOCs and development. Figure. 4 shows a also has been found effective for
are the only organics of concern, how- typical air-stripping process (32, 33). groundwater cleanup operations, in-
ever, air stripping alone may be pre- cluding treatment of drinkingand proc-
ferred; economic comparisons show Adsorption ess waters, treatment of waters for arti-
that this process is significantly more Adsorption is a partitioning process ficial recharge of aquifers, and aquifer
cost-eWve than GAC treatment for in which a contaminant is transferred decontamination by treatment of water
these contaminants (26,27). from a dissolved state in the aqueous from purge wells (39-41).

S74 Envimn. Sci. Technol., Vol. 20, No. 10, 1988

 service. Mass transfer descriptions,
Design and application features for air stripping and hence design approaches, also are
similar for GAC and exchange adsorb-
Typical application em. Ion exchange resins are generally
Packed-tower aerator for stripping of volatile organics from groundwai synthetic cross-linked hydrocarbon
polymers with attached functional
Primary dasign considerationsand approach groups. The polymer matix and the
Preliminary considerations number and type. of functional groups
Influent: concentration and effluent requirements for target compounds; associated with the matrix can be varied
eflects of background components; effects of temperature to impart ion selectivity, exchange ca-
Stripping column: dimensions; type and size of packing; volumetric air/ pacity and rate, regeneration means and
water ratio; air and water loading rates; allowable gas pressure drop
efficiency, stability, and tolerance to
Reactor systems
ODtbns: PFR sDrav towers: cocurrent. countercurrent. or cross-flow
PkR countercukerhdesignequations:
I fluctuations in pH and temperature.
The five primary resins are strong and
weak acid (cation) exchangers, strong
Henry’s law in terms ot total pressure (0and solute mole fractions in water and weak base (anion) exchangers, and
(qand air (v) streams: intermediate exchangers, which con-
KH = Henry’s constant = (P)(Y)/(X) tain strong and weak base groups (M).
The properties of selectivity associ-
z = (HWJ pro) ated with commerciaUy available ion
exchange materials pose problems for
application to the heterogeneous innu-
= (S/(S- 1))In [[(X,,/X,J (S- 1) + ents encountered in many municipal
re mole fractions of solute in influent and effl waters and wastewaters. Municipal
StriDdna factw, S, defined in terms of sumrficialmolar w wastewater applications of exchange
adsorption for removal of organic ma-
terial are virtually nonexistent. In ex-
periments aimed at determining their
suitability for municipal water supply
use, weak base exchangers have been
&a is mass transfer coefficient for liquid phase; V, is molar volume of water found to remove humic substances. Al-
though strong base resins have a higher
I Source: Reference33.Adapted with permission ham
@ lW5. John Wiley 8 Sans
lhgw TrealmentPrinc!pfes end oeagn ion exchange capacity, weak base resins
are more practical because of their
higher regeneration efficiencies (45,
46). The cost-effectiveness of exchange
Most adsorption applications use IPCT systems in municipal wastewater adsorption for removal of organics in
GAC in fixed beds in paraUel or in se- treatment applications, both have been water treatment is debatable.
ries. As noted earlier, GAC adsorption plagued with design problems and rela- Ion exchange treatment for organic
can be accompanied by air stripping to tively high operational quirements substances has had more widespread
remove readily adsorbable contami- and costs. Efforts to address these application in industrial waste pollution
nants and certain less adsorbable but shortcomings have been accompanied control. It is effective for removing or-
volatile organic solvents. Preaeration in by investigations of technically and ec- ganic coloring agents from textile man-
groundwater applications of GAC can onomically feasible alternatives. One ufacturing, weaving, and finishing
lenethen column runs to the extent that promising option is a process that inte- wastes (47) and from pulp and paper
operating costs can be reduced by 30- grates activated sludge and powdered mill discharges (48). Highly effective
50% 1.29. activated carbon (PAC) by adding PAC phenol removal and recovery (49) and
host effective applications of k t l y to the aeration basii of acti- virtually complete removal of part-per-
GAC technology in municipal waste vated-sludge systems. Studies indicate million and part-per-billion levels of
water treatment have been in a tertiary that PAC enhances biological assimila- pesticides also have been reported (50).
mode that follows secondary biological tion of organics and, in turn, that its Anion exchangers have been used to
systems. In this configuration GAC ad- adsorptive capacity can be partiaUy re- remove high-molecnlw-weight organ-
sorption functions as a polishing opera- newed by concurrent microbd degra- ics from raw wastewater for prepara-
tion for removing biologically resistant dation of adsorhid or desorbing organic tion of high-quality process water for
compounds.Independent physicochem- compounds (42, 43). The most attrac- reuse (51).
ical treatment (lF’CT) is an alternative tive features of this process are its cost- Other environmental applications of
that uses GAC columns to treat clari- effectivenessand the ease with which it exchange adsorption include the con-
fied raw wastewater dimtly, thus by- can be adapted to existing activated- centration and recovery of organic con-
passing conventional biological treat- sludge facilities. taminants for analytical purposes; for
ment. IPCT is an attractive option for As the name implies, ion exchange, process water treatment and byproduct
industrial pretreatment of wastewater or ion exchange adsorption, is a proc- recovery in certain chemical, pharma-
for discharge to municipal systems ess in which ions held by electrostatic ceutical, and food production opera-
where selective removal of only a small forces to charged functional groups on tions; and for protecting demineralizer
number of particularly adsorbable haz- the surface of a solid are exchanged for exchange resins from organic fouling
ardous organic contaminants is re- ions of l i i charge in bulk solution. As by humic acids (4447).
quired, or when problem waste streams with GAC adsorption units, the most In general, synthetic polymer resins
can he readily identified and isolated common mode of operation is with are expensive, contributingto high c a p
from main industrial flows (35). granular adsorbent resins contained in ital investments for exchange adsorp-
Although tertiary systems generally packed, fixed beds that can be ex- tion systems. Influent water quality is
have performed more successfully than hausted, regenerated, and replaced for another important consideration, be-

Envimn. %I. Technol., MI. 20. NO.10, 1980 975

 FIGURE 5
GAC adsorption

0,c.

1,
Fixe

cause elevated levels of suspended sorkr design and operating conditions carbonaceous adsorbeuts incorporating
solids can produce excessive head for specific applications. Figure 5 is a appropriate surface functional groups
losses in the exchanger bed and resins diagram of the process (52,53). 0ffe.l particular potential.
can be oxidized or fouled by certain Amendment of modeling methodolc-
raw-water contaminants. Other signifi- gies to account for the complex compo- Membrane separatiom
cant sources of expense include the sition of many waters and wastes (such The earliest applications of mem-
chemicals required for regeneration as the presence of specific organic con- brane separation for water purification
and the nature of the regenerant. The taminants and unidentified background involved small-scale treatment of
cost of the system takes into account organic matter) is one of the major brackish waters for process and potable
whether it is possible to recover valu- challenges in the field today. Although use. Technological advances have ex-
able materials and whether additional sophisticated conceptual adsorption panded the utility of such processes to
disposal problems persist. models for multicomponent system are largescale applications ranging from
The design of efficient and economi- available, remaining uncertainties in seawater d e s a l i i o n to treatment of
cal GAC and exchange adsorber sys- the parameter evaluations used to cali- complex industrial wastes that include
tem requires accurate assessment of brate these models accurately have con- mixtures of organic and inorganic com-
the water or waste to be treated and a strained their application to complex pounds. Ultrafiitmtion (UF) and re-
fundamental understanding of related water and wastewater system. verse osmosis (RO) are the two most
bulk solution and interfacial phase phe- Other areas of pursuit include re- commonly used processes fpr removal
nomena. Adsorption from solution in- search into the potential use of synthetic of organic contaminants. Both are con-
volves the transfer of soluble species carbonaceous adsorbents for special- sidered here because they address
from bulk liquid phase to the surface of ized organic pollution abatement and somewhat different molecular ranges of
an adsorben-a transfer governed by for solute recovery applications, devel- organic matter commonly found in wa-
specific system dynamics that results in opment of more efficient means for ter and wastewater.
a characteristic equilibrium distribution transfer and regeneration of adsorb- Ultrafiltration operates by the same
or partitioning of these species between ents, and determination of the effects principles as conventional Septum fii-
the liquid and solid phases. and operative mechanisms of bioactiv- tration; the driving force is a pressure
Mathematical models incorporating ity on the surfaces of adsorbents. Al- gradient across a relatively thin barrier
the hetic and thermodynamic charac- most unliited possibilities exist for of lited porosity, and the predomi-
teristics of a given adsorbent-solute synthesizing new resins having control- nant separation mechanism is selective
system can be used to predict the be- lable properties that can be used to sieving through fiiter barrier pores.
havior of the adsorption process and re- solve specific problems of organic con- The primary difference is that the pore
sulting phase distribution, and thus to tamination. Intermediate, or difunc- sizes of UF membranes are typically
function as bases for prescription of ad- tional, base exchangers and synthetic lo00 times smaller than those of ordi-

976 Envimn. Sci.Technol., Vol. 20, No. 10, 1986

 pulp and paper bleach plant effluents by
RO processes that use thin-fdm, non-
?ypkal applkatlon cellulosic, composite membranes (56).
Removal of priority organics from drinking wate The same kind of membrane has been
Mmary design conslderatlons and approach shown to provide high levels of rejec-
tion of mixtures of organic (phenolic
Pre/im/narvconsideretions
("a compounds) and inorganic material
r: Source.components: nature, concentration, and treatment objective; from coal gasification wastewaters
.i!! background substances may alter adsorption of target compounds; multiple (57).Recent work on the use of RO for
2; target compounds require prediction of competitive interactions
i*C a b n : optimum type and particle size for a plication treatment of industrial laundry waste-
:i6 Contact time: emotv-bed contact time lEBC8for orimarv adsomtion or waters has led to development of a
mass transfer zone-for each a n membrane made of inert polymeric ma-
Carbon use rate: replacement or terial that can reduce 1.0-10.0-mglL
process conditions and design concentrationsof chloroform, benzene,
perchloroethylene, and toluene to lev-
els that are suitable for discharge or re-
cycling (5s).
Laboratory research and field appli-
adsorption isotherm cations have demonstrated that mem-
brane processes can remove many
classes of organic compounds, includ-
ing macromolecular organics such as
humic and fulvic acids. For most mem-
branes, rejection of un-ionized organic
Liquid-phasemass balance: molecules increases with the decreasing
-v,- = --&- solubility and polarity of the solute.
a-
"A
at
"L
a
"-2 ai
V.
Undissociated low-molecular-weight
organic acids tend to be poorly -re-
v, is interstitialvelocity in direction (2) oftrow;t is time; & is the jected, whereas their salts are well re-
hydrodynamic dis rsion coefficient;p is the fluid density; c ISthe void
fraction of the 2 jected (6). Many chlorinated and or-
ganophosphoric pesticides are rejected
Wid-phase mass balance (homogeneous_surfaceditfusion model): at levels that exceed 98%; however, a
significant portion of their removal is
amibuted to adsorption onto the mem-
brane (54).
Prefreatment requirements for mem-
brane processes depend on the charac-
ary conditions include the film transfer term, k,: ter of the water or wastewater to be
a9/ar = (k,/D&)(C- C,) treated and on treatment objectives for
effluent quantity and quality. The con-
ventional water treatment sequence of
coagulation, sedimentation, and filtra-
tion often is adequate to remove excess
turbidity and suspended solids that
might otherwise clog membrane pores.
nary septum fdters (54). UF mem- molecular shape and flexibility, size, Membrane Sensitivity may require ad-
branes function best for separation of ionic charge, and solubility of a sub- justment of feed stream pH or tempera-
macromolecular organics of molecular stance as well as on the operating con- ture, although more tolerant mem-
weight >2ooO. ditions and kind of membrane used. branes are now bemg constructed. High
Reverse osmosis is a higher pressure Industry has led the way in develop ConCenvBtiolls of certain organic mate-
process in which the primary solute- ing and applying membrane processes rials can react with membrane polymer
solvent separation mechanism is related in water and wastewater treatment over matrixes to cause degradation or swell-
more to the osmotic diffusion proper- the past decade. RO can provide ing (59);pretreatment with GAC may
ties of molecules and to permselectivity enough organic and overall contami- be indicated in such situations. Low-
properties of the membrane than it is to nant removal by itself to meet the needs level chlorination often is used to in-
strictly pore-molecule dimensions. RO of production operations, such as semi- hibit excess biological growth on mem-
and UF membranes alike are produced conductor manufacturing, that require brane surfaces.
from synthetic polymers, such as cellu- high-purity water (55). Both UF and The issue of membrane fouling is
lose acetate and polyamide. RO mem- RO have been applied successfully in highly critical to UF and RO processes.
branes are continuous gels that reject the food and pharmaceutical industries The effectiveness of each process
even low-molecular-weight contami- for hctionation and recovery of pro- would be enhanced by the development
nants, whereas UF membranes are rel- teins, regulation and redudon of the of more foul-resistant membranes, the
atively porous materials more suitable alcohol content of beverages, concen- design of better membrane-cleaning
for rejecting larger molecules (54). Re- tration of process effluents, and purifi- procedures, and the optimization of
cent developments in composite mem- cation of drugs (6). The two processes pretreahnent. Additional development
branes have extended the range of UF also have been used for separation and might profitably focus on improving re-
separations to include many intermedi- recovery of organic dyes in textile op jection of low-molecular-weight organ-
ate and even low-molecular-weight or- erations. ics and on accommodating broader
ganic materials. The precise level of re- Organic removal exceeding 90% bas ranges of influent variables to minimize
jection depends on the concentration, been demonstrated for treatment of pretreatment requirements. There is

Emimn. Sci.Technol..M(. 20,NO. 10,1986 977

 substantial mom for improvement in
FiGURE 6 the predictive modeling of organics re-
Reverse osmosiS. moval as it is related to the concentn-
tion of dissolved organic contaminants
Influent Concentrate and the operating parameters of sys-

I Pressure vessel
t e m designed to remove complex mix-
tures of organics (50). Figure 6 is a
diagram of an RO process (54.53.
PelqKctive
Permeate
Physicochemical processes have un-
dergone decades of development for
Membrane section
application to the problem of organic
Circ
contanination of water. Oxidation tech-
niques offer a degree of flexibility in
1 High pressure A2 LOW pressure 1 tailoring treatment to a specific water
(Feedside) + -, i (Product side) or wastewater at a reasonable cost.
Chemical oxidation is usually most ef-
fective as a complementary rather than
as a self-sufficient process, however,
especially in wastewater applications,
and its use requires carelid consider-
ation of the chemical and biological in-
tegrity of effluent streams. The poten-
tial of air stripping and membrane
processes for removal of organic sub-
stances has not been fully r e a l i i , al-
though each has limited application.
Air stripping is practically confined to
treatment of VOCs, and although mem-
brane technology can remove a broad
range of organics and inorganics simul-
taneously, it is still relatively expensive
for most largescale applications. Even
Design and application feature though adsorption, particularly by
GAC, is the most thoroughly proven
technology for many organic pollution
problem, further design and system
refinements are desirable to make it
more economically attractive and oper-
Primary design considerations and approsc ationally practical.
Preliminary wnsideratrons It is evident that continuing effort
must be dedicated to the advancement
of treatment technologies for reducing
organic contaminant levels in aqueous
systems. Several specific needs have
been cited. Other less process specific
research and development needs in-
clude quantificationof relationshipsbe-
tween the structure. and solution charac-
teristics of organics and their extent of
removal by different unit processes; de-
velopment of rapid, low-cost organic
contamination monitoring techniques to
be used before and during treatment;
Ju and J. are fluxes of water and s and evolution of improved decision-
making tools for achieving the best bal-
ance between the extent and cost of
treatment.
In broader perspective, more inte-
grated approaches to the evaluation and
design of treatment facilities for partic-
ular applications that involve optimiz-
ing unit processes in the context of
overall plant performance are required.
This is the case for municipal treatment
systems, which can benefit from the
Souren: RBfemnW 54 (EM) and 57 numerous industrial applications of
0 l $63, American Inmuteof Chem such approaches.
Finally, given the complex nature of

978 Envimn. Sci. Technol., bl.20, NO. I O , 1986

the organic contamination problem and I. S., Eds.; American Sociely ofcivil Engi- (43) Schultz. 1. R.; Kcinath, T.M. Water Sci,
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Envimn. S i . Technol.. MI.20, No. 10. 1986 979