ES8cT

Subsurface transport of
contaminants
Mobile colloids in the subsurface environment
may alter the transport of contaminants
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John F. McCarthy ability to predict the velocity at which Many contaminants readily sorb to
Oak Ridge National Laboratory contaminants move through the vadose immobile aquifer media and therefore
(unsaturated) and saturated zones. are considered to be virtually immobile
'

Oak Ridge. TN 37831-6036

However, attempts to describe and pre- in the subsurface and to present little
John M. Zachara dict contaminant transport cannot suc- danger to groundwater supplies. For
Battelle Pacific Northwest Laboratory ceed if major pathways and mecha- example, in soil and aquifer material,
Richland. WA 99352 nisms for transport are not defined. many metals and radionuclides bind
Most approaches to describing and strongly to mineral components; fur-
predicting the movement of contami- thermore, many nonpolar organic con-
nants treat groundwater as a two-phase taminants tend to bind to particulate or-
Contaminants originating from human system in which contaminants partition ganic matter. Colloids in the solid
activities have entered the subsurface between immobile solid constituents phase, however, also may be mobile in
environment through waste disposal and the mobile aqueous phase. Con- subsurface environments. Because the
practices, spills, and land application of taminants that are sparingly soluble in composition of colloids is expected to
chemicals. The establishment of effec- water and that have a strong tendency be chemically similar to that of the sur-
tive disposal and isolation procedures to bind to aquifer media are assumed to faces of immobile aquifer material,
for chemical wastes, the protection of be retarded (to move much more slowly these particles also could sorb organic
public health, and the amelioration of than the rate at which groundwater and inorganic contaminants and stabi-
subsurface contamination rely on the flows) (Figure la). lize them in the mobile phase. The col-

496 Environ. Sci. Technol., Vol. 23, No. 5, 1989 0013-936X/89/0923-0496$01.50/0 © 1989 American Chemical Society
loids act as a third phase that can in- tion of colloids, especially Fe(IlI)-
crease the amount of contaminant that FIGURE 1
oxides (4, J); the rapid pumping of a
the flow of groundwater can transport Contaminant movement well can force otherwise immobile aq-
(see Figure lb). in groundwater uifer solids into the well or can disrupt
This article calls attention to the po- fragile colloidal aggregates (6, 7).
(a) Two-phase system
tentially critical but poorly understood Clearly, the issue of proper sampling
role of colloids in facilitating contami- protocols is central to progress in eval-
nant transport. Failure to account for uating the role of colloids in contami-
this mode of transport can lead to seri- nant transport. Critical evaluation of
ous underestimates of the distances that (groundwater) |[ the occurrence, composition, nature,
contaminants will migrate. For exam- and abundance of subsurface colloids
ple, at a Defense Programs site at Los requires testing and validation of sam-
Alamos National Laboratory, pluto- pling methodologies that correctly sam-
nium and americium disposed of at a ple mobile material in groundwater so
liquid seepage site migrated up to 30 m (b) Three-phase system that suspended colloidal particles are
(/); predictions that were based on lab- included but immobile particles are ex-
oratory measurements of radionuclide cluded.
binding to immobile subsurface materi-
als and that ignored colloids forecast Colloidal material in groundwater
that migration would be limited to a The occurrence of colloids in
few millimeters. At another site at Los groundwater should not be surprising;
Alamos, not only were plutonium and colloidal-sized substances are known to
americium detected in monitoring wells be associated with geologic matrices.
over a mile from a liquid waste outfall, Coarse-grained aquifer material can
but the transported radionuclides were contain up to 5% clay-sized materials
shown by ultrafiltration to be present as (<2 /im) that may be detrital (con-
colloids (0.025 to 0.45 /on in diameter) tained in the original parent geologic
(2). material) or authigenic (formed in situ
Colloids are particles with diameters through geochemical alteration of pri-
less than 10 /an (Figure 2) (3). A vari- mary mineral solids in groundwater
ety of organic and inorganic materials •Particulate organic matter zones). Detrital colloidal material can
exist as colloids in groundwater, includ- be diverse in nature and is a function of
ing macromolecular components of the depositional environment as well as
“dissolved” organic carbon (DOC) of the mineralogic composition of the
such as humic substances, “biocol- original source geologic material.
loids” such as microorganisms, mi- Sampling difficulties Various layer silicates, as well as iron
croemulsions of nonaqueous phase liq- Existing information is sufficient to and aluminum oxides, can be detrital in
uids, mineral precipitates and raise concernsabout the potential effect subsurface sediments. Authigenic col-
weathering products, precipitates of of colloids the mobility of ground-
on loidal-sized particles composed of sec-
transuranic elements such as pluto- water contaminants. Nevertheless, cur- ondary hydrous oxides, aluminosili-
nium, and rock and mineral fragments. rent approaches to monitoring and pre- cates, and silica, as well as complex
In this article, colloidal materials sus- dicting contaminant transport generally mixtures and solid solutions of these
pended in water are referred to as parti- ignore colloid-facilitated transport phases, also form on the surfaces of
cles; the term media or matrix refers to mechanisms because little, if any, infor- larger mineral grains as a result of the
the fixed bed of porous or fractured mation is available on the abundance alteration of thermodynamically unsta-
subsurface material through which a and identity of colloids in groundwater, ble primary minerals. Other solids such
solution may flow. their tendency to bind contaminants, or as calcite and iron sulfide have been
We will discuss the genesis and stabi- their mobility in subsurface systems. observed to form directly as a result of
lization of groundwater colloids and the Our understanding of the subsurface downgradient changes in groundwater
chemical and hydrologic factors con- environment is limited by the tech- hydrochemistry. Surface analyses of
trolling their transport through porous niques we use to characterize it, and sediments typically show various col-
media; we also will assess the evidence nowhere in geochemistry is this more loidal-sized secondary precipitates
that contaminants bind to mobile col- evident than in the study of subsurface coating larger grains.
loids in groundwater. We then will re- colloids. The presence of a clay-sized fraction
view the status of current capabilities to Drilling redistributes material, cre- in many aquifer materials suggests that
incorporate the facilitated transport by ates fine particles, introduces materials the colloidal fraction is not intrinsically
colloids into predictive hydrogeo- (drilling muds, for example) into the mobile. Indeed, the isolation of clay-
chemical models as well as the potential borehole, and provides a conduit for air sized materials from subsurface sedi-
application of colloid mobilization and to contact groundwater. Sampling pro- ments often requires the use of ultra-
deposition to waste management strate- cedures also can introduce artifacts, in- sonic or chemical dispersion because
gies. Finally, we identify research that cluding the removal of existing col- the fines are aggregated or are bound to
is needed to understand and predict the loids, the creation of colloids during larger particles by cementing agents or
role of colloids in the subsurface trans- sampling, or changes in the chemical electrostatic forces. Typical cementing
port of contaminants. First of all, how- and physical properties of the natural agents include iron oxides, carbonates,
ever, it is important to call attention to colloids because of alterations in oxy- and silica. Stable aggregates of layer
the critical caveat in research on gen and carbon dioxide (CO2) content, silicates are promoted by saturation
groundwater colloids: Are colloids in temperature, pH, Eh (redox potential), with divalent ions, such as Ca2+, that
water recovered from a well bore rep- and light as the groundwater is brought coagulate single crystallites.
resentative of those present within the to the surface. For example, introduc- A first but essentia] step in the gene-
porous media? tion of oxygen can lead to the produc- sis of mobile colloids in groundwater is

Environ. Sci. Technol., Vol. 23, No. 5, 1989 497

 neath a sewage infiltration basin (8).
FIGURE 2 Also, iron oxide colloids have been ob-
Size spectrum of waterborne particles served to precipitate in groundwaters as
Diameter (m) a result of both pH changes and oxy-
genation (9). Moreover, certain
10'1° 10'9 10‘8 to'7 i°-6 10'5 10'4 10’3 to-2 strongly hydrolyzing radionuclides
I—...... <-1- I
1
! t
I
form colloids whose particles are nano-
1 1/tm 1 mm meter-sized (10).
Molecules
1

i i 1

Colloids _i i i 1 Colloidal materials also can be re-

leased to groundwater as a result of
1

e.g., Clays Suspended particles

FeOOH l II
geochemical and biologic processes
Si02 Bacteria acting upon larger inorganic or organic
CaC03 Algae I
particulate materials in the aquifer ma-
I i i 1 trix. Organic macromolecules such as
Viruses
”"'1
I
1
1

1
1

1
1

1
humic substances can be made soluble
1

1
1
>

1
1
from kerogen, bitumen, or lignitic ma-
Source: Reference 3 1 1

terials in the aquifer matrix as a result

of microbial activity and abiotic hydrol-
ysis. Silica colloids are released during
the diagenesis of amorphous silica.
Similarly, radionuclide-bearing silica
colloids are released from vitrified
waste under simulated groundwater
leaching conditions (II). Bacteria at-
tached to aquifer solids may secrete
various exocellular materials or release
cell fragments to groundwater.
In addition, colloids can be released
to groundwater if inorganic cementing
agents that bind colloidal-sized materi-
als to larger mineral grains dissolve or
if stable aggregates are deflocculated.
The reductive dissolution of iron oxide
cements appears to be a mechanism by
which colloids can be mobilized in nat-
ural waters or in contaminant plumes
containing levels of DOC high enough
to promote microbial activity and an-
oxic conditions. The dissolution of iron
oxides in oxide-cemented sand under
anoxic conditions liberates layer silicate
clays previously bound to the aquifer
matrix (7). Similarly, siliceous colloidal
material is released into groundwater in
a calcareous environment because infil-
tration of waters of different composi-
tion dissolve carbonate cements (12).
Attached subsurface bacteria may be-
come unattached under high nutrient
and carbon concentrations associated
the formation of a colloid suspension in pressures) or from contaminant infiltra- with contaminant plumes. Colloidal
the pore water (Figure 3). This step can tion. Geochemical gradients are com- material also may be mobilized through
involve a number of mechanisms in- mon between contaminant plumes and disaggregation if the ionic strength of
cluding the homogeneous nucleation of associated uncontaminated groundwat- the groundwater is decreased or if the
inorganic solids in the fluid phase, the ers because plumes often are of differ- ion balance is shifted from one domi-
release of colloidal material from the ent pH, DOC concentration, and inor- nated by Ca2+ to one dominated by
geologic matrix, and the translocation ganic ion composition. Na+. Permeability reductions in sub-
of inorganic and organic substances The precipitates that form can con- surface sediments and sandstones that
from the vadose or recharge zone. tain both major ions (hydrous oxides of accompany groundwater electrolyte
Colloidal-sized precipitates can form iron and manganese, calcium carbon- changes have been ascribed to mobili-
in the aqueous phase if gradients in ates, iron sulfides) and minor ions zation of colloids.
geochemical parameters such as (metal and radionuclide oxides, hy- Colloids also can be moved to
groundwater pH, ion composition, re- droxides, carbonates, and sulfides) in groundwater from the vadose or root
dox potential, or CO2 partial pressure groundwater. Homogeneous precipita- zone (Figure 4). Humic substances can
induce supersaturation with respect to tion initially can yield large molecular be flushed from upper, organic-rich soil
readily precipitable solid phases. Such clusters and colloidal-sized precipitates horizons to the vadose and saturated
gradients may result either from natural that are suspended in the groundwater. zones during storms and major periods
geochemical processes (including mi- As examples, Gschwend and Reynolds of infiltration such as snowmelt (13).
crobiological activity that can reduce observed the precipitation of ferrous Significant bacterial populations (104—
redox potential or influence CO2 partial phosphate solids in groundwater be- 107 microorganisms/g) have been

498 Environ. Sci. Technol., Vol. 23, No. 5, 1989

found in groundwater zones (14), and
their origin has, in part, been ascribed FIGURE 4
to migration from the upper soil zone. Colloid transport through the vadose zone
Although humic substances and mi-
crobes can adsorb to mineral surfaces,
their movement to a given depth appar-
ently is facilitated by transport through
preferential flow paths in porous media
such as macropores and cracks associ-
ated with soil structure (15, 16). Layer
silicate clays also can be mobilized
from the soil zone by large storm
events that lead to the infiltration of low
ionic strength meteoric waters. The ar-
tificial recharge of groundwater by ap-
plication of water to soils can lead to
turbidity in groundwater and permea-
bility reductions in soil, exacerbating
the effects of mobilization of colloidal-
sized materia] (17).

Stabilization and filtration

The preceding discussion has shown
how colloidal-sized material may be re-
leased from, transported to, or formed
in groundwater. To be mobile over sig-
nificant lateral distances and thus facili-
tate contaminant transport, suspended
colloidal material must be stable (resist-
ing aggregation with other like parti-
cles) and must not be susceptible to par-
ticle filtration in passing through
porous media (Figure 3). Whether a
particle will be stable, aggregated, fil-
tered, or will settle in groundwater de-
pends on a complex combination of
density, size, the surface chemistry, the
water chemistry, and the water flow
rates. The complicated interdepen-
dency of these factors makes it difficult
to predict particle behavior, based on
current understanding and models;
however, general concepts are well es-
tablished for assessing these interac-
tions qualitatively.
According to the theory of Derja-
guin, Landau, Verwey, and Overbeek
(the DLVO theory), the stability of a
homogeneous colloidal suspension is thickness, and divalent ions coagulate tion behavior of layer silicate clays is
determined by van der Waals attractive colloids at much lower aqueous con- complicated because the edges and
forces that promote aggregation and by centrations than do monovalent ions faces of the crystallites may carry op-
electrostatic repulsive forces that drive (Schulze-Hardy rule). posite charge, giving rise to premature
particles apart. When electrostatic re- Sorbable species (alkali earth cat- aggregation through edge-to-face asso-
pulsions are dominant, the particles are ions, hydrolyzable metals such as Fe3+, ciation.
electrostatically stabilized and remain and weak acid anions) and natural poly- The destabilization of suspended col-
in a dispersed state. Colloid stabiliza- electrolytes such as humic substances loids in groundwater as a result of fac-
tion therefore is influenced by particle form surface complexes on colloidal tors such as increasing ionic strength or
mineralogy and surface chemistry, by material and influence net particle equivalent fraction of Ca2+ over Na+,
other chemical factors controlling sur- charge and stability. Strongly sorbing or through strong ion adsorption, does
face charge, and by the extent of the species may destabilize colloids at low not necessarily mean that they will be
electrical double layer (18, 19). These concentrations and restabilize them at rendered immediately immobile. Coag-
chemical factors are summarized in Ta- higher concentrations as their sorption ulation kinetics are complex, and elec-
ble 1. induces charge reversal and an increase trostatic interactions that occur during
Particles are stabilized when their in <jp. Indeed, even under chemical con- particle collisions are not well under-
double layers are expanded (by de- ditions that should promote stability, stood (20). These interactions are a
creasing electrolyte concentration and coagulation of colloids in groundwater function of many variables, including
ionic strength) and when the net parti- may occur if the surface charges on the particle concentration, particle size,
cle charge (ap) does not equal zero. The suspended colloids are heterogeneous and particle size distribution, all of
converse promotes coagulation. Coun- and permit interparticle electrostatic in- which can influence the extent of parti-
terion valence controls double-layer teractions. For example, the coagula- cle-particle collisions in the ground-

Environ. Sci. Technol., Vol. 23, No. 5,1989 499

water. Moreover, destabilized colloids tial flow paths with high relative veloc- studies of colloidal material in surface
in groundwater still may be transported ity. Thus, Harvey et al. (22) found that waters; very few data are available for
as aggregates if the aggregates are suffi- larger microspheres were transported colloids isolated from groundwater.
ciently small with respect to the pore greater distances than were smaller Humic substances from surface wa-
diameters. ones in a permeable sand aquifer and ter or soil bind hydrophobic organic
Even if hydrochemistry promotes suggested that the larger spheres expe- contaminants, enhance the pollutant’s
their stability, suspended colloids can rienced fewer diffusion-induced parti- apparent solubility in water, and reduce
be mobile only if they are not filtered cle-surface collisions that could lead to its apparent affinity for binding to sedi-
by porous media. Particle filtration in attachment or collection (20). Microor- ment particles and to reverse-phase
groundwater can occur by physical ganisms and organic macromolecules chromatographic columns and soil col-
straining or by physical-chemical col- are transported through aquifers and in- umns (28). Biopoly meric material aris-
lection by attractive surfaces on the im- tact soil cores more rapidly than chemi- ing from microbial cell lysis and
mobile matrix. Straining filtration is cal tracers are because their movement fragmentation also sorb hydrophobic
controlled by the pore dimensions and is limited to channels and to the second- contaminants (29). The polyelectrolytic
geometry relative to the colloid particle ary pore structure rather than extending character of humic and fulvic acids en-
size. Straining filtration may be of sec- through the intergranular pore space ables them to associate with metal ions.
ondary importance to physical-chemi- (22-24). Laboratory and field studies have dem-
cal collection for most groundwater Theoretical considerations aside, onstrated the significance of humics to
colloids because their size is suffi- the speciation of metals (30) and radio-
ciently small (typically 1 /tm or less) to nuclides (31). Humic and fulvic acids
permit them to move unimpeded from soil and sediment bind actinides
through the large pore spaces of sandy strongly (32), and colloidal organic
aquifers (27). Straining filtration can be matter from lakes also binds radionu-
important for bacteria, which are often clides and inhibits their adsorption to
bigger than abiotic colloids (Figure 1). sediments (57). Moreover, metals bind
Filtration by physical-chemical col- to functional groups on the cell surface
lection is controlled by electrostatic, of biological particles (55).
chemical, or van der Waals forces. In other studies, inorganic particles
These phenomena are similar to those identified as mobile colloids in ground-
described for particle-particle interac- water have been shown to strongly ad-
tions, except that the colloidal particles sorb contaminants. Layer silicate clays
associate not with other particles but adsorb metallic and organic cations by
with the mineral or organic components ion exchange (34). Surfaces of iron,
of the immobile aquifer media. Collec- manganese, aluminum, and silicon ox-
tion of colloids is favored on surfaces ide particles strongly adsorb certain
of opposite charge. Negatively charged metallic cations and organic and inor-
colloids are expected to be more mobile there is ample evidence that colloidal- ganic acid anions (55). Metals and or-
than positively charged ones because sized particles can move in aquifers. ganic acids may adsorb to the surface of
most groundwater matrices carry a net Bacteria have been reported to migrate calcium carbonate by complexation or
negative charge. Mobile groundwater up to 920 m and viruses up to 900 m exchange with structural ions (36). The
colloids that have been observed to (75). Asbestos fibers have been de- humate coatings that mobilize layer sili-
carry a negative charge include organic tected in an aquifer recharged from a cate clays and oxide colloids alter their
macromolecules, layer silicates, silica- reservoir containing high levels of fi- surface properties, making them more
rich particles, bacteria, and iron ox- bers (25). Layer silicate clays mobi- or less reactive with contaminant ions
ides. lized from surface soils have been (37).
The adsorption of humic substances found to account for turbidity observed Contaminant binding to all of the
can impart a negative surface charge to in wells several hundred meters distant substrates noted above is influenced to
colloids such as oxides, layer silicates, from the recharge site (17). Humic sub- varying degrees by other solutes that
and calcium carbonate with positively stances can migrate rapidly in some may compete for common adsorption
charged surface sites, thereby increas- aquifers. The migration of colloidal- sites on the colloid surface. The impor-
ing the stability and mobility of these sized tannin and lignin (molecular tance of these colloids in facilitating
particles. The adsorption of silica on weight > 2000 daltons) from a waste contaminant transport in groundwater
iron and aluminum oxides may achieve pulp liquor migrated through a sand aq- depends on the colloid surface area, the
a similar effect. Ryan (7) postulated uifer at the same rate as the ground- number of reactive sites pier unit of sur-
that coatings of adsorbed humic sub- ,
water flow (26). Rapid movement of face, the preconditioning of surfaces by
stances develop a negative charge on both layer silicate clays and organic strongly bound cosorbates, and the
mobile layer silicate and iron oxide col- matter through the vadose zone also has strength of the contaminant-surface re-
loids in anoxic Atlantic coastal plain been observed (16, 27). action. Unfortunately, few data of this
groundwaters. Nevertheless, colloidal type exist for groundwater colloids.
material also may be collected by sur- Colloids and contaminant transport In some instances, the association of
faces of like net charge because hetero- If organic and inorganic colloids are contaminants with colloidal material
geneous surface domains can exist with present and mobile in groundwater, can has been demonstrated in groundwater.
opposite charge where attractive forces they facilitate the transport of contami- Both transition element (manganese,
exceed repulsive forces. nants? Knowledge of the chemical cobalt) and lanthanide (cerium, euro-
Stable colloids in groundwater can be mechanisms of contaminant-colloid in- pium) radionuclides have been associ-
mobile even under conditions that favor teractions and our ability to predict the ated with inorganic colloids in ground-
physical-chemical collection if particle extent of the association vary widely water outside a nuclear detonation
surface collisions are minimized by depending on the nature of the contami- cavity at the Nevada Test Site (38). In
slow interpore transport rates or if wa- nant and the colloid. Furthermore, groundwater several hundred meters
ter movement occurs through preferen- much of the information is drawn from downgradient from a uranium ore de-

500 Environ. Sci. Technol., Vol. 23, No. 5, 1989

posit in Australia, uranium and daugh- not appropriate for most inorganic sol- Even more daunting, however, are
ter species such as thorium were found utes because their sorption is nonlinear. the difficulties in predicting preferential
to be sorbed to iron- and silicon-rich Moreover, geochemical gradients in flow paths. These field-scale features
colloidal particles between 0.018 jxm pH, redox potential, and major ion are difficult to characterize and cannot
and 1 fim in size (5). composition (conditions favoring col- be adequately simulated at a laboratory
Radioactive cobalt and uranium have loid mobilization) are likely to cause scale. Because of the size and surface
been associated with high molecular major changes in the Kj between reac- charge that may promote filtration, col-
weight organic material in groundwater tive solutes and both the aquifer matrix loid transport may be strongly influ-
near a disposal trench at the Oak Ridge and the mobile colloids. More appro- enced by preferential paths such as
National Laboratory (39). Likewise, priately, colloidal material may be fractures, and these features need to be
radionuclides in groundwater of four treated as a reactive component or lig- incorporated into models directly or
contaminant plumes at the Chalk River and of the fluid phase. Mass action stochastically.
Nuclear Laboratory in Canada were equations may be written between sol-
found to be associated with anionic or- utes (including contaminants and major Applications to hazardous wastes
ganic ligands in the 500-10,000-dalton ions) and colloids akin to those of aque- The emphasis of this article has been
molecular weight range (40). A number ous and surface complexation (35), but on the potential role of colloids in en-
of other studies have demonstrated that this requires information on the con- hancing the mobility of contaminants.
colloidal material isolated from ground- centration of colloid surface sites and The manipulation of colloid mobiliza-
water is capable of sorbing organic and equilibrium constants for surface com- tion and deposition, however, could be
inorganic contaminants (41). Further- plexes. These approaches are compati- a useful tool for the mitigation or reme-
more, insoluble metals and radionu- ble with reaction-based surface com- diation of waste sites. For example, if
clides may themselves form colloidal- plexation models (35) and geochemical aquifer remediation is a goal, then re-
sized precipitates which may be mobile transport codes (42). Other modeling moval of highly adsorbed contaminants
(8. 10). approaches may be required if organic from groundwater could be enhanced
groundwater colloids, like humic sub- by the controlled mobilization, collec-
a predictive capability
Developing stances, exhibit significant heterogene- tion, and treatment of colloids from the
Currently, scientific understanding is ities in surface properties and reactivity affected groundwater zone. Colloid
not adequate to identify, a priori, the toward inorganic ions. mobilization may affect aquifer perme-
groundwater zones in which colloids Calculations of colloid-facilitated ability, however, and the benefits of
may exist and be important to contami- transport are hampered by an inability contaminant solubilization versus pore
nant migration. More observations are to predict physicochemical dynamics of clogging must be carefully assessed. In
needed on suspended colloids in differ- colloids in the groundwater zone. Sur- many cases, the removal of existing
ent groundwaters before the combined face complexation models and diffuse contaminants is not necessary or desir-
influence of groundwater chemistry, able. Effective waste management may
porous media lithology, and hydrology require only that the migration of
on colloid occurrence and behavior can colloid-associated contaminants be con-
be generalized to the predictive level. tained within the boundaries of a con-
From what is understood, it appears trolled waste facility. It may be suffic-
that the colloid-mediated transport of ient simply to limit the magnitude of
contaminants may be important if this factor by treatments that promote
• contaminants associate strongly with deposition of colloids.
particles (e.g., metals, radionuclides, Therefore, an improved understand-
and hydrophobic organic com- ing of the mobilization and deposition
pounds); of colloids in groundwater may be ap-
• DOC levels are relatively high; plied not only to solving problems of
• aquifers are porous or fractured and colloid-facilitated contaminant trans-
flow rates are relatively high; or port, but to developing strategies for
• aqueous chemistry is dominated by the in situ isolation or remediation of
sodium or undergoes natural or con- hazardous wastes.
taminant-associated alterations that
would produce or mobilize colloids. double layer models have been used to Research needs
The effects of mobile colloids on interpret coagulation phenomena of The weakness of current predictive
contaminant migration cannot be pre- simple solute-solid combinations under capabilities highlights the inadequacy
dicted accurately with current models; static conditions. Although appropriate of our understanding of mechanisms
several approaches, however, offer theory exists (18, 19), existing models controlling the transport of highly re-
promise. Empirically, the colloid inter- do not predict coagulation under condi- tarded contaminants. Existing data sug-
action can be factored into a distribu- tions relevant to groundwater. Calcula- gest that mobile colloidal particles may
tion coefficient (K^) between the mobile tions from filtration models deviate be important mechanisms of contami-
and immobile phase, thus decreasing from observations when electrostatic nant transport through the vadose zone
the retardation factor. This approach is effects predominate, especially when and within the saturated zone. How-
appropriate for many hydrophobic con- colloids and porous media have a like ever, this information is largely anec-
taminants that exhibit linear partition- charge (20). Filtration models have not dotal and is inadequate either to evalu-
ing and the absence of competitive been applied to groundwaters in which ate the general significance of the
sorption with other like solutes. An the water flows slowly and horizontally phenomena or to develop a capability to
advection-dispersion model has been rather than vertically. Clearly, the com- include colloid-facilitated transport in
developed that incorporates a mobile plexity of particle-particle and parti- computer models that predict contami-
organic macromolecule and exhibits cle-media interactions is a significant nant migration in the subsurface. Fu-
linear adsorption behavior for hydro- challenge in developing a capability to ture research must address a number of
phobic organic contaminants (24). predict the effect of mobile colloids on issues related to the occurrence and
A constant Kj approach, however, is contaminant transport. mobility of subsurface colloids and

Environ. Sci. Technol., Vol. 23. No. 5. 1989 501

 ciety: Washington, DC, 1989; pp. HI-
SS.
Key questions that require research (43) (29) Bell, J. B.; Terzos, M. Water Res. 1988,
22, 917-26.
Occurrence and properties of subsurface colloids (30) Perdue, E. M. In Aquatic Humic Sub-
• Are colloids stances: Influence on Fate and Treatment
present in groundwater? If so, why, and how do we sample them
without introducing artifacts? of Pollutants; Suffet, I. H.; MacCarthy,
P., Eds.; Advances in Chemistry Series
• Can the
presence of stable colloids be understood and predicted based on 219; American Chemical Society: Wash-
the mineralogy and hydrochemistry of specific subsurface environments? ington, DC, 1989; pp. 281-96.
• What is the composition, physicochemical nature, and abundance of colloidal (31) Nelson, D. M. et al. Environ. Sci. Tech-
nol. 1985, 19, 127-31.
particles in subsurface environments? (32) Nash, K. L.; Choppin, G. R. J. Inorg.
Nucl. Chem. 1980, 42, 1045-50.
Mobility of subsurface colloids (33) Xue, H. B.; Stumm, W. Water Res. 1988,
• Do colloids move through aquifers? 22, 917-26.
• Can the chemical and hydrologic factors controlling the stabilization, (34) Maes, A.; Gremero, A. In Geochemical
Processes at Mineral Surfaces; Davis,
transport, and deposition of colloidal particles be described and incorporated J. A.; Hayes, K. F., Eds.; ACS Sympo-
in predictive transport models? sium Series 323; American Chemical So-
Implications for contaminant transport ciety: Washington, DC, 1986; pp. 254-
95.
• Do mobile colloids sorb and transport contaminants?
(35) Sposito, G. The Surface Chemistry of
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The authors are supported by the Subsur- in Groundwater Due to Infiltration of Wa- (43) McCarthy, J. F. “Role of Colloidal Parti-
cles in the Subsurface Transport of Con-
face Science Program of the Ecological ter Near an Electric Generating Station,"
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Research Division, Office of Health and Energy Laboratory Report M1T-EL 88- for the Department of Energy Subsurface
Environmental Research, U.S. Depart- 004; Massachusetts Institute of Technol-
Science Program”; U.S. Department of
ment of Energy, under contract DE-AC05- ogy Energy Laboratory: Cambridge,
MA, 1988. Energy: Washington, DC, 1989; DOE/
840R21400 with Martin Marietta Energy ER-0384.
(13) Thurman, E. M. In Humic Substances in
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502 Environ. Sci. Technol., Vol. 23, No. 5, 1989