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74 g o ' K
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APPENDIX C
IMPORTANT FATE AND
TRANSPORT PROPERTIES OF
ENVIRONMENTAL CONTAMINANTS

C.l CONTAMINANT FATE AND TRANSPORT

IN THE ENVIRONMENT
i The existence of contaminated sites may result in the release of chemicals into air
(via volatilization and fugitive dust emissions), surface water (from surface runoff/
overland flow and groundwater seepage), groundwater (through infiltration/leaching),
soils (due to erosion - including fugitive dust generation/deposition and tracking),
sediments (from surface runoff/overland ilow), and biota (due to biological uptake and
I bioaccuniulation). Contaminants released into the environment are controlled by a
complex set of processes including transport, transformation, degradation and decay,
intermedia transfer, and biological uptake. In addition, many toxic chemicals are
persistent and undergo complex interactions in more than one environmental medium.
Environmental fate analyses can be used to assess the movement of chemicals between
environmental compartments.
The fate of chemical compounds released into the environment forms an impor-
tant basis for evaluating the exposure of biological receptors to hazardous chemicals.
Multimedia transport models are generally employed in the prediction of the long-term
I fate of such chemicals in the environment.

C.2 CONTAMINANT DISTRIBUTION BETWEEN

ENVIRONMENTAL COMPARTMENTS
I
Chemicals present in one environmental medium are affected by several complex
processes and phenomena, facilitating transfers into other media. The potential for
intermedia transfer of pollutants from the soil medium to other media is particularly
significant; in fact, contaminated soil can be a major source for the contamination of
groundwater, atmospheric air, subsurface soil gas, sediments, and surface water. For
example, chemical constituents having a moderate to high degree of mobility can leach
from soils into groundwater; volatile constituents may contribute to subsurface gas in
the vadose zone and also possible releases into the atmosphere. Conversely, the
potential for intermedia transport of constituents from other media into soils does
i exist; for example, chemical constituents may be transported to soils via atmospheric
deposition, and also through releases of subsurface gas.
 contaminants include hydraulic dispersion and molecular diffusion (which is caused
by the random Brownian motion of molecules in solution that occurs whether the
solution in the porous media is stationary or has an average motion). Furthermore, the
transport and concentration of the solute(s) are affected by reversible ion exchange
with soil grains, the chemical degeneration with other constituents, fluid compression
and expansion, and in the case of radioactive wastes by the radioactive decay.
Examination of a chemical’s physical and chemical propeities can often allow an
estimation of its environmental partitioning. Qualitative analysis of the fate of a
chemical can also be made by analogy with other chemicals whose fate properties are
well documented; that is, if the chemical under investigation is structurally similar to
a previously well-studied one, some parallels can be drawn to the environmental fate
of the analogue. In addition, several site characteristics inay influence the environmen-
tal fate of chemicals, including the amount of ambient moisture, humidity levels,
temperatures and wind speed, the geologic, hydrologic, pedologic and watershed
Biota (Fish) characteristics, topographic features of the site and vicinity, vegetative cover of site
and surrounding area, and land use characteristics. Several important properties affect-
Figure C.l contaminant partitioning between environmental compartments. ing environmental fate and/or intermedia transfers of environmental contaminants are
briefly annotated below. Further details, including elaboration of a variety of estima-
The affinity that contaminants have for soil affects their mobility by retarding tion methods for evaluating the important parameters, are elaborated elsewhere in the
transport. For instance, hydrophobic or cationic contaminants that are migrating in literature (e.g., Lyman et al., 1990; Swann and Eschenroeder, 1983).
solution ai-e subject to retardation effects. The hydrophobicity of a contaminant can
greatly affect its fate, which explains some of the different rates of contaminant Physical State
migration occurring in the subsurface environment. Also, the phenornenon of adsorp-
Lion is a major reason why the sediment zones of surface water bodiedsystems may
become highly contaminated with specific organic and inorganic chemicals. On the port of contaminated
other hand, a number of natural processes work to lessen or attenuate contaminant materials can act as significant release mechanisms.
concentrations in the environment; the mechanisms of natural attenuation include
dispersionidilutioii, ion exchange, precipitation, adsorption and absorption, filtration,
gaseous exchange, and biodegradation.
Water SolubiliQ
The solubility of a chemical in water is the maximum amount of the chemical chat
In general, the distribution of organic chemicals among environmental compart-
will dissolve in pure water at a specified temperature, usually expressed in terms of
nients can be defined in terms of the simple equilibrium expressions shown in
Figurc C. 1 (Swann and Eschenroeder, l983), where the K,, K,,, and BCF symbols weight per weight (e.g., ppb, ppm, mg/kg) or weight per volume (e.g., ppb, ppm, pg/L,
mg/L). Several different approaches to the estimation of water solubility are described
refer to partitioning coefficients that are elaborated in the next section. The general
in the literature (e.g., Lyman et al., 1990).
assumption is that all environmental compartments are well mixed to achieve equilib-
Solubility is an important factor affecting a chemical constituent’s release and
i - i u i i i between them.
subsequent migration and fate in the surface water and groundwater environments. In
The partitioning of inorganic cheinicals is somewhat different from organic
constituents. Typically, metals generally exhibit relatively low mob fact, among the various parameters affecting the fate and transport of organic chemi-
(Evans, 1989). Rather, the inorganics will tend to adsorb onto soils (which may cals in the environment, water solubility is one of the most important, especially with
become airborne or be transported by surface erosion) and sediments (that may be regards to hydrophilic compounds.
In general, highly soluble chemicals are easily and
transported i n watcr).
hydrologic system. Such chemicals tend to have relatively
for soils and sediments, and also relative1
biota. Furthermore, they tend to be
C.3 IMPORTANT FATE AND TRANSPORT PROPERTIES
AND PARAMETERS Diffhision arid Dispersion
As pollutants are released into various environmental media, several factors Diffusive processes create inass spreading due to molecular diffusion in response
contribute to their migration and transport. For instance, in the groundwater system, to concentration gradients. The higher the diffusivity, the more likely a chemical is to
the solutes i n the poro~ismedia will move with the mean velocity of the solvent by move in response to concentration gradients. Thus, diffusion coefficients are used to
advective niechanism; in addition, other mechanisms governing the spread of describe the movement of a molecule in a liquid or gas medium as a result of
 dil’lcrences i n concentration; it can also be used to calculate the dispersive component Vapor Pressure
o l chemical transport. Vapor pressure is the pressure exerted by a chemical vapor in equilibrium with its
Dispcrsive processes create mass mixing due to system heterogeneities (e.g., solid or liquid form at any given temperature. It is a relative measure of the volatility of
vclocity variations). Consequently, for example, as a pulse of contaminant plume a chemical in its pure state, and is an important determinant of the rate of volatilization.
iiiigraks Ihrough a soil system, tlie peaks i n concentration are decreased by spreading. It is used to calculate the rate of volatilization of a pure substance from a surface, or in
estimating a Henry’s law constant for chemicals with low water solubility.
Volatilizntioir In general, the higher the vapor pressure, the more likely a chemical exists in
Volatilization is the process by which a cheinical compound evaporates into the significant quantities in a gaseous state. Thus, constituents with high vapor pressure
\ q ~ o phase
r li.oni another environmental compartment. The volatilization of chenii- are more likely to migrate from soil and groundwater, to be transported in air.
cals is an iniportnnt mass-transfer phenomenon. Knowledge of volatilization rates is Numerous estimation procedures exist in the technical literature (e.g., Lyman et al.
iiccessary to determine the amount. o f chemical that enters the atmosphere and the 1990) for the estimation of this parameter.
change of pollutant concentrations in the source media. The transfer process froin the
sotircc (e.g., water body, sediments, soil) to the atmosphere is dependent on the Boiling Point (BP)
physical and chemical properties o f the chemical compound in question, the presence The boiling point is the temperature at which the vapor pressure of a liquid is
of other pollutants, the physical properties of tlie source media, and the atmospheric equal to the atmospheric pressure on the liquid. At this temperature, the substance
conditions. Volatility is indeed a very important parameter for hazard assessments. transforms from a liquid into a vapor phase. Besides being an indicator for the physical
Several estimation methods lor evaluating this parameter are elaborated in the litera- state of a chemical, the BP also provides an indication of its volatility. Other physical
ture (c.g., Lyman et al., 1990). properties, such as critical temperature and latent heat (or enthalpy) of vaporization,
may be predicted by use of its normal BP as an input.
HP///.V’S La\\’ coi7stni7t
Ilenry‘s law constant prov Water/Air Partition Coefficient ( K J
between air and water at equilib The water/air partition coefficient (K,) relates the distribution of a chemical
to volatilize froin aqueous solution to the atmosphere, based on the competition between water and air. It consists of an expression that represents the reciprocal of
hclwcen its vapor picssure and water solubility. This parameter is important in Henry’s law constant (H), given by:
dcteiinining the potential for intermedia transport into air. As an example of its
application, the concentlation i n soil gas is related to the concentration in an under-
lying aquiler by:

where:

C,, = concentration of the chemical in air ( m g k )

where: C,,,,, = concentration of the chemical in water ( m g k )

C, = concentration of the chemical in soil gas (mg/in’)

C,$ = coiiccntration of the chemical in groundwater (VEIL) OctnnolNater Partition CoefJicient (K,,,,)
H = Henry’s law constant (atm-m’/inol)
The octanol/water partition coefficient (Kow)is defined as the ratio o f a chemical’s
I< = gas constant (atin-ni3/mol K) concentration in the octanol phase (organic) to its concentration in the aqueous phase
T = teinperature (K) of a two-phase octanol/water system, represented by (Lyman et al. 1990):

Scvcral other forms of expressing H also exist in the technical literature (e.g., Lyman concentration in octanol phase
Kow =
et al. 1990). concentration in aqueous phase
Contaminants with low Henry’s law constant values will tend to favor the
; I C I L I ~ O L Iphase
S and will therefore volatilize to the atmosphere more slowly than This dimensionless parameter provides a measure of the extent of chemical partition-
’ constituents with high values. As a general guideline, for H values in the range of
I 0 to 1 O-i atm-iii3/inol volatilization is low, for H between lo-’ and lo-? atm-m3/inol
ing between water and octanol at equilibrium. It has become a particularly important
parameter in studies of the environmental fate of organic chemicals.
1 volatilization is not rapid but possibly significant, and for H >lo-? atrn-m3/mol KO, can be used to predict the magnitude of an organic constituent’s tendency to
i
j volatilization is rapid. The variation in H between chemicals is indeed extensive. partition between the aqueous and organic phases of a two-phase system, such as
 SLIIface water and aquatic Therefore, the sorptive capacity must be deteimined with reference to a particular
tendency of an organic co constituent and soil pair: The soil-water partition coefficient (K,) is generally used to
appreciable organic carbon quantify soil sorp[iori. It provides a soil- or sediment-specific measure of the extent of
to water solubility, soilkedi chemical partitioning betwecn soil or sediment and water, unadjusted for dependence
101 aquatic life. on organic carbon.
In general, chemicals with low K,," (<lo) values may be considered relatively The distribution of a chemical between water and adjoining soil or sediment may
hyclrophilic, wheieas those with high K,,, (> 104) values are very hydrophobic. Thus, indzed be described by an equilibriurn expression that relates the amount of chemical
thc gieatci the K,,,",
the more likely a chemical is to partition to octanol than to remain sorbed to soil or sediment to the amount in water at cquilibriuni. For inost environmen-
i n water. The hydrophilic chemicals tend to have high water solubilities, small soil or tal concentrations, the soiI/water distribution coefficient, K,, can be approximated by:
sediment adsorption coetiicients, and small bioaccumulation factors for aquatic life.
tIigh K,,,"valucs are genetally indicative of a chemical's ability to accumulate in fatty (concentration of adsorbed chemical in soil, C,)
[issues and therefore bioaccuniulate in the foodchain. It is also a key variable in the
estimation of skin permeability. Kd 'mL'gl = (concentration of chemical in solution in water, C,)

The Oiganic Cciiboii Adsorpti,on Coefficient (K(><) or

The sorption characteristics of a chemical may be normalized to obtain a sorption
conslant based on organic carbon which is essentially independent of any soil. The [(kg chemical per g soil)]
organic cat-bon adsorption coefficient (Koc) provides a measure of the extent of I Kd 'mL'gl = [(pg chemical per g water)]
partitioning of a chemical constituent between soil or sediment organic carbon and
water at equ i li bri uni . On this basis, K,describes the sorptive capacity of the soil and allows estimation of
K,,,is the ratio of the amount of constituent adsorbed per unit weight of organic
the concentration in one medium, given the concentration in the adjoining medium.
carbon i n the soil or sediment to the Concentration of the constituent in aqueous
For hydrophobic contaminants,
solution at equilibrium. Also called the organic carbon partition coefficient, KO, is a I
measui-e of the tendency for organics to be adsorbed by soil and sediment, and is
expressed by: Kd = f"CK",

where f,, is the fraction of organic carbon in the soil.

1-18chemicalabsorbed per g soil organic carbon
K3, [ mL/g] = K, is the ratio of the adsorbed contaminant concentration to the dissolved concen-
pg chemical dissolved per m L of water tration at equilibrium. The higher the value of K,, the less mobile is the contaminant;
this is because, for large values of K,, most of the chemical remains stationary and
The extent to which an organic constituent partitions between the solid and attached to soil particles due to the high degree o f sorption. Thus, the higher the K,
solution phases o f a saturated or unsaturated soil, or between runoff water and the more likely a chemical is to bind to soil or sediment than to remain in water.
scclinicnt, is determined by the physical and chemical properties of both the constituent

I and thc soil (or sediment). The K,,, is chemical-specific and largely independent of the
soil o r sediment properties. 'The tendency of a constituent to be adsorbed to soil,
Iiowever, is clependcnl on its properties and also on the organic carbon-content of the
Bioconcentration Factor (BCF}
The bioconcentration factor (BCF) is the ratio of the concentration of a chemical
constituent in an organism or whole body (e.g., a fish) or specific tissue (e.g., fat) to
soil or sediment. the concentration in water at equilibrium, given by:
When constituents have a high K,,,, they have a tendency to partition to the soil
or sediment. This value is a measure of the hydrophobicity of a chemical. The more
(concentration in biota)
highly sorbed, the more hydrophobic (or the less hydrophilic) a substance becomes. BCF =
Vnlucs of K,,, typically range from 1 to lo7; the higher the KO,, the more likely a (concentration in surrounding medium)
chemical is to bind to soil or sediment than to remain in water, Several estimation
mcthods for evaluating this parameter are elaborated in the technical literature (e.g., [(pg chemical per g biota,e.g.,fish)l
-
Lyman et al., I990). [(pg chemical per g medium,water)]

Soil- Water Pnrtitiori Coeflicierit (K[J The partitioning of a chemical between water and biota (fish) also gives a measure
The mobility of contaminants in soil depends not only on properties related to the of the hydrophobicity of the chemical. Ranges of BCFs for various constituents and
physical structure of t h e soil, but also on the extent to which the soil material will organisms can be used to predict the potential for bioaccumulation, and therefore to
I-etain, or adsorb, the chemical constituents. The extent to which a constituent is determine whether sampling of the biota is a necessary part of a site characterization
adsorbcd depends on the chemical properties of the constituent and of the soil. program.
 In f a c ~ ,the accumulation of chemicals in aquatic organisms is of increased Plzotolysis
concern as a significant source of environmental and health hazard. The BCF indicates Photolysis can be an important dissipative mechanism for specific chemical
the degree to which a chemical residue may accumulate in aquatic organisms, coin- constituents in the environment. Similar to biodegradation, photolysis (or
cident with ambient concentrations of the chemical in water; it is a measure of the photodegradation) may cause the ultimate fate of a constituent introduced into an
tendency o l a chemical i n water to accumulate in the tissue of an organism. The environmental system (e.g., surface water, soil, etc.) to be different from the constitu-
concentration of the chemical in the edible portion of the organism's tissue can be ent originally released. Hence, the photodegradation potential should be carefully
cstimated by multiplying the concentration of the chemical in surface water by the fish evaluated in designing sampling and analysis as well as monitoring programs.
BCF [oi-that chemical. Indeed. the BCF is an estimate ofthe bioaccumulation potential
Ibr biota in general, riot just for fish. Thus, the average concentration in fish or biota Clzemical Degradatiori (Hydrolysis and Oxida fion/Reduction)
is given by Similar to photodegradation and biodegradation, chemical degradation, primarily
through hydrolysis (i.e., a chemical transformation process i n which an organic
molecule reacts with water, forming a new carbon-oxygen bond and cleaving the
carbon bonding with the original molecule) and oxidation/reduction (redox) reactions,
wlicre C,,,:,,,, is the concentration in water. This parameter is indeed an important can also act to change chemical constituent species from what the parent compound
cletcrminnnt for human intake via ingestion of aquatic foods. used to be when it was first introduced to the environment. For instance, oxidation may
Values of BCF typically I-ange from I to over lo6. Constituents exhibiting a BCF occur as a result of chemical oxidants being formed during photochemical processes
greater than 1 .O are potentially bioaccumulative. Generally, constituents exhibiting a in natural waters. Similarly, reduction of constituents may take place in some surface
BCF greater than 100 cause the greatest concern (USEPA, 1987). Several estimation ! water environments (primarily those with low oxygen levels). Hydrolysis of organics
methods [or evaluating this parameter are elaborated i n the technical literature (e.g., ~ i s ~ t a l lresults
y in the introduction of a hydroxyl group (-OH) into a constituent
Lyman et nl., 1990). structure. Hydrated metal ions (particularly those with a valence 2 3 ) tend to form ions
in aqueous solution, thereby enhancing species solubility.
De~izlclatinii/Clierriical Half-Lives
Degradation, whether biological, physical, or chemical, is often reported in the Retardation Factor
literature as a half-life, which is usually measured in days. It is usually expressed as Retardation is the chemical-specific, dynamic process of adsorption to and de-
the time it takes lor one-half of a given quantity of a compound to be degraded. sorption from aquifer materials. In the assessment of the environmental fate and
Half-lives are used as measures of since they indicate how long a transport properties of chemical contaminants, reversible equilibrium and controlled
chemical will remain i n varioiis environ ia. Long half-lives (e.g., greater sorption may be simulated by the use of a retardation factor or coefficient.
than a month or a year) are characteristic of persistent constituents. Media-specific A retardation factor, R, can be calculated for a contaminant as a function of the
liall-lives provide a relative measure of the persistence of a chemical in a given chemical's organic carbon partition coefficient (KO'), and also the bulk density (p) and
medium, although actual values can vary greatly depending on site-specific condi- porosity (n) of the medium through which the contaminant is moving. Typically, retarda-
lions. For example. the absence of certain microorganisms at a site, or the number of tion factors are calculated for linear sorption in accordance with the following formula:
microo~ganisiiis,can influence the rate of biodegradation and, therefore, the half-life
lor specific compounds. As such, half-life values should be used only as a general
indication of a chemical's persistence in the environment (USEPA, 1987). In general,
Iiowevci-, the greater the half-life, the more persistent a chemical is likely to be. where K, = K,, x f,,, and f,, is the organic carbon fraction. Thus, the retardation
coefficient is reduced to the following relationship:
Uiocleg I-orlrrticiti.
Biodegradation is one 0 1 the most important environmental processes affecting R = [l + pK,f,#~]
the bt-cakclown of organic compounds. It results from the enzyme-catalyzed transfor-
m:itioii of organic constituents, primarily from microorganisms. The ultimate fate of In general, if a compound is strongly adsorbed then it also means this particular
21 constituent introdirced into several environinental systems (e.g., soil, water. etc.) compound will be highly retarded. In the aquifer system, the retardation factor gives
may bc any compound other than the parent compound that was originally released a measure of how fast a compound moves relative to groundwater (Nyer, 1993). For
into the environment. For example, trichloroethylene (TCE) biodegrades to produce example, a retardation factor of two indicates that the specific compound is traveling
1,2-clichloroetliyleiie ( I ,2-DCE), vinyl chloride, and other compounds; from a toxicity at one-half the groundwater flow rate. This will usually become a very important
viewpoint 1,Z-DCE is less toxic and vinyl chloride more toxic than TCE. parameter in the design of groundwater remediation systems.
Biological degradation may also initiate other chemical reactions such as oxygen
tlepletion i n microbial degradation processes, creating anaerobic conditions and the
Miscellnrieous Equilibriunz Caristarits Associated with Speciation
initiation of redox potential-related reactions. The biodegradation potential should
Equilibrium constants are important predictors of a compound's chemical state in
thcrel'ore be carefblly evaluated in the design of monitoring programs.
solution. For example, a constituent which i s dissociated (ionized) in solution will be
 more soluble and therefoi-e more likely to be released into the environment, and more 1

likely to migrate i n a surface water body. Many inorganic constituents, such as heavy
melals and mineral acids, can occur as different ionized species depending on pH.
Organic acids, such as the phenolic compounds, exhibit similar behavior. It should
also be noted that ionic metallic species present in the environment may have a
tcntleiicy to bind to particulate matter, if present in a surface water body, and to settle
out to the sediment over time and distance. In fact, heavy metals are removed in natural
attenuation by ion exchange reactions, whereas trace organics are removed primarily
1
hy adsorption. Metallic species also generally exhibit bioaccuniulative properties.
Typically, when metallic species are present in the environment, the sampling and
analysis of both sediment and biota would be a necessary part of a site characterization
o r rcmedial investigation effort.

REFERENCES
Evans, L.J. 1989. Chemistry of Metal Retention by Soils. Eiivirori. Sci. Teclzrzol., Vol. 23,
NO.9. 1017-56.
, Lyman, W.J., W.F. Reel11 and D.H. Rosenblatt. 1990. Haridbook of Chemical Properi'y
, Esliurcitiori Meiiiotls: ~iiiJir-orzri2eiitalBehavior of Orgniiic Compowicls. American
i Cheinical Society, Washington, D.C.
Nycr, E.K. 1993. Prnctical Techniqiles ,for Cro~iriclwatern r i d Soil Rernerliatiori. Lewis
Publishers, Boca Raton, FL.

1 Swatin, R.L. and A. Eschenroeder (Eds.). 1983. Fate of Chemicals in the Eizvirorznzent.
ACS Symp. Ser. 225, American Chemical Society, Washington, D.C.
USEPA. 1987. RCRA Facility Investigation (RFI) Guidance, EPA/530/SW-87/001. U.S.
Environmental Protection Agency, Washington, D.C.