w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/watres

Targeting treatment technologies to address specific

stormwater pollutants and numeric discharge limits

Shirley E. Clark a,*, Robert Pitt b

a
Penn State Harrisburg School of Science, Engineering and Technology, 777 W. Harrisburg Pike TL-105, Middletown, PA 17057, USA
b
University of Alabama, Department of Civil, Construction and Environmental Engineering, Tuscaloosa, AL 35487, USA

article info abstract

Article history: Stormwater treatment is entering a new phase with stormwater management systems
Received 21 July 2011 being required to meet specific numeric objectives, as opposed to the historic approach of
Received in revised form meeting guidance-document-provided percent removal rates. Meeting numeric discharge
7 March 2012 requirements will require designers to better understand and apply the physical, chemical,
Accepted 6 July 2012 and biological processes underpinning these treatment technologies. This critical review
Available online 20 July 2012 paper focuses on the potential unit treatment operations available for stormwater treat-
ment and outlines how to identify the most applicable treatment options based on the
Keywords: needed pollutant removal goals.
Stormwater runoff ª 2012 Elsevier Ltd. All rights reserved.
Stormwater chemistry
Treatability
Sedimentation
Filtration
Biological treatment systems

1. Introduction stormwater discharge quality increases, some regulatory

Stormwater runoff contributions to urban receiving water
degradation have been documented by many researchers over
the past four decades (Booth and Jackson, 1997; Stanfield and
Kilgour, 2006; Wenger et al., 2008). To prevent further degra-
dation and to potentially recover some ecological function-
ality, it is critical that new and re-developments urbanization
activities limit their discharges of stormwater-borne pollut-
ants and flows. In the U.S., these requirements are enforced
typically through National Pollutant Discharge Elimination
System (NPDES) permits and Total Maximum Daily Load
(TMDL) regulations. Historically, dischargers selected treat-
ment technologies from a guidance document based on listed
pollutant percent removals or that were the best practical
treatment option available. As the impetus to improve
agencies are pursuing numeric limits on stormwater pollut-
ants by specifying either effluent concentrations or docu-
mentable numeric load reductions. This critical review
focuses on the unit processes underlying common storm-
water treatment devices and how the properties of the
pollutants and unit processes can be exploited effectively.
Good stormwater design starts first with prevention of
excess runoff quantities and pollutant generation through
source control and other non-structural measures. Pitt and
Clark (2008) show how rethinking site design can be used to
reduce the hydrologic impacts of a site. However, even sites
designed following integrated stormwater management
principles have the potential to discharge contaminated
runoff. The selected treatment technologies must address
appropriately the site’s specific pollutants.

* Corresponding author. Tel.: þ1 717 948 6127.

E-mail addresses: seclark@psu.edu (S.E. Clark), rpitt@eng.ua.edu (R. Pitt).
0043-1354/$ e see front matter ª 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.watres.2012.07.009
6716 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
This paper does not address specifically the volume
reduction provided by some stormwater management prac-
tices, but addresses their pollutant treatability potential based
on an improved understanding of the physical, chemical and
biological properties of the pollutants and the control tech-
nologies. This paper is a critical review of the unit processes
available for treatment. Extensive control practice perfor-
mance data is available from several sources, most notably
from the International BMP Database (http://www.
bmpdatabase.org/, accessed 07/18/2011), where data from
several hundred studies of stormwater control practices are
presented, along with statistical evaluations of those data.
2. Characterizing stormwater runoff
The first steps in developing an approach to address specific
discharge objectives are to determine which pollutants can be
anticipated from the potential sources and at what concen-
trations. These pollutants may have been identified already
through monitoring or may be estimated based on land use
and historic monitoring from similar sites. For sites where
historical monitoring data are not available, runoff quality can
be estimated based on land use and geographical location
using the National Stormwater Quality Database (NSQD)
(http://rpitt.eng.ua.edu/Research/ms4/mainms4.shtml). The
NSQD data were collected during various sampling efforts,
primarily from Phase 1 NPDES MS4 (municipal separate storm
sewer system) stormwater permit holders, supplemented
with additional data from the Nationwide Urban Runoff
Program (NURP) (U.S. EPA, 1983), the International BMP Data-
base (www.bmpdatabase.org), and the U.S. Geological Survey
Urban-Stormwater Database (Smullen and Cave, 2002; Driver
et al., 1985). Analyses showed the main factors that affected
the runoff concentration were land use and geographical
location (Pitt and Maestre, 2005; Pitt et al., 2008b; Bochis and
Pitt, 2010). Pitt and Maestre (2005), using NPDES outfall
monitoring data from Phase I MS4 cities, noted the following
conclusions that are directly related to treatment selection:
 Substantial fractions of the pollutants at the outfall (50e75%
of most metals, for example) were particulate-associated.
 Critical source areas of urban runoff pollution include large
impervious areas, heavy vehicular traffic or areas with
many vehicular starts, and the outdoor use and/or storage of
problem pollutants, such as commonly occur in commercial
and industrial land uses.
 Other large areas, especially residential land uses, may
discharge large quantities of pollutants, but typically at
lower concentrations.
2.1. Particle size and pollutant association
Stormwater solids and other pollutants can be characterized
by their size (House et al., 1993; Li et al., 2005; Morquecho et al.,
2005; Kim and Sansalone, 2008), which affects their treat-
ability. In addition, some pollutants associate/react with the
solids, and their treatability is controlled first by the removal
of the associated solids. Table 1 is an example for
a southeastern U.S. city showing percent concentration
reductions after controlling for specific particle sizes
(Morquecho et al., 2005). Polycyclic Aromatic Hydrocarbons
(PAHs) also associate strongly with solids, especially organic
solids and those with large surface area to volume ratios. PAH
associations with solids generally increase as the molecular
weight and number of aromatic rings increases.
Once the anticipated runoff pollutants have been identi-
fied, appropriate treatment technologies can be selected and
designed. While this paper focuses on surface runoff concerns
and treatment, the potential for pollutant transport and
resultant water quality degradation also should be evaluated
for discharges to the subsurface (Pitt et al., 1996). Clark and Pitt
(2007) outline two levels of evaluation for estimating the
potential for groundwater contamination.
3. Separating pollutants from stormwater
runoff
Targeting treatment for specific stormwater pollutants, such
as dissolved metals and organics, requires an understanding
of both stormwater and treatment-technology science (Davis
et al., 2010; Clark and Pitt, 2011). The challenge is that most
of the stormwater literature does not address on a funda-
mental level the interaction of the treatment processes with
the stormwater pollutants based on the pollutants’ and runoff
water’s physical, chemical, and biological characteristics.
Important physical and chemical properties that form the
basis of treatment include the following: molecular size and
shape; density (pollutant and associated solids); Temperature
at phase change (melting and boiling points); volatility; solu-
bility (water and organic); and valence charge/polarity/surface
charge (especially relating to solids’ association).
This limited number of stormwater characteristics that can
be exploited as a basis for treatment result in a small list of
potential conventional and emerging treatment processes. For
practical use, though, the list shrinks again because storm-
water runoff has large and highly variable flow rates, large
volumes, relatively low concentrations, and large variabilities
in the biochemical characteristics, all of which affect treat-
ment effectiveness. The following sections describe the
treatment processes and the applicable physicalechemical
properties of the pollutants that can be exploited to enhance
treatment. Specific results from many additional studies,
published as part of a decade of annual literature reviews, are
in Clark et al. (2007).
3.1. Removal of solids plus particulate-associated
pollutants
Solids removal typically occurs through physical treatment
processes, with solids treatment efficiency being a function of
particle size, density, and shape. Pollutant removal requires
an association between the solid and the pollutant and is
affected by the solids removal efficiency.
3.1.1. Sedimentation
Sedimentation efficiency for discrete particle settling can be
predicted using Stokes’ Law (for laminar flow settling
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
Table 1 e Average pollutant percentage reduction in Tuscaloosa, AL Sheetflow samples after controlling for different
particle sizes (adapted from Morquecho et al. (2005)).
Percent pollutant reductions after removing all particulates greater than size shown
20 mm 5 mm
Suspended solids 76 81
Total-P 68 82
Nitrate 0 0
Cadmium 20 22
Copper 26 34
Lead 41 62
Zinc 64 70
conditions which occur for the small particles) and Newton’s
law (for turbulent settling conditions more associated with the
larger particles) and the surface overflow rate (SOR) of the
device (the discharge rate divided by the settling chamber’s
surface area), assuming ideal particle settling, e.g., spherical
particles and no interaction between settling particles. The
smallest particle with 100% sedimentation efficiency,
assuming discrete particle settling, is calculated by setting
SOR ¼ Vparticle (settling velocity of the critical particle size) and
using Stokes’ Law to calculate the particle diameter. Particles
whose settling velocities are less than the SOR will not
completely settle out before the water exits the device (Droste,
1996).
The sedimentation process is based on the density differ-
ences between the particles and the water, with many
stormwater solids having specific gravities of between 1.5 and
3.0 (Johnson et al., 2003; Li et al., 2006). Because of this large
density difference, sedimentation can be very effective for the
removal of relatively large particles and associated pollutants
from stormwater runoff. However, bacteria have a specific
gravity typically slightly above 1, which substantially reduces
the effectiveness of sedimentation as a primary control
measure (Harvey et al., 1996; Sharma et al., 1998). However,
bacterial agglomerations and attachment to particulates allow
a greater bacteria removal by sedimentation than typically
would be assumed, based on size and specific gravity alone
(Characklis et al., 2005; Schillinger and Gannon, 1985;
Hathaway et al., 2009). Clays, and bacteria, also are difficult to
settle because they typically have surface charges at the pHs
of surface runoff (Bolland et al., 1998; Baygents et al., 1998;
Clark et al., 2010); these charges encourage repulsion between
separate individual particles and bacteria and limit sedimen-
tation effectiveness. Sedimentation devices are not 100%
efficient, even for ‘ideal’ particles, and an adjustment, usually
applied through an efficiency factor, must be included in the
calculations. There are five reasons for non-ideal behavior. (1)
Many particles are not spherical in shape. (2) Particle settling
may be hindered by the behavior of other particles in the
water. (3) Many basins experience short-circuiting, plus have
areas that act as dead storage, especially near the inlet and
outlet of the basin. (4) Stratification due to density and/or
temperature differences may reduce the effective depth of the
basin. (5) Previously-captured particles may be resuspended if
an appropriate basin depth is not provided (Metcalf and Eddy,
2003). To prevent solids resuspension, overlying water depths
of at least 10 cm were needed in catchbasin sumps, while
30 cm may be needed for larger ponds (Avila et al., 2011).
6717
1 mm 0.45 mm
98 100
89 92
12 17
22 22
34 37
76 82
70 72
Minimizing resuspension and short-circuiting have resulted
in some ponds achieving removal efficiencies >95% for sus-
pended solids for individual storm events and typical influent
size distributions. Median suspended solids removals are in
the range of 70e80% (Hossain et al., 2005; International
Stormwater BMP Database, 2011), but decrease if the influent
includes many small solids (Greb and Bannerman, 1997).
Sedimentation efficiency can be increased by using
inclined settlers and/or coagulationeflocculation. Inclined
plate and tube settlers operate by reducing the distance
required for particles to fall before they contact a solid surface.
Because the plates/tubes overlap at an angle, more sedimen-
tation surface area is available per footprint area than
conventional sedimentation basins. These enhanced settlers
work best when operated in laminar flow conditions with
Reynolds’ numbers less than 800 (AWWA, 1999). Efficiencies
are assumed as approximately 60% (Lin, 2001). Inclined plate
settlers have been used successfully to treat runoff solids and
prevent scour of previously-trapped particles (Clark et al.,
2009; Pitt et al., 1999).
The second enhancement for sedimentation is through the
use of coagulants to create larger particles (flocs). Coagulation
destabilizes colloids by reducing repulsive forces between
particles. The coagulant also creates chemical bridges
between particles, creating larger particles that settle more
effectively, even though the bulk particle specific gravity may
be close to 1. However, coagulant particles cannot be consid-
ered to be ideal particles since they typically are not spherical
and likely have larger drag forces acting on them. Because the
reaction between the solids and the coagulant is unique, there
are no equations to predict sedimentation efficiency for flocs
(Droste, 1996). Coagulants have been used to treat stormwater
runoff (Harper et al., 1999; Annadurai et al., 2003; Sansalone
and Kim, 2008), but typically where removal efficiencies
must exceed that of traditional settling basins and to target
specific pollutants, such as phosphorus.
3.1.2. Physical filtration
Solids removal through physical filtration is based on both the
pollutant particle size and the media pore size. Typically
larger pore sizes are associated with higher treatment flow
rates; however, the treatability of small sized pollutants
decreases as the media pore size increases. Traditional
filtration design equations are based on the development of
head loss or resistance to flow, translated to stormwater
design as ponding/drawdown time. Because many regulations
require limited surface ponding of water to control aquatic
6718 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
insect populations, the lifespan until headloss reaches a crit-
ical headloss is important. Two common design equations for
estimating clean-bed, prior-to-use, head loss are the Car-
maneKozeny and Ergun equations (Droste, 1996; Metcalf and
Eddy, 2003). These equations, however, are difficult to trans-
late into practice where the filtration treatment flow rate
declines with time as a function of particle loading. Several
researchers have proposed equations to predict the flow rate
loss as a function of time/solids loading (Li and Davis, 2008a,b;
Siriwardene et al., 2007a,b; Dechesne et al., 2004, 2005;
Urbonas, 1999). The Urbonas (1999) equation for downflow
sand filter treatment of stormwater is the simplest to apply
because it is a power equation relating solids loading per unit
area, an easily measured/estimated parameter, to the flow
rate through the media. Although developed for Lakewood,
Colorado, sand filters, the Urbonas equation has been applied
to a variety of media in locations worldwide (Barrett, 2003;
Gironas et al., 2008; Clark and Pitt, 2009a). The equation,
though simple, requires calibration for each media and
influent size distribution (Clark, 2000).
The ability of media filters to remove particles of specific
sizes is a function of the media grain size, porosity, pore space
size, and pollutant size and shape (Fig. 1 shows sizes of
pollutant categories versus filter pore size). The above discus-
sion focused on media filters, which can remove successfully
solids in the silt and sand textural classes, including cysts, plus
a fraction of the clay-sized particles, including some bacteria.
The removal of viruses, colloids, and dissolved ions and
molecules is not possible through conventional physical
straining, however, and requires filters with smaller pore size
openings than a media filter, i.e., membrane filters. Creating
the driving force for membrane filtration requires a substantial
energy input to generate the difference, or gradient, of
Fig. 1 e Pollutant particle sizes versus filtration types (Adapted from www.freedrinkingwater.com, www.ultrapure.com,
www.prep-tec.co.uk, www.coolabahwater.com.au, and www.liquidfiltration-products.com. Adapted by these companies
from source material of Water Quality Association and Osmonics, Inc).
pressure, electrical potential, or concentration between the
influent water and the treated water. In addition to providing
molecular size selection, membranes also can allow or exclude
certain particles, based on the membrane’s chemical charac-
teristics, specifically charge/polarity (Droste, 1996).
Membranes are not suitable for most stormwater treatment
applications for the reasons outlined above.
Even though membrane filtration is not practical in most
stormwater applications, pollutant removal in the size range
considered “dissolved” by media filtration, plus possible addi-
tional removal of the smaller material, may be necessary in order
to meet permit requirements and reduce surface and ground
water degradation. Appropriate removal levels can be achieved
at most sites through combinations of unit processes that
incorporate sedimentation and chemically- and biologically-
active filtration.
3.2. Removal of colloidal, non-charged, and ionic
pollutants based on chemical characteristics
The removal of small-sized pollutants (colloidal and other
filterable forms, generally <1 mm in size, e.g., filterable heavy
metals, nitrates, many pesticides, etc.) typically has not been
the focus of stormwater runoff treatment, except where
TMDLs or known receiving water stressors were a regulatory
focus. The following sections address the impact that the
pollutant chemical characteristics will have on the treatability
of these especially problematic stormwater pollutants.
3.2.1. Temperature at phase change (freezing and boiling
points)
Many liquids have freezing or boiling points that are
substantially different than water and that theoretically could
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
be exploited for treatment. Similarly, the addition of dissolved
ions to water, such as sodium chloride associated with
snowmelt, when at sufficient concentration, will alter either
the freezing or boiling point of water and affect treatability.
For stormwater treatment, however, the exploitation of
freezing and boiling points has limited value to date, with no
known full-scale applications.
3.2.2. Stratification/separation of pollutants based on density
Many substances found in stormwater runoff have densities
either substantially less than or greater than the approximately
1000 kg/m3 density of water. These density differences can be
exploited for treatment, such as by oilewater and floatables
separators. However, for separation to be effective, not only
must the pollutants have densities substantially different than
water, but the pollutants also should not interact with water
(low water solubility, nonpolar organic compounds are most
likely to separate from water). Surface charges and large dipole
moments increase the solubility of pollutants in water and
decrease the effectiveness of density-specific separations
(Streitwieser and Heathcock, 1985). While density separation
occurs in practices such as northern climate detention ponds in
winter due to increased salt inputs, its practical use in storm-
water runoff treatment has been limited to only a few appli-
cations, such as the Dunkers Flow-Balancing System (DFBS).
The DFBS is a series of connected cells constructed at a storm-
water outfall using suspended/weighted plastic curtains
attached to pontoons. During rainfall events, the receiving
water is displaced through the cells by stormwater runoff,
starting with the cell closest to shore. After the storm event
ends, the trapped water in the first cell is pumped back to the
treatment plant with receiving water displacing the water in
the last cell. This system has been applied to trapping, pump-
ing, and treating combined sewer overflows that discharge to
saline waters, and for phosphorus treatment when used in
conjunction with ferric chloride coagulation and inclined plate
separators (Pitt and Dunkers, 1993).
3.2.3. Volatility
Removing a pollutant from an aqueous solution by volatiliza-
tion is a function of its vapor pressure and its water solubility,
as measured by its Henry’s Law constant, KH. If the water
solubility is sufficiently low, though, even compounds with
low vapor pressure will volatilize, e.g., DDT. According to Watts
(1998), Henry’s Law constants of 107 indicates that
compounds are essentially non-volatile. These compounds
have the potential to concentrate in solution if the surrounding
water evaporates. Volatilization is the fundamental process
behind air stripping and is especially important for small
compounds (molecular weight and size) that are sparingly
water soluble, such as volatile organic compounds (VOCs). The
Multi-Chambered Treatment Train (MCTT) uses volatilization
to remove petroleum-based VOCs (Pitt et al., 1999).
3.2.4. Solubility
Compounds that are not soluble in the solvent, e.g., storm-
water runoff, whether solid or a liquid, will appear separate
from the water. Water solubility for a liquid is described by its
solubility constant, KS, while water solubility of a solid is
described using the solubility product, KSP, for the precipitate.
6719
For organic compounds, solubility also is described in terms of
the compound’s solubility in water-saturated octanol
compared to octanol-saturated water, KOW (Watts, 1998).
KOW or log KOW can be used to estimate the tendency for an
organic pollutant to be transported with the water or to attach
to sediment in the water or in a filter media. However, the use
of these constants in predicting phase separation may not be
accurate for dynamic, non-equilibrium systems. Differences
between predicted sorption coefficients and measured coef-
ficients were observed by Hwang and Foster (2006) in the lower
Anacostia River, where the concentrations of particulate-
bound PAHs were higher than the predicted equilibrium
concentrations.
Many ions, especially carbonates, phosphates, and hydrox-
ides, react with metals to form insoluble precipitates (Stumm
and Morgan, 1996) with the maximum water concentrations
of these ions at a given pH estimated from the solubility
product, KSP. For example, precipitation and co-precipitation
may occur at the surface of Fe and Al oxides in stormwater
sedimentation and media filters, after the pollutant has been
adsorbed to the media/sediment surface, as noted by Sheoran
and Sheoran (2006) in their work on acid-mine drainage. The
use of water-treatment residuals from either aluminum sulfate
or ferric chloride coagulation processes has been investigated in
agriculture as a method to immobilize phosphorus in runoff
(Makris et al., 2004; Wagner et al., 2008). The use of water-
treatment residuals to capture phosphorus in stormwater has
been investigated by Lucas and Greenway (2011a) and O’Neill
and Davis (2012 a,b). Biologically-generated sulfides also can
precipitate copper, zinc, nickel and other metals (Jong and
Parry, 2003); however, maintaining the anaerobic conditions
that generate the sulfides is problematic in stormwater runoff
treatment because of the other reactions occurring in the media
when the porewater and media become anaerobic (Clark and
Pitt, 2009b). For example, nitrate-reducing bacteria and their
extracellular compounds can increase the rate of dissolution of
iron-phosphate precipitates in stream sediment under anoxic
conditions (Jansson, 1987).
As opposed to physisorption, where the electrical bonds
between the pollutants and the media are weaker and
reversible, the chemisorption and precipitation reactions
result in permanent retention, assuming that the pH and
dissolved oxygen do not change substantially (Evangelou,
1998; Watts, 1998). However, estimating precipitation of one
of these ions is complicated by the occurrence of soluble
complexes of the ions. For example, in addition to the
precipitate, zinc reacts with hydroxide ions to form a variety
of soluble Zn(OH)x complexes that range in valence charge
from þ1 to 2 (Snoeyink and Jenkins, 1980). Complexation can
explain, at least partially, the difference between ionic
concentrations predicted using KSP and the measured
concentrations in water. Solubility is related to the next
property, surface charge. Since water is a polar molecule,
pollutant ions/complexes/colloids/clays with surface charges
tend to associate with the water and are less likely to be
removed easily without exploiting other chemical properties.
3.2.5. Valence charge/polarity/surface charge
The charge distribution either on the surface of or within
a pollutant molecule will affect treatability. Removal reactions
6720 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
such as sorption and ion exchange are a result of electrostatic
interactions between media and pollutants. Precipitation
reactions are dependent on the reaction of ions with
complementary valence charge.
Most inorganic pollutants exist in the form of chemical
salts that may dissolve in the water to some extent, or
completely, releasing ions that then can potentially react with
other runoff ions, solids, and/or with removal media. Because
water is a polar molecule, the compounds/ions that are more
soluble in water also tend to be charged, and include many
inorganic species, plus polar organic compounds. Inorganic
cations and anions have a wide range of water solubilities,
depending on the presence of other ions in solution. For
example, carbonate as a species is soluble; however, when
certain metals also are in solution, carbonates participate in
precipitation reactions (Snoeyink and Jenkins, 1980; Stumm
and Morgan, 1996). Several inorganic anions, such as chlo-
rides and hydroxides, participate in complexation reactions
and increase the water solubility of many metals above what
is predicted by the KSP (Snoeyink and Jenkins, 1980), but also
exist in water as free ions. For organic compounds, shape, size
and functional groups affect solubility (Watts, 1998).
The interaction of pollutants with a removal media have
been categorized historically into one of two types: sorption or
ion-exchange. These two treatment processes are presented
as distinctly different, but they are both based on electro-
chemical bonding between pollutants and media. Adsorption,
or physisorption, is reversible and involves weak chemical
bonds, such as hydrogen bonds, van der Waals forces, and/or
dipole-induced interactions (McKay, 1996; Cooney, 1999).
Adsorption, because it is accompanied by desorption, retards
the pollutant movement through the media, but pollutant
retention is not permanent. Sorption media need to be
regenerated or replaced before the pollutant is transported
through the entire media depth. Some media, such as soils
and other organic media (compost and peat), also participate
in chemisorption reactions, including precipitation. Chemi-
sorption results in bonding that is mostly irreversible because
the bonds between the pollutant and the media are strong
(Watts, 1998; Evangelou, 1998).
Ion exchange, mostly associated with zeolites, is the
process where the exchanging ion is trapped in or on the
structure of these materials and balances the charge of the
material itself. This captured ion can be exchanged with other
ions, such as pollutants, if the pollutant has a higher valence
charge and/or concentration and has an appropriate size to fit
in the lattice space (Ruthven, 1988; Robinson et al., 1994). Ion
exchange resins are regenerated using an ion that has weaker
exchange potential but that is introduced into the media in
sufficiently high concentration to overwhelm the potential
exchange sites. Regeneration of any media, however, is not
100% efficient because a fraction of the pollutants penetrate to
the inner areas of the lattice and cannot be removed (Watts,
1998). A complication occurs when snowmelt enters a treat-
ment system that relies on ion exchange for the removal of
cations such as metals. The high sodium in the snowmelt can
“recharge” the ion exchanging capacity of the media, releasing
the previously captured metals back in the effluent.
Treatability in filtration media also is complicated by the
oxidationereduction conditions in the media itself. Aryal et al.
(2007) noted that the associations of heavy metals with acid-
exchangeable, reducible, and oxidizable fractions affected
their potential mobility in the media, especially if the redox
conditions change during or between storms. Typically the
runoff entering a filter/infiltration system is aerated, which
should ensure that the surface layer of the media remains
aerobic during a storm event. However, deeper in the media
and between storms, the biological activity may reduce the
dissolved oxygen content of the porewater, which will affect
the redox conditions and potentially result in pollutant
release or leaching of compounds from the media (Clark and
Pitt, 2009b). Similar releases may occur when anoxic zones
are improperly designed for nitrate control by denitrification.
Releases of phosphorus from sediments where ferric iron
(Fe3þ) has been reduced to ferrous ion (Fe2þ) have been
documented in lakes (Correll, 1998), indicating the potential
for phosphorus release occurring in treatment devices where
the redox conditions change, e.g., wet detention pond sedi-
ments and organic filtration media. In all cases, inadvertent
releases of compounds associated with media degradation or
ion-exchange releases of previously-captured pollutants must
be considered.
3.2.6. Predicting treatability of dissolved organic and
inorganic pollutants
Because many chemical properties are inter-related, i.e.,
solubility is related to surface and internal charge distribu-
tions, prediction models for treatability have focused on
a generic surface interaction between the pollutant and the
removal media, without separating the reaction type. This
focus on an unnamed interaction also acknowledges that
adsorption and ion-exchange are gradations of the same
process, e.g., a charge interaction between the pollutant and
the media. The testing methodology, e.g., batch vs. column, is
the divider between the model types. Batch testing exposes
media to the anticipated pollutant concentrations for suffi-
ciently long to ensure equilibrium. Batch testing results fitted
to the Langmuir and Freundlich isotherms may be used to
predict the capacity of the media (Watts, 1998). Johnson et al.
(2003) ran stormwater batch tests at two concentrations: one
typical of stormwater and one typical of low-to-medium
strength industrial wastewater. The results showed the
importance of testing at the anticipated runoff concentrations
because, at higher concentrations, the isotherms had different
shapes and favorability than those at typical runoff concen-
trations (Johnson et al., 2003). Batch kinetic testing, where
samples are analyzed after specific exposure intervals, also
can be used to predict rate constants for the mediaepollutant
interactions (Watts, 1998; Clark, 2000).
The second approach is to model the removal as a flow-
through system, using a fixed-bed adsorber equation, in
order to address the impact of contact time in the media.
Applying batch testing results to a fixed-bed column requires
assuming an instantaneous equilibrium, with all adsorption
sites available to a pollutant during its passage through the
bed (Watts, 1998; McKay, 1996). However, for many media, not
all active sites are available, especially the interstitial sites,
when the contact time is minutes versus many hours. Recent
research has focused on diffusion limitations, assuming that
adsorption is instantaneous once the pollutant reaches the
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
active site. Several models, including the film-pore diffusion
model, the film-solid diffusion model, the film-branched pore
diffusion model, and the homogeneous surface diffusion
model, have been proposed and evaluated for the design of
fixed bed adsorbers (McKay, 1996). The problem with these
diffusion-limited models is that the diffusion coefficients are
difficult to determine, and the results are not easily transfer-
able because of surface and interstitial phenomena. A second
concern about using this approach is that the different types
of diffusion affect sorption at different flow rates, and it is
known that the filter flow rate will vary both as the suspended
solids loading on the filter increases and as the length of
drying time between filtering events potentially causes
a recovery in the filter’s treatment ability (Clark, 2000).
The alternative to detailed process models is a model that
lumps all the rate-limiting steps into one rate constant. For
example, the Bohart and Adams (1920) model, which assumes
that the rate of the sorption reaction is proportional to the
fraction of sorption capacity still remaining, has been applied
to many industrial applications. Clark (2000), however,
showed the difficulty of applying this model, and likely other
fixed-bed models, to runoff treatment. These models assume
a substantial concentration gradient between the pollutant
and the media surface, with adsorption overwhelming
desorption. The large concentration gradients often do not
exist in stormwater runoff treatment. In addition, pollutant
removal, especially in natural systems, is due to many
phenomena, most of which cannot be mathematically quan-
tified at this time.
3.3. Unit processes to remove microorganisms (filtration
and disinfection)
Microorganisms, including both indicator and pathogenic
species, can be removed from water using the filtration and
chemical removal systems described above. However, the size
of many bacteria and viruses are such that physical straining
cannot be the only removal mechanism (Fig. 1). Cyst species
typically, though, are larger and can be removed by physical
means. Many bacteria and viruses are removed by sedimen-
tation and filtration due to their surface charges (Baygents
et al., 1998) and/or biofilms and exopolymers, such as carbo-
hydrates, polysaccharides, proteins, and nucleic acids (Ford
et al., 1991; Zinkevich et al., 1996), that enable their attach-
ment to settleable/filterable solids or to the filter media itself
(Clark et al., 2010).
Filtration and sedimentation do not permanently destroy
the microorganism, although they could be destroyed in the
media after entrapment through natural predation or desic-
cation. Desiccation is unlikely in most stormwater filters since
these media rarely dry out between storms (Johnson et al.,
2003). The wastewater engineering solution to reducing/
removing the activity of pathogenic species is deactivation/
disinfection using one of three common methods: chlorine,
ozone, or ultraviolet (UV) light (Droste, 1996; Metcalf and Eddy,
2003). Each of these disinfection techniques has been applied
to stormwater runoff or combined sewer overflows (Pavia and
Powell, 1969; Lainé et al., 1998; Arnett and Boner, 2009);
however, each has disadvantages. Chlorine disinfection
requires the storage of a hazardous chemical or on-site
6721
generation. Ozone and UV light require power. In addition,
because current U.S. regulations require the monitoring of
indicator organisms, rather than pathogens, once disinfected
runoff is mixed with the receiving water or travels over
surface soils where pets and wildlife have defecated,
measured bacteria concentrations may not reflect the disin-
fection activity.
3.4. Biological processes for pollutant removal
Biological processes have been used for decades to treat
polluted water. Cells, whether individual cells such as bacteria
or complex organisms such as plants, are comprised primarily
of carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulfur
(Metcalf and Eddy, 2003). These cells use many other
compounds as macro- or micro-nutrients (Wilkie et al., 1986;
Rahman et al., 2003). Many pollutants, when in non-toxic
concentrations, can be incorporated into the organism’s
biomass, used as an energy source and then excreted, or stored
in the organism’s body in a location that is not hazardous to the
organism (Banik et al., 1996). For example, hyperaccumulating
plants reduce soil metals’ concentrations and transfer those
metals to the plant’s biomass (which then must be harvested at
an appropriate time to reduce toxicity to the plant and to
reduce the chance of the metals reentering the environment
upon the plant’s decomposition) (Baker and Brooks, 1989;
Callahan et al., 2006; Xiong, 1998; Yang et al., 2004).
The use of planted treatment systems for runoff has
expanded substantially as part of low impact development/
green infrastructure. Planted systems provide many benefits,
including habitat and aesthetics. For stormwater treatment,
planted systems provide four additional benefits. (1) Soil water
is taken up by the plant and either incorporated into the
biomass or evapotranspirated (Read et al., 2008; Pitt et al.,
2008a; Denich and Bradford, 2010; Hickman et al., 2011;
Fassman and Stokes, 2011). (2) Nitrogen and phosphorus
transported by the water are incorporated into the plant’s
biomass (Pate, 1973; Schachtman et al., 1998; Henderson et al.,
2007). (3) The plant’s root systems reduce clogging and
improve infiltration rates through their expansion into the
soil. (4) The root zone microbial activity maintains nutrient
cycling and soil productivity in the soil (Atlas and Bartha,
1998). One potential drawback, though, is appropriately
timing the biomass harvesting. For some plants, harvesting
biomass during the growing season can result in reduced
nitrogen uptake and increased nitrogen leaching (Baker and
Clark, 2012).
Bacteria also play a role in treatment. The wastewater
industry has shown that a biologically-active upper layer in
filtration systems improves pollutant removal, especially at
low concentrations (Metcalf and Eddy, 2003). In stormwater
filter testing, however, the results have been mixed. Johnson
et al. (2003) showed that there was no difference in copper
adsorption and breakthrough between sterile mixed media
filters and non-sterilized filters when the filter columns were
dosed with exceptionally high influent concentrations
(w100 mg/L). Other researchers have shown that metals can
be adsorbed by microorganisms (bacteria, fungi) or by filters
inoculated with selected bacteria that are tolerant to the
heavy metals (Matis et al., 1996; Nakajima and Sakaguchi,
6722 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
1986). While the impact of native bacteria on pollutant
removal currently cannot be predicted, bacteria are important
in the treatment process and likely are responsible for initial
soil sequestration of nutrients, prior to uptake by the plant
mass.
4. Applying theory to the selection and
design of treatment systems
Preferred treatment technologies require no electrical power
and infrequent maintenance since they are dispersed in the
urban environment. The dispersed installations, plus the
power and infrequent, easy maintenance requirements,
generally eliminate large-scale air stripping, distillation,
disinfection, and membrane filtration as viable treatment
options. This section focuses on those processes that better
meet the requirements and provide effective treatment.
4.1. Solids removal
Similar to water and wastewater treatment plants, solids
removal must be evaluated as the first step since runoff solids
can clog treatment devices and/or block access of the
pollutant to treatment sites in chemically-based systems.
Droste (1996), based on guidance published by the AWWA,
recommends that sedimentation precede filtration unless the
water quality meets the following parameters: color < 40 color
units and turbidity < 5 NTU (deep filters may be used to treat
higher turbidity waters). Because many pollutants are at least
somewhat associated with the particulate matter in runoff,
sedimentation removes pollutants other than solids. The
effluent concentrations and removal efficiencies of
particulate-associated pollutants can be predicted based on
the removal efficiency of the solids themselves and the
association of the pollutants with the settling solids. Sedi-
mentation has been particularly effective at sites where the
particles are large, such as highways, and the metals associ-
ated with the larger particles (Kim and Sansalone, 2008). At
sites where large-size particle generation and transport is not
likely, many of the pollutants are associated with very-small
solids (Table 1; Morquecho et al., 2005). The selection of the
desired particle-size control is critical. Effective wet detention
ponds have lower SORs and limited short-circuiting; however,
there is a limit to sedimentation basin efficiency for small
solids, given the repulsive charges on the colloidal and clay-
sized solids. For enhanced sedimentation using coagulation/
flocculation, testing will be required since floc settling cannot
be predicted theoretically (Metcalf and Eddy, 2003).
4.2. Removal of solids associated pollutants
As indicated above, pre-treatment by sedimentation is a rec-
ommended step before advanced treatment phases. For pre-
treatment sedimentation, the design particle size goal should
be between 5 and 20 mm. The smallest particle size for which
reliable sedimentation can be assumed, and without
substantial charge interference of the settling particles, is
between 2 and 5 mm (Camp, 1952). Because, for some metals,
a substantial fraction is associated with clay-sized and
colloidal particles, filtration, likely using a chemically-active
media, also may be required to meet potentially very low
numeric discharge limits. Table 1 shows that cadmium and
copper, for example, may be associated with particles that are
not easily treated using sedimentation and physical filtration.
For sites where permits require substantial metal removal
(Pitt and Clark, 2010; for example), particles < 1 mm also must
be removed, typically through chemical interactions between
the filter media and the particles.
4.3. Removal of colloidal and ionic pollutants through
physical and chemical processes in media filters
4.3.1. Selecting treatment processes for the pollutants
The first step in selecting an appropriate filter medium is
identifying the pollutants and their forms that require
removal. Sand without surface amendments such as oxide
coatings is considered relatively inert compared to other
media and minimal removal likely would occur for colloidally-
sized pollutants. Sand, though, often is incorporated into
stormwater media to provide structure and to minimize
fluctuations in flow rate through the media (Clark, 2000). Sand
removal efficiencies typically increase as the media/filter ages
because the trapping of particles typically decreases the pore
openings, especially on the surface, allowing smaller particles
to be captured, plus the coating of chemically active materials
and biofilms on the inert sand particles occurs with time
(Metcalf and Eddy, 2003; Geesey et al., 1998). The performance
of these enhancements, though, has not been quantified.
The valence state and complexation of metals will affect
their treatability in specific media. Clark and Pitt (2011)
showed that zeolites can be effective for the fraction of
metals in the þ2 valence state. However, the overall effec-
tiveness of zeolites, and potentially other ion-exchange media
such as oxide-coated sands, was reduced because a substan-
tial fraction of the metals likely existed in valence forms other
than the favored þ2 due to complexation with inorganic ions
and organic matter. The effectiveness of ion exchange
decreases as the valence charge approaches zero and as the
size of the complex increases. For example, metallic mercury
exists in the þ2 form. However, in the presence of organic
matter, it can methylate to form methyl mercury. Methyl
mercury is an organometallic compound and is polar. Because
of its size and its organic component, it likely will not be
removed by zeolites, which have both a size exclusion and
a preference for strongly charged, small molecules. Mercury
also complexes with inorganic ligands in the water, such as
chlorides, creating inorganic molecules whose surface charge
and/or size may reduce the effectiveness of ion-exchange
media (Snoeyink and Jenkins, 1980).
Organic compounds and larger, less charged complexes of
metals can be chemically attracted to or bonded with a media
that exploit dipole moments and hydrogen bonds, as well as
a mixture of negatively and positively charged surface sites.
KOW will provide an indication of the preference for the
molecule to attach to an organic media (peat, compost, GAC)
versus remaining in the stormwater runoff. KS indicates the
likelihood that the organic compound will remain dissolved in
solution. These constants are qualitatively inversely related,
i.e., high KOW compounds typically have low KS values.
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
The removal of some inorganic anions, such as nitrates
and chlorides, is problematic because most media specifica-
tions require high cation exchange capacities (CEC). High CEC
media typically have low anion exchange capacities (AEC).
CEC and AEC provide an estimate of the potential for
exchanging a less-desirable compound in or on the media
with a pollutant whose chemical characteristics are more
favorable. Nitrate, fortunately, is a plant nutrient and it may
be removed by microbiological and chemical immobilization
in the root zone of the vegetated system (Lucas and Greenway,
2011b), assuming that the flow rate through the root zone is
within the range for microbial immobilization and resultant
plant uptake.
4.3.2. Selecting the filtration media
In industrial wastewater treatment, granular activated carbon
(GAC) is used to retard the pollutant transport through mecha-
nisms such as van der Waals forces and hydrogen bonding. GAC,
though, is expensive. Its use may be justified when the treat-
ment is required to achieve very low permit limits. GAC is not
suggested for routine incorporation into stormwater treatment
media because of its cost and because not all GAC performs
equally well for all pollutants, depending on its native material
and how it is activated (Pitt and Clark, 2010; Clark, 2000).
If the treatment system is vegetated, most guidance
documents recommend that organic matter, such as compost
or peat, be added, although recent studies have shown that
plants can grow in low organic matter media (Henderson
et al., 2007). Peat has been extensively studied for its treat-
ment effectiveness in both industrial wastewater and storm-
water applications (Clark and Pitt, 1999). Peat can be very
effective at removing many metals and hydrocarbons, and
likely metal complexes, down to very low concentrations
because of the variety of binding sites (carboxylic acid, etc.)
found in the humic materials and lignins in the peat (Cohen
et al., 1991; Sharma and Foster, 1993). Many sites are
involved in chemical bonding reactions that are more
permanent (chemisorption versus the hydrogen bonding and
van der Waals’ reactions occurring during physisorption).
According to Cohen et al. (1991), peat’s ability to treat metals
can be directly related to its degree of decomposition with
Sphagnum peat, the least decomposed, being less able to treat
metals than Carex peat, which is more decomposed. However,
Clark and Pitt (1999) showed excellent removals of several
heavy metals with Sphagnum peat, potentially to the level that
would meet many permits, and Sphagnum peat is readily
available at nurseries. In addition to the release of colored
humic and fulvic acids, peat’s primary noted disadvantage,
especially the Sphagnum peat, is that it tends to exchange
hydronium ions when it removes metals. The release of
hydronium ions reduces the pH of the treated water, often by
1e2 pH units (Clark and Pitt, 1999). This may reduce the pH to
where many of the metals attached to the media or runoff
solids may become more soluble. As an advantage, Pitt and
Clark (2010) showed that peat could effectively remove many
heavy metals using relatively short contact times (as little as
10 min), compared to the other non-organic media tested
(several hours of contact time).
Compost, especially municipal leaf waste compost and
since it is considered sustainable compared to peat, has
6723
a variety of potential reaction sites for metals, organics and
other pollutants (Sharma and Foster, 1993; Guisquiani et al.,
1995). Unlike peat, it does not tend to drop the pH of the
treated stormwater (Clark and Pitt, 1999), but it commonly
releases nutrients as it degrades during the first several years
of use (Pitt et al., 1999; Pitt and Clark, 2010). Compost’s ability
to treat pollutants and the likelihood that it will release
nutrients is directly related to its source material and
percentage in the mixture (Hathaway et al., 2008). Other
organic materials, especially those from waste materials
including coir peat and biosolids, are being investigated in
stormwater treatment devices. Coir peat is used as a growing
medium in horticulture to improve water retention and
reduce nutrient leaching, while biosolids have been used in
agriculture to replenish soil nutrients.
These organic media, like all filtration media, have irre-
ducible concentrations below which no removal occurs.
These irreducible concentrations are related to the hydraulic
loading (flow rate per unit area) and to the parent material
and its background contamination. Slower flow rates
increase contact time between the media and the pollutants,
providing sufficient time for slower reactions such as diffu-
sion to occur. Pitt and Clark (2010) showed that most metals
require contact times of between 10 and 100 min for the
majority of metals removal to occur. However, both compost
and peat release nutrients in the first flush of water from the
filter if microanaerobic environments develop in the media
between storms (Clark and Pitt, 2009b). Therefore, the layers
containing peat and compost should be kept aerobic and
should not be left saturated between storms. Research is
ongoing as to whether adding a slowly-biodegradable organic
material such as sawdust, etc., enhances denitrification in
specially-designed filters or whether sufficient organic
matter exists in the water to promote denitrification. In
addition, minimizing the organic content should reduce the
nutrient release both during the early years and between
storms (Hunt et al., 2006; Bratieres et al., 2008; Hatt et al., 2008;
Davis et al., 2009).
Nitrite and nitrate are difficult to remove from solution
chemically. Large removals of nitrate, but with limited
chemical capacity, were seen in tests with a virgin coconut-
hull GAC (Pitt and Clark, 2010). Other commercial resins and
some native soils and zeolites also may have the potential to
remove nitrogen. Typically, AEC values, when compared to
CEC values, are low, indicating limited lifespan for removing
negatively charged pollutants (Evangelou, 1998). In addition,
because these pollutants have a 1 valence, they are not
preferentially taken up if pollutants with larger negative
valence charges are in the runoff. Removal of nitrite and
nitrate typically is best performed by vegetated systems, as
shown by Baker and Clark (2012) and Lucas and Greenway
(2008, 2011b). Effective nutrient uptake by plants, however,
requires low flow rates through the media, so that the nutri-
ents are not flushed past the root zone before the microbial
community can immobilize them for future plant use. Bio-
logical denitrification, where the bioretention system’s
underdrain has been modified to create an internal water
storage zone to retain water between storms and allow deni-
trification, has been investigated by Hunt et al. (2008).
However, if the labile organic layer in the media becomes
6724 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
anaerobic, nitrate leaching would be expected (Clark and Pitt,
2009a,b).
Where phosphorus removal is an issue, the particulate
associated fraction could be treated with sedimentation and
the dissolved/colloidal-bound fraction either chemically or
through uptake by vegetation (Lucas, 2009). Sedimentation
can provide partial removal (since phosphorus reacts with the
aluminum and iron components of stormwater-borne solids
and/or soil. These chemical reactions typically are permanent.
Lucas and Greenway (2011a) and O’Neill and Davis (2012 a,b)
demonstrated the effectiveness of aluminum in water treat-
ment residuals to remove and retain phosphorus. The reac-
tions of phosphorus with iron and aluminum also have been
exploited in stormwater coagulationesedimentation and
iron-enhanced filtration investigations (Trejo-Gayton et al.,
2006; Erickson et al., 2007).
Similar to nitrate, phosphorus leaching is a concern. Hunt
et al. (2006) investigated the likelihood of phosphorus reten-
tion versus leaching. The results showed that high P-index
(an indication of phosphorus content) values resulted in
phosphorus leaching. Because P-index is calculated region-
ally based on the potential for soil erosion, water runoff, and
the concentrations and methods of application of various P-
containing fertilizers with different weights given to these
factors based on regional concerns, Treese et al. (2012) and
Clark et al. (2010) investigated phosphorus retention simply
as a function of initial phosphorus content of the media. The
preliminary results show that if a soil fertility test shows that
phosphorus fertilizer is needed, then phosphorus retention
chemically in the soil is likely. If the phosphorus content is
labeled as “high,” then leaching is likely to occur. Phosphorus,
like nitrogen, can be released from organic media if micro-
anaerobic environments develop between storms (Clark and
Pitt, 2009b).
4.4. Removal of organic pollutants through density
differences and air stripping
The use of density differences between water and the pollut-
ants are most applicable to those rare cases where free
floating oil, i.e., more than an oil sheen, is visible. In these
instances, an oilewater separator may be useful. Oilewater
Table 2 e Selecting treatment technologies for stormwater pollutants.
Pollutant Treatment process
Solids
Diameter > 5e10 mm Sedimentation
separators also may be useful to separate floatable litter from
the water. Air stripping would be applicable to sites where
volatile organic carbons are present. The MCTT, for example,
uses packing/aeration balls to remove gasoline-related VOCs
from the influent runoff before it enters the underground
sedimentation chamber to avoid a buildup of volatile gases
underground (Pitt et al., 1999).
4.5. Summary of stormwater treatability options
4.5.1. Treatment options by pollutant
Table 2 lists many of the pollutants of primary interest in
stormwater runoff and potential treatment options, as well as
some considerations in the design.
4.5.2. Additional design considerations for stormwater filters
These design factors also must be considered because of their
impact on performance and longevity: sodium adsorption
ratio (SAR) and clogging potential. An excess of sodium ions,
such as potentially from sodium-based deicing agents, will
disperse soil clays, resulting in a media that is almost imper-
meable to passing water. Similar to the minimization of
organic matter in a filtration media to address nutrient
leaching, the percentage of clay in the media mix should be
minimized or clay should be removed from the mix, especially
in northern climates. If sodium inputs to the treatment device
cannot be reduced, then filtration devices may not be the
appropriate treatment technology for that drainage area.
Media filters also are subject to clogging due to the solids
loading on and in the media. If the appropriate coefficients are
known, the Urbonas (1999) equation can be used to estimate
the flow rate as a function of media loading. However, these
coefficients rarely are known, and the current guidance
suggests that clogging, i.e., unacceptably low flow rates and
extended drawdown times, will occur in unvegetated systems
with accumulated solids loadings between 10 and 25 kg/m2
(Clark and Pitt, 2009a; Pitt and Clark, 2010). The solids loading
to clogging is substantially reduced if the media was com-
pacted during construction and the depth of the media cannot
be used for solids retention. Healthy, deep-rooted vegetation,
because of the development of a healthy soil structure, can
extend the media life before clogging.
Design notes
Determine whether sedimentation is pre-treatment
(critical particle size of 10e20 mm) or primary
treatment (critical particle size of 5 mm).
Sediment forebay (sumps and vaults also) for
rapid settling of particles 20e50 mm and
greater effective for large influent concentrations.
For large concentrations of particles between 5 and
20 mm, increasing sedimentation efficiency using
inclined plates and tubes possible.
Design: Vparticle ¼ SOR for critical particle size,
assuming that basin is not 100% efficient
(design critical particle size smaller than desired
100% particle size to account for inefficiencies).
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0 6725

Table 2 e (continued )
Pollutant Treatment process Design notes

Diameter 1e5 mm Physical filtration Sand filtration effective for particles greater than
1e3 mm.
Physical filtration enhanced with media with smaller
pore sizes; however, clogging and lifespan before
maintenance must be considered.
Physical filtration enhanced with preceding coagulation
and sedimentation, although chemical addition likely
not attractive due to dispersed nature of devices and
need for residual management.
Diameter < 1 mm Membrane filtration Membranes likely not attractive due to power/
Chemically-reactive filtration maintenance needs.
Small particles with surface charges can be attracted
electrostatically to chemically-reactive media.
Coagulation destabilizes charges and create larger particles;
coagulation requires chemical storage and dispensing,
plus residuals management. May not be attractive if
passive means can address the problem.
Nutrients
Ammonia Ion-exchange At pH of most runoff, majority of ammonia exists as
Oxidation and plant ammonium ion (NHþ 4 ). Ion exchange possible but þ1 is
uptake weak exchanger and ion-exchange may require zeolites
with small lattice openings that exclude larger cations.
Ammonia/ammonium in runoff, during decomposition of
organic N, and in upper layer of soil may be oxidized to
nitrate and then immobilized and taken up by plants.
Slow flow rates recommended.
Nitrate and Nitrite Ion-exchange Ion-exchange possible, but anion exchange difficult
Plant uptake (most zeolites have weak anion exchange capacity).
Primary removal through soil microbial retardation and
plant uptake. Requires slow flow rate through root
zone e rapid infiltration promotes bypassing of root
zone activity.
Can be removed by denitrification (internal water storage
design).
Can be released from organic media if microanaerobic
environments develop between storms or if background
content of nitrate in media is higher than the plants need
or if unvegetated and soil fertility reports shows media
has more nitrogen than needed for crop growth.
Phosphate Chemically-active media filtration Phosphate is strong anion and could participate in ion-exchange,
Plant uptake but difficult (weak anion exchange capacity of organic filter
media).
Reacts strongly with Fe, Al, and/or Mn in soil or residuals.
Also reacts with these elements in stormwater-borne
solids and may be settled out.
Can be released from organic filter media if microanaerobic
environments develop in filter between storms or if
background content of phosphorus in media is higher
than the plants need (want soil fertility report to show
that phosphorus needs to be added for good crop growth).
Metals
Lead Ion-exchange Lead attaches strongly to solids. Substantial removal by
Chemically-active media filtration sedimentation and/or physical filtration of solids to which
lead is attached.
Lead < 0.45 mm may be ionic and could be removed using
ion-exchange with zeolites, but filtered, ionic lead is
usually at very low concentrations and it would be unusual
to require treatment.
Lead complexes with hydroxides and chlorides to a certain
extent. Removed in media with variety of binding sites
(peat, compost, soil).
(continued on next page)
6726 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0

Table 2 e (continued )
Pollutant Treatment process Design notes

Copper, Zinc, Cadmium Chemically-active These metals can attach to very small particles, with attachments
filtration being a function of the particulate organic content, pH, and
oxidation-reduction conditions (filterable fractions vary from
25 to 75þ%). Physical filtration may be limited depending on size
association of the pollutants.
These metals complex with a variety of organic and inorganic
ligands to create soluble complexes of varying valence charges
(2 to þ2). Small amount of ionic species (metal as þ2 ion only)
reduces ion-exchange effectiveness. Complexes require variety
types of sorption/exchange sites. Organic complexes may be
removed by GAC. Peat, compost and soil will remove most
inorganic and organic complexes.
Concern about background contamination of media with metals.
Mercury Chemically-active filtration Mercury reacts with both organic and inorganic compounds to
with organic media form complexes, plus it methylates to form methylmercury
(log KOW ¼ 1.7e2.5), which is somewhat soluble in water.
Complexes require multiple types of sorption/exchange sites.
Organic complexes and methylmercury may be removed by GAC.
Other potential media include peat, compost and soil. Reducing
mercury to very low levels with filtration may be difficult if parent
material has mercury contamination. Hyperaccumulating plants
have been successfully used for reducing Hg from sediments and
soils (requires harvesting and plant management).
Organics and pesticides
Volatile Organic Air stripping Passive air stripping can be accomplished using step aeration or
Compounds (VOCs) Chemically-active filtration by passing runoff over packing balls or other air entrainment
mechanisms as the water enters the treatment device. See below
for filtration.
PAHs/Oil and Grease Chemically-active filtration These compounds have high KOW and low KS and are strongly
(O&G)/Dioxin associated with particulates. Sedimentation’s effectiveness is
function of particle size association. Preferential sorption to
organic media, such as peat, compost, soil. Some O&G components
can be microbially degraded in filter media. Reductions to very low
levels with filtration may be difficult if parent material is
contaminated. If low permit limits, may have to use clean material
such as GAC.
Organic Acids and Chemically-active filtration Tend to be more soluble in water than PAHs and more likely to be
Bases transported easily in treatment column. Need media with multiple
types of sorption sites, such as peat, compost and soil. GAC
possible if nonpolar part of molecule interacts well with GAC or if
GAC has stronger surface active reactions than just van der Waals
strength forces.
Pesticides Chemically-active filtration Tend to be soluble in water and need multiple reaction sites to be
removed. Breakdown time in biologically-active filtration media is
compound-dependent. Breakdown has the potential to restore
surface-active sites, and may result in more soluble daughter
products, which may or may not be more toxic. Organic media
such as peat, compost, soil, GAC likely to be most effective since
size of compound will exclude substantial removal in ion-exchange
resins such as zeolites.
Microorganisms
Cysts and Large Pathogens Physical filtration Large enough to be physically strained from the water.
(such as Giardia or
Cryptosporidium)
Bacteria Physical filtration Most bacteria are in the lower limits of the size range for effective
Organic media (chemically-active) physical filtration using a sand medium. Removal not 100% effective.
filtration However, as the filter ages, removals will tend to increase, partly
due to reduction in the effective pore sizes and due to the
exopolymers that many bacteria excrete. These exopolymers
will provide surface reactive sites, even on a relatively-inert sand
media. Exopolymers and surface active sites on cell membranes
also enhance the attachment of bacteria to surface sites on
filtration media.
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 6 7 1 5 e6 7 3 0
Table 2 e (continued )
Pollutant Treatment process
Viruses Chemically-active filtration
5. Conclusions
As more stormwater discharges are subject to numeric
effluent limitations, it becomes increasingly necessary to
design stormwater treatment systems based not on assumed
percent removals currently found in many guidance docu-
ments, but instead based on an understanding of the perfor-
mance requirements and the unit processes operating in the
various treatment technologies. Understanding both the
influent water chemistry and the ability of the treatment unit
processes to remove specific forms of pollutants will allow the
designer to create a tailored system that addresses the permit
requirements.
Acknowledgments
This paper has its foundation in many years of research on
stormwater treatability by the authors and others. The
authors express their gratitude to the following organizations
for their sponsorship of our research over the past decades:
U.S. Environmental Protection Agency (Mr. Richard Field,
Project Officer, Urban Watershed Management Branch); Boe-
ing, Inc., and Geosyntec Consultants, Inc. (Mr. Brandon Steets,
Project Manager at Geosyntec); and the Water Environment
Research Foundation (Mr. Jeff Moeller, Ms. Christy Terhune,
and Ms. Jane Casteline, Project Managers). The authors also
wish to thank all the graduate students at the University of
Alabama, Penn State Harrisburg, and the University of
Alabama at Birmingham whose work over the years has
contributed to the projects that are the backbone of this paper.
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