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By Gary R. Minton

This
is the last in a series of articles examining design criteria for
stormwater treatment systems. The first three articles focused on
the removal of settleable sediment with attached
(particulate) pollutants by basins , fine-media
filters , and flow-through
swales . The fourth article considered removal
of dissolved pollutants in wet basins. This article discusses
removal of dissolved pollutants by fine-media filters and briefly
flow-through swales. This article discusses removal of dissolved
pollutants by fine-media filters and briefly flow-through swales.
The previous article
established that three regulated metals are primarily found in a
dissolved state: zinc, copper, and cadmium. Nitrogen is dissolved
or may become dissolved in the system by bacteria. While dissolved
phosphorus is generally less than 50% of the total, this fraction
is nonetheless important given its bioavailability.
Fine-Media Filters
Fine-media filters have several advantages over wet basins.
Filters can be placed beneath the surface allowing for continued
use of the land. They do not freeze if placed below the frost line.
The original media can be replaced with more appropriate media if
performance objectives change. The performance of filters does not
depend on and is not affected by the vicariants of plants. Performance
may therefore be more reliable and consistent. Filters do not attract
waterfowl, which adds to the pollutant load. Sand is the most commonly
used fine medium. A second medium may be included to enhance removal
of soluble pollutants.
Sand
One would think sand is inert, incapable of removing dissolved
pollutants. Nonetheless, removal of dissolved phosphorus and metals
(Caltrans 2004, City of Portland 2003) has been observed, but not
consistently. It has not been observed in laboratory studies. Firm
conclusions are hampered by sampling too few storms and the low
influent concentrations, usually close to the respective detection
limits with the exception of dissolved zinc. Removal of dissolved
pollutants may occur by one or a combination of three mechanisms:
precipitation, biological growth, and sorption to organic litter.
Precipitation of dissolved
phosphorus can occur with iron, aluminum, manganese, and calcium
phosphate. The surface chemistry of the sand is likely a significant
factor in whether removal occurs by this mechanism. One study found
sands with sorption capability vary significantly with the source
(Arias, Bubba, and Brix 2001). Calcium phosphate may form on the
sand if the hardness, alkalinity, and pH are appropriate (Aulenbach
and Meisheng 1988), particularly if the sands are calcareous. The
possible mechanism of precipitation of dissolved metals is with
iron and/or aluminum oxide on the sand, either original to the sand
or from aluminum and/or iron in the stormwater. Sorption of zinc
and other metals to aluminum-iron oxide is known to occur in soils
including wetlands (Minton 2002).
Reduction of dissolved
metals by biological growth has been observed (Anderson et al. 1997),
primarily by a bacterial biofilm that grows on the sand media and/or
on the sediment removed by the filter. Growth likely occurs primarily
on the bed surface and within the top few inches of the sand (Horner
and Horner 1990). Removal may be due to the growth of the biomass
and/or sorption to polymeric materials extruded by the bacteria
in the case of dissolved metals (Johnson et al. 2003).
Dissolved metals sorb
to humic organics in wetponds and wetlands. Humic organics are available
for sorption through the degradation of leaves and other organic
matter that enter the filter.
Deducing from existing
field and laboratory studies the primary mechanism(s) and the conditions
under which each sorption process may occur is not possible. There
are too few studies and most are limited in scope. Often field studies
are limited to the first year of operation. Field studies of a mature
filter showing apparent continued removal after many years may be
misleading. Periodic loss may not be observed as typically not all
storms are sampled. Comprehensive laboratory and field studies are
needed, covering the array of different sands and stormwater chemistries.
It would seem that as
a field filter matures, removal by biomass reaches equilibrium:
The amount of organic matter produced is equaled by the die-off
or sloughing of biomass. After a period of time this mechanism would
no longer result in net removal. However, should the interevent
time between storms be significant and/or the filter be in an area
with a distinct dry season, the bed may dry, causing desiccation
of the biomass. The previously removed pollutants may be lost in
the first storm of the following wet season. The biofilm reestablishes
as the wet season proceeds.
One study (DeBusk et
al. 1997) suggests that metal-oxide-metal or metal-phosphorus complexing
occurs but that the mechanism is short-lived, likely a year or less
in wet climates. This suggests that iron and aluminum in the stormwater
do not play a role. The aggregate concentration of dissolved aluminum
and iron can be substantial in stormwatermore than a milligram
per liter. It is possible that the metal-oxide complex mechanism
is dependent on the chemistry of the particular sand. The loss of
both iron and phosphorus has been observed during what was believed
to be an anaerobic incident, although monolayer absorption tests
of the sand suggested that ferric phosphate precipitation was a
minor contributor to high phosphorus removal (Bell 1995). The mechanism
if it occurs may function longer in semi-arid climates with fewer
storms and therefore a lighter loading rate.
The few laboratory studies
of this question have generally found no removal of either dissolved
phosphorus or metals, with one exception. However, neither lab nor
field studies have examined the chemistry of the sand prior to use.
Given the dichotomy between field and laboratory studies, the limited
evidence might suggest that the primary removal mechanism with dissolved
metals is humic organics provided by the degradation of organic
litter. However, laboratory studies have generally not observed
the removal of dissolved metals or lent credence to this mechanism.
Table 1 shows performance
data for five sand filters (Caltrans 2004). The table shows a decline
in performance from year two to year three. Data from the first
year are not shown because there were too few samples. The differences
in removal efficiencies between the filters and the decline in performance
appear unrelated to influent concentrations. Despite the decline,
the efficiencies remained high in the third year. One filter was
considerably less effective than the other filters for unknown reasons,
with negative performance in the third year. The decline of all
filters may reflect stabilization of the bacterial mass, but may
also reflect a decline in sorption capacity. It is possible that
after bacterial mass stabilization and saturation of the soprtion
capacity inherent to the sand, continued removal is limited to surface
coating by incoming ferric-aluminum-manganese oxides, which may
be minor or non-existent in most cases.
| Table
1. Removal of Dissolved Metals |
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Experience With Additive
Media
The removal of dissolved pollutants may be enhanced by modifying
the media, either by the addition of a second media or by modification
of the surface of the sand. The mechanism of sorption to metal-oxide
coatings (iron, aluminum, or manganese) has been exploited for many
years with metal-laden wastewaters (Edwards and Benjamin 1989) and
more recently with stormwater (Sansalone 1999). Oxide-coated sand
removes dissolved phosphorus (Benjamin 1995). Dissolved metals and
phosphorus removal over a three-year period has been observed in
sand filters to which calcite or iron filings were added (Shapiro
and Associates and the Bellevue Utilities Department 1999). Organic
media of various types are known to remove dissolved metals including
peat, leaf compost, and soybean hulls (Johnson et al. 2003, Tobiason
2004). Additionally, leaf compost is used in a manufactured stormwater
filter. A multitude of other organic materials have been found to
remove metals (Minton 2002). Calcite in various forms, including
crushed seashells, removes dissolved phosphorus (Leszczynska, Dzurik,
and Michalowski 2002).
Organic media, as well
as sand, remove petroleum hydrocarbons, given their extremely hydrophobic
nature. Organic media, including activated carbon, remove pesticides.
However, laboratory and field experience is limited.
Stormwater Chemistry
The chemistry of stormwater is complex and as yet little understood.
Removal by any of the mechanisms previously described requires the
metal or phosphate ion to be in the ionic form, not bound to dissolved
humic organics or fine colloid sediment. As discussed in the fourth
article of this series (Stormwater, May/June 2005, www.stormh20.com/sw_0505_revisiting.html),
dissolved does not mean the pollutant is in the ionic
form. Dissolved metals bind to humic organics and sorb to very fine
colloidal sediments (inorganic and organic). They complex with carbonates
and ferric-aluminum oxide complexes. The later forms sorb to media.
Humic-bound metals do not sorb to media, apparently not even to
activated carbon. Small colloidal-metal complexes will not sorb
and are too small to be removed by straining. Research suggests
that most of the zinc and cadmium remains in the ionic form, but
that most copper binds to colloids (Grout, Wiesner, and Bottero
1999; Johnson et al. 2003; Morrison et al. 1984). Copper is particularly
attracted to humic organics as well.
Reducing the concentration
below receiving-water standardsparticularly that of copper
with its very low standardmay not be possible in many situations.
A study (Caltrans 2004) of sand filters suggests a lower effluent
limit of about 10 µg/L for dissolved copper and about 20 µg/L
for dissolved zinc, similar to observations with zeolite and organic
media (Johnson et al. 2003).
Organic media are general-purpose
removers. They remove all heavy metals to varying degrees irrespective
of whether we want the particular metal removed. But each type of
organic medium has a hierarchy of preference. The results of one
study are shown in Table 2 (Johnson et al. 2003). Note the interest
in iron, a pollutant not typically of concern. Organic media also
remove aluminum.
The above observations
suggest that when conducting performance studies the stormwater
samples need to be analyzed for constituents other than just the
pollutants of immediate interest. Analytes to include are aluminum,
iron, and dissolved organic carbon. Both aluminum and iron are present
in substantial concentrations, exceeding the aggregate concentrations
of the remaining metals.
Drawdown Time
Manuals differ with respect to the specified drawdown time:
24 to 48 hours. The choice of design drawdown time affects the size
of the filter: The greater the drawdown time, the smaller the surface
area of the filter. Doubling the drawdown time halves the filter
area. The choice of drawdown time is therefore not trivial.
The most common reasons
given for specifying a short drawdown time (relative to the interevent
time between storms) are avoidance of temporary anaerobiosis at
the bottom of the filter and/or clogging by the bacteria biofilm.
Bacteria consume dissolved organic compounds and nitrify ammonia
with the passage of stormwater through the filter bed. The oxygen
available in the stormwater may be consumed by the time it reaches
the lower part of the filter. This may occur during each storm or
it may only occur periodically during a period of extended wet weather.
Continued wetness sustains the bacterial biomass. With time its
thickness may be sufficient to inhibit if not terminate flow.
| Table
2. Dissolved Metal Preference |
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| *Note:
a. Likely differs with different zeolites |
The evidence for either
concern is anecdotal. Clogging of fabric by bacteria has been observed
(Johnson et al. 2003) in submerged sidewall sand filter-berms in
wetponds (Horner and Horner 1990). To what extent algae from the
pond contribute to the later observation is not known. Anaerobiosis
has been documented in one filter (Shapiro and Associates and the
Bellevue Utilities Department 1999). However, the filter had a bed
thickness of 36 inches, a drawdown time of 72 hours, and iron filings
mixed with the sand, and the filter was located in a wet climate:
conditions that provide the maximum potential for anaerobic conditions.
As anaerobiosis was limited to the lower 24 inches, substantial
removal of dissolved metals and phosphorus still occurred.
A laboratory study (Johnson
et al. 2003) suggests that drying of the upper part of a sand filter
requires several days and that the lower remains wet regardless.
It is likely that clogging is driven by the accumulation of sediments,
possibly in concert with the biofilm, and that focusing on just
the biofilm is unwarranted. However, definitive studies under field
conditions are needed.
Whether anaerobic conditions
are inherently undesirable has not been established. A concern is
the loss of previously removed dissolved phosphorus or metals. But
where neither is a focus, the concern for anaerobiosis is overstated.
Loss of phosphorus or metals previously removed is limited to that
portion complexed with iron or manganese. In an anaerobic condition
these two oxides disassociate, losing sorbed metals. Aluminum oxide-metal
complex and calcium phosphate are unaffected. The question has not
been evaluated under conditions representative of field conditions
and is hampered by a lack of understanding of each mechanism.
Anaerobic conditions
in the bottom of the filter are desired if the objective is nitrogen
removal. Ideally, nitrification occurs in the upper part of the
filter and denitrification in the bottom. Denitrification may be
enhanced by purposely flooding the lower portion of the bed. This
is achieved by placing the outlet several inches above the bottom
of the bed. The bed is configured to direct the water downward through
the bed before exiting. However, nitrification-denitrification may
be limited by the low concentration of dissolved organic matter
in the stormwater. As most dissolved organic matter is likely removed
in the upper aerobic zone of the filter, the remainder may be insufficient
to sustain denitrifiers in the bottom of the filter.
A final possible benefit
of a short drawdown time is temporary improvement in the filtration
rate during the next storm (Johnson et al. 2003).
Operating Capacity
How long a medium will effectively remove a pollutant is determined
by its operating capacity (Minton 2002). The operating capacity
is the amount of a dissolved pollutant that is removed to the point
where the concentration of the pollutant in the effluent of the
filter reaches the specified allowable concentration. Such a specification
does not occur with stormwater unless a total maximum daily load
has been established for the particular receiving water.
The operating capacity
is presented visually in Figure 1. A medium is placed in a column.
Water with the pollutant of interest is passed downward through
the column. The effluent concentration is monitored. With time the
medium becomes saturated with the pollutant. The saturation
front moves downward through the medium. The concentration
of the pollutant begins to increase, dramatically increasing when
the saturation front nears the bottom. When the allowable effluent
concentration is reached, the medium is replaced. This value is
identified at a relatively low concentration in Figure 1. It more
often may be located farther to the right where the curve rises
dramatically. In this case the medium should be replaced when the
slope of the curve changes abruptly, called the breakpoint. The
y-axis, C/C°, is the ratio of the effluent to influent concentration.
| Figure 1. Classic Column Test |
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Operating capacity is
not the same and is considerably less than the maximum saturation
capacity. Operating capacity is a function of the concentration
of the pollutant seen by the medium. The lower the operating
concentration, the lower the operating capacity in proportion to
the maximum capacity.
The maximum capacity
is determined by mixing different known quantities of water with
the pollutant of interest and with the medium. The mixture is then
mixed for several hours. The residual concentration of the pollutant
is determined, and the difference between the initial and final
pollutant concentration in water gives the maximum capacity.
It is imperative that
column and batch tests be performed within the influent concentration
range found in stormwater. If metals are the pollutant of interest
the tests should be done with a mixture of the metals known to be
present in stormwater, including iron and aluminum. It is also preferable
that the test water be stormwater, not potable water to which salts
are added. The chemistry of stormwater is complex as previously
noted. The medium should be tested for the leaching of regulated
pollutants, which may occur at the low concentrations present in
stormwater (Johnson et al. 2003).
Operating capacity is
affected by the size and porosity of the medium. A more porous medium
has more sorption sites, as do smaller media. Smaller media also
enhance contact of the pollutant with the media. However, using
a smaller medium is limited by hydraulic conductivity considerations.
Given the rather low
concentrations of dissolved pollutants in stormwater, it follows
that the operating capacities of most, if not all, media are very
low. The sizing of media filters must be based on the operating
capacity, not the maximum capacity. The medium with the highest
capacity does not necessarily have the best performance (Johnson
et al. 2003).
Which Comes First: Clogging
or Capacity Exhaustion?
What will occur first:
clogging by sediments or exhaustion of the sorption capacity? Likely
the former will (Johnson et al. 2003), despite the relatively low
operating capacities. The maintenance solution is to periodically
remove the sediment and the top inch (2.5 centimeters) of sand to
return its hydraulic capacity, with less frequent replacement of
the entire bed.
Design Criteria
The limited number of studies of either natural or amended
sand prevents definitive conclusions regarding design criteria for
sorptive filters. Bed surface area matters for the removal of sediment.
Bed volume matters for dissolved pollutants. Volume defines both
performance and long-term capacity. In the second article of this
series (Stormwater, January/February 2005, www.stormh20.com/sw_0501_revisiting.html)
it was proposed that a bed thickness of 18 inches is likely excessive
if the sole objective is the removal of sediment with attached pollutants.
A depth of 18 inches or more may be appropriate for the removal
of dissolved pollutants. In short-term laboratory studies, 15 minutes
were sufficient for maximum removal of dissolved metals, suggesting
a shallow bed is satisfactory. However, the need for volume and
therefore operating capacity may require otherwise deeper beds than
suggested by removal rates. The exception would be the removal of
dissolved metals by organic litter as it is likely a bed surface
phenomenon.
The appropriate mix of
amendment media with sand depends on the particular amendment medium
and its operating capacity. Best performance may be obtained with
two or more amendments. There is not necessarily a correlation between
performance and capacity. Best results may be obtained with two
amendments: one with a relatively high capacity but lower performance,
and another that exhibits the reverse (Johnson et al. 2003).
Few studies of operating
capacity have been conducted, preventing the definition of mixture
percentages at this time. Capacities likely differ considerably
between media of the same generic type: for example, zeolites. Consequently,
tests should be foregone only if the particular medium has been
previously evaluated. Manufacturers of filter systems should test
their media under realistic conditions and should develop appropriate
specifications to ensure continuity of media quality. Tests should
be performed on sands available in each region to ascertain if removal
of dissolved phosphorus or metals occurs and, if so, to determine
their capacity. Local jurisdictions can specify the most effective
sand in their region. Test procedures are well established (Minton
2002).
Flow-Through Swales
The distinction of flow-through swales is made from infiltration
swales in which essentially all of the stormwater escapes the swale
by infiltrating the ground. Here the focus is with swales in which
the majority of the stormwater passes to the far outlet of the swale,
continuing as surface flow to the receiving water. The soils in
these swales have a relatively poor infiltration rate. Care is advised
when considering the benefit of infiltration. Keep in mind that
infiltration does not result in 100% removal of the pollutants from
the infiltrated stormwater. Furthermore, the higher the infiltration
rate, the less effective the soil at removing pollutants, because
there is less contact time.
Grass and other rooted
vegetation do not remove dissolved pollutants directly from stormwater
as it passes through the swale. Plants obtain nutrients for growth
from the pore water in the soil. Hence, dissolved pollutants to
be removed must contact the soil. This is not likely for the majority
of the stormwater, although turbulence may provide the opportunity
with sufficient residence time. The question therefore arises as
to potential effectiveness of vegetated swales absent infiltration.
Dissolved metals, pesticides,
and petroleum hydrocarbons may be removed by dead organic litter
that has accumulated at the base of the grass stems. Free petroleum
hydrocarbons are so hydrophobic that they sorb directly to grass.
Studies of bioretention systems have established that a surface
layer of mulch provides high reductions in metals; however, all
of the stormwater passes through the mulch. This is not the case
with flow-through swales.
The removal of dissolved
metals has been observed but with a loss of dissolved phosphorus,
likely from fertilization and/or fall dormancy (Caltrans 2004; Cammenmeyer,
no date).
Final Observations
An understanding of the specific mechanisms of removal in both
swales and sand filters is needed. Lacking is an understanding of
whether and why removal capacity differs among sands and decreases
with time and influent concentration. Classic sorption capacity
tests used for decades in wastewater and potable water treatment
are applicable to stormwater treatment (Minton 2002). The tests
should be performed on each medium, sand or otherwise, before placement
in a filter. This is particularly important when determining the
amount of an amendment to add to sand. The amount of bacterial mass
that grows in sand filters is unknown and therefore its potential
effects on the concentrations of dissolved metals and nutrients
are also unknown.
Final Observations
on the Series
The time of simply measuring what is coming into and out of
a treatment device to measure performance is long past. Such studies
were useful early in the development of our understanding of treatment
systems. It is, however, no longer of value to know only how well
a system performs. It is also necessary to know how a system performs.
This requires the analysis of constituents not of direct concern,
such as iron, aluminum, and sulfate, and both the particulate and
soluble species. It requires a definition of influent and effluent
particle size distributions. It requires inclusion of gross solids,
such as leaves and litter. It requires sampling of most if not all
storms during the monitoring period, the continuous monitoring of
flow, and the analysis of mass balances.
Such understanding of
how a system performs also requires analysis of soils in wetponds
and wetlands before flooding as to chemistry and sorption capacity
for pollutants of interest and a similar analysis of media used
in filtration and infiltration devices, including seemingly simple
sand and soil. It requires analysis of the chemistry of wetland
vegetation. It also requires an understanding of all of the factors
that affect performance and a full description of the test facility
in reports so that engineers are able to consider the relationship
of specific design criteria to performance.
References
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Gary R. Minton, Ph.D.,
P.E., is an independent consultant on stormwater treatment with
Resource Planning Associates. He is author of the book Stormwater
Treatment: Biological, Chemical, and Engineering Principles.
SW
July/August 2005
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