W ETLAND C HEMISTRY OF C ARBON Dissolved Inorganic Carbon Of the hundreds of carbon compounds that may occur in the wetland environment, relatively few are inorganic.. O RGANIC C ARBON B
Trang 1Carbon compounds interact strongly with wetland
ecosys-tems The carbon cycle in wetlands is vigorous and typically
provides carbon exports from the wetland to receiving
eco-systems Many internal wetland processes are fueled by
car-bon imports and by the carcar-bon formed from decomposition
processes
Treatment wetlands frequently receive large external
supplies of carbon in the added wastewater Any of several
measures of carbon content may be made, with biochemical
oxygen demand (BOD) being the most frequent in the
treat-ment of municipal wastewater Degradable carbon compounds
are rapidly utilized in wetland carbon processes At the same
time, a variety of wetland decomposition processes produce
available carbon The balance between uptake and
produc-tion provides the carbon exports In general, the amounts of
carbon cycled in the wetland are comparable to the quantities
added in domestic wastewater
The growth of wetland plants requires carbon dioxide
(CO2) for photosynthesis A variety of organisms release CO2
as a product of respiration Many pathways lead to the
micro-bial production of CO2, as well as methane (CH4) Both gases
dissolve in water to a limited extent; so there are active
trans-fers of carbon to and from the atmosphere
In terms of treatment, it is therefore not surprising to find
good carbon reductions for the added wastewater,
accompa-nied by nonzero background levels of various carbon
com-pounds and the related BOD For purposes of wetland design
for BOD removal, the challenge is to find relatively simple
design tools despite the enormously complex set of wetland
functions
8.1 WETLAND CARBON SPECIATION
AND PROCESSING
A wide spectrum of carbon compounds exists in either
dis-solved or particulate forms in aquatic systems The usual
dividing line is a 0.45-Mm filter The following distinctions
are made as a result of analytical methods:
TC total carbon (includes all dissolved and
In soils or biomass, samples are subjected to combustion and dissolution, followed by analysis for total carbon
BOD, COD, AND TOC
Different analytical techniques are used to measure the amount
of organic material in the wastewater BOD is a measure of the oxygen consumption of microorganisms in the oxidation
of organic matter It is measured as the oxygen consumption
in an airtight incubation of the sample This test normally runs for five days, and the result is then more properly des-ignated as BOD5 Some oxygen may be used in nitrification
if the necessary organisms are present in the sample If this potential nitrogenous oxygen demand is inhibited chemically during the test, the result is carbonaceous biochemical oxy-gen demand (CBOD5)
Chemical oxygen demand (COD) is the amount of a cal oxidant, usually potassium dichromate, required to oxidize the organic matter This measure is larger than BOD, because the strong oxidant attacks a larger group of compounds How-ever, nitrogenous compounds, such as ammonia, are not oxi-dized by the COD test Oxygen or oxidant consumption may
chemi-be measured chemi-before or after filtration, leading to measures of total and soluble BOD and COD In the wetland environment, the presence of humic materials leads to COD values that are much larger than BOD values In a northern peatland, the ratio was approximately 0.05 (BOD5 5 mg/L:COD 100 mg/L) (unpublished data from the Houghton Lake, Michigan, peatland) At Tres Rios, Arizona, wetlands treating nitrified secondary effluent, four wetlands gave ratios of 0.055 o 0.004, averaged over seven years In municipal wastewaters, the ratio
is typically 0.4–0.8 (Metcalf and Eddy, Inc., 1991) Industrial wastewaters may have lower ratios
Total organic carbon (TOC) is measured by chemical oxidation followed by analysis for CO2 In a northern peat-land, the ratio BOD5:TOC was approximately 0.2 (BOD5 5 mg/L:TOC Lake peatland), and was 0.28 at Estevan, Saskatchewan At Tres Rios wetlands treating nitrified secondary effluent, four wet-lands gave ratios of CBOD5:TOC 0.25 o 0.08, averaged over
Trang 2seven years In municipal wastewaters, the ratio is 1.0:1.6
(Metcalf and Eddy Inc., 1991)
The interrelation among the various measures of carbon
and oxygen demand are given in Table 8.1 The interpretation
of these ratios is that natural wetlands cycle at low levels of
biologically usable carbon compounds, whereas municipal
wastewaters are rich in usable carbon compounds
Wetlands are efficient users of external carbon sources,
manifested by excellent reductions in BOD5 and COD
How-ever, wetlands possess nonzero background levels of both
BOD and COD, which depend on the type and status of the
wetland Typical ranges for background concentrations are
1–10 mg/L for BOD5 and 10–100 mg/L for COD
W ETLAND C HEMISTRY OF C ARBON
Dissolved Inorganic Carbon
Of the hundreds of carbon compounds that may occur in the
wetland environment, relatively few are inorganic Dissolved
inorganic carbon consists primarily of CO2, carbonate, and
bicarbonate
In pure water solution, the principal carbonate species
are related to atmospheric CO2by the temperature and
pH-dependent dissolution and dissociation series:
2
3
H CO2 3
(8.6)
the notation of Pankow (1991) has been adopted Brackets indicate the concentration of the chemical species, in molar-ity; and all are in water except for atmospheric CO2 The
value of the equilibrium constant Ky 650, and hence most
of the dissolved carbon is present as CO2 Equations 8.1–8.6 may be solved for concentrations, given the partial pressure
of CO2 and the various equilibrium constants
K
TABLE 8.1 Comparison of Oxygen Consumption Parameters for Various Waters
From Crites and Tchobanoglous
Source: WWTP values from Crites and Tchobanoglous (1998) Small and Decentralized Wastewater Management Systems McGraw-Hill, New York; Metcalf and Eddy Inc (1991) Wastewater Engineering, Treatment, Disposal, and Reuse Tchobanoglous and Burton (Eds.), Third Edition, McGraw-Hill, New York.
Trang 3CO H CO
2 3
2
§© ¶¸ K K H K P
The equilibrium constants, and hence the various
concentra-tions, are all pH- and temperature-dependent These forms
are distributed in water at 25°C as shown in Figure 8.1
(Pan-kow, 1991) However, it must be noted that wetland waters
are more complex than the pure water system and therefore
will not follow such idealized chemistry precisely
Modifi-cations of the calculation (APHA, 1992) deal with expected
deviations due to dissolved solids, but not the full suite of
biological variations that may be expected in wetlands
Pro-duction and consumption of CO2 in the wetland may
signifi-cantly alter the chemical balance in the water
An important feature of the carbonate system is its
influ-ence on pH under mediation by algae Algal consumption of
CO2 drives pH upward, and may give rise to 9 pH 10 in
unshaded wetland environments or ponds
Precipitates
A variety of cations can precipitate carbonates under certain
conditions The most important is calcium carbonate, CaCO3
A major process in periphyton-dominated wetlands is
chemi-cal precipitation of CaCO3 under conditions of high pH created
by the algae (Gleason, 1972) Similarly, in beds of submerged
aquatic vegetation, CO2 and bicarbonate are consumed during
photosynthesis, thereby raising the water column pH and
pro-moting CaCO3 precipitation (Dierberg et al., 2002).
A variety of cations can precipitate carbonate under
cer-tain conditions Some important mineral precipitates in the
wetland environment are:
Calcite: CaCO
Aragonite: CaCO
Magnesite: MgCO
3 3 3D
Dolomite: CaMg(CO )3 2
Calcium carbonate saturation indices may be calculated in
a number of ways (APHA, 1992) However, overall carbon
mineral chemistry is very complex; consequently, accurate calculations of solubilities are generally not possible, espe-cially in wetland environments
O RGANIC C ARBON
Biomass: Growth, Death, Decomposition
The wetland cycle of growth, death, and partial decomposition uses atmospheric carbon, and produces gases, dissolved organ-ics, and solids (Figure 8.2) Decomposition involves the sugars, starches, and low molecular weight celluloses in the dead plant material Gaseous products include methane and regenerated
CO2 A spectrum of soluble large organic molecules,
collec-tively termed humic substances, are released into the water The
solid residual of plant decomposition is peat or organic ment, which originated as celluloses and lignins in the plants These wetland soil organics are broadly classified as fulvic material, humic material, and humin, based upon whether they are acid soluble, base soluble, or insoluble (NRCC, 1979).The sediments, soils, and biomass in a wetland contain major proportions of carbon The carbon content of 28 species
sedi-of wetland plants has been reported by Boyd (1978) as 41.1%
o 0.7% (dry weight, mean o SE) Typha latifolia values from
30 sites ranged from 43.3% to 47.2% (Boyd and Hess, 1970)
Reddy et al (1991) reported 44.0% o 2.5% for peats in the
upper 30 cm of the soil column Soil scientists sometimes use
a concentration of 58% for the carbon content of soil organic matter (the Van Bemmelen factor; Collins and Kuehl, 2001) Thus nearly half of the dry wetland plant and soil material is carbon
The internal wetland carbon cycle is large A general idea
of the magnitudes of the various carbon transfers in a northern treatment marsh may be gained from considering the annual growth and decomposition patterns (see Chapter 3) A eutrophic treatment marsh grows about 3,000 dry g/m2 of aboveground biomass each year, with a carbon content of about 43% This translates to an annual average requirement for 35 kg/ha·d of carbon In northern climates, this requirement is utilized dur-ing a growing season of approximately four months In the case of emergent macrophytes, some of this carbon may be withdrawn from the atmosphere However, submerged veg-etation draws carbon from the aquatic carbonate system.Decomposition of the resultant litter returns a significant portion of that carbon to the atmosphere and to wetland waters, but in treatment wetlands, a small fraction, on the order of 15%
or 20%, is stored in accreted soil and sediments That storage (burial) fraction therefore amounts to about 5 kg/ha·d as an annual average for the eutrophic marsh example The balance, about 30 kg/ha·d, is processed via one or more mechanisms involving a variety of electron acceptors (oxidants), or via anaerobic digestion which generates methane
The oxygen consumed by aerobic decomposition of sediments and litter is termed the sediment oxygen demand (SOD) In stream environments with large wastewater influ-ences, the rate of consumption of oxygen by the stream sediments may be estimated as 20–100 kg/ha·d (Metcalf and
FIGURE 8.1 Distribution of carbonate species in water at 25°C The
partial pressure of CO 2 in the air is taken as 3.16 r 10 −4 atm (From
Metcalf and Eddy Inc (1998) Wastewater Engineering, Treatment,
Disposal, and Reuse, Tchobanoglous et al (Eds.), Fourth Edition,
McGraw-Hill, New York Reprinted with permission.)
Trang 4Eddy Inc., 1991) In the eutrophic marsh example, if all the
decomposition were to proceed via oxidation with dissolved
oxygen as the electron acceptor, and CO2 as the product, the
equivalent SOD loading would be (32/12) r 30 80 kg/ha·d
As will be subsequently shown, this potential SOD loading is
at the upper end of the range of external BOD loadings (BLI)
for treatment wetlands
The wetland environment is more complicated than the
stream environment Some of the carbon is processed
above-water, as standing dead material oxidizes Some of the
sub-merged sediments and litter are processed into soluble organic
compounds that contribute to CBOD in the water, thus
cre-ating a nonzero background CBOD in a wetland
environ-ment Starches, sugars, and cellulose are degraded to amino
acids and fatty acids (Reddy and Graetz, 1988) In addition
to dissolved oxygen, a variety of electron acceptors may be
involved in decomposition
C ARBON P ROCESSING IN W ETLAND N ECROMASS AND S OILS
A rough representation of the various decomposition
“reactions” may be set down (Mitsch and Gosselink, 1993)
These occur in different horizons in the wetland, as indicated
3
2 +
FIGURE 8.2 Carbon storages and transfers in the wetland environment DC dissolved carbon; PC particulate carbon; DIC dissolved
inor-ganic carbon; DOC dissolved orinor-ganic carbon; CH 4 methane; CO 2 carbon dioxide Biomass carbon consists of living and dead biomass, as
well as organic decomposition products (From Kadlec and Knight (1996) Treatment Wetlands First Edition, CRC Press, Boca Raton, Florida.)
Trang 5CH COO3 4 H2l 2 CH4 H O2 OH
The relative percentages of these reactions were
inves-tigated in controlled SSF wetland microcosms by Burgoon
(1993), using acetate as the carbon source His results
dem-onstrated that all routes can be important, depending upon
physical and chemical conditions
It is apparent that the wetland provides a spectrum of
potential pathways for the utilization of organic carbon
com-pounds Sufficient information is not available to quantify
both the complex chemistry and the spatial distribution of
chemical compounds Therefore, the interactions must be
described via correlations and rate equations, which are
sup-portable by wetland performance data
8.2 BOD REMOVAL IN FWS WETLANDS
A large amount of BOD data now exists for FWS wetlands
treating a variety of wastewaters There are a number of ways
to summarize this information, including removal rate
mod-els and graphical summaries When waters with moderate
to large concentrations of BOD flow through a wetland, a
decrease in concentration to a nonzero plateau is typically
observed This behavior is illustrated in Figure 8.4 for one of the continuous flow Sacramento, California, wetlands (Nolte and Associates, 1997) Samples were taken along the wetland
Zone IV and V
Eh = –300 to 100 mV Anaerobic respiration
Dissimilatory nitrate reduction
Fe S
Short chain fatty acids
Energy
Methane formation
Organic
CH4
H2
FIGURE 8.3 Pathways of organic carbon decomposition in wetland soils Aerobic, facultative anaerobic, and obligate anaerobic processes
are all typically present at different depths in the soil (From Reddy and Graetz (1988) In The Ecology and Management of Wetlands Hook
(Ed.), Croom Helm, London, United Kingdom, pp 307–318 Reprinted with permission.)
5 4
3 2
Time (days) 1
0 0 5
10
15 20 25
FIGURE 8.4 Profiles of BOD concentration in Cell 7B of the
Sacra-mento, California, treatment wetlands on May 3 and May 4, 1995 The
plateau is at 3.1 mg/L (Data from Nolte and Associates (1997)
Sac-ramento Regional Wastewater Treatment Plant Demonstration lands Project 1996 Annual Report to Sacramento Regional County
Wet-Sanitation District, Nolte and Associates: Sacramento, California.)
Trang 6length, at positions corresponding to increasing nominal
deten-tion time The same sort of response is seen in the results
of Lakhsman (1981) for batch wetland treatment of lagoon
effluents A set of wetlands were charged with wastewater,
then closed in, with no water additions or withdrawals Typical
response data showed a sharp decrease in BOD5 to a nonzero,
fluctuating background (Figure 8.5) The decrease is steep—
perhaps exponential—but to a nonzero background BOD5
A NNUAL I NPUT –O UTPUT C ONCENTRATION R ELATIONS
The concentration of carbonaceous compounds is reduced
in FWS wetlands for incoming concentrations above
back-ground If, however, incoming BOD is below background,
concentrations may increase upon passage through the
sys-tem As inlet concentrations increase, outlet concentrations
increase, in a log-linear progression (Figure 8.6) There is
considerable intersystem variability, but the data exhibit a
lower bound, which may be interpreted as the lowest
back-ground concentration corresponding to a given inlet
concen-tration This curve is approximated by
iimit background BOD concentration, mg/L
Depending on hydraulic conditions, and the character of the
incoming BOD, individual wetlands will typically exhibit
different C*-values as model calibration parameters, which
may be larger than C**.
F IRST -O RDER M ODELING
The P-k-C* first-order model can readily account for
obser-vations, for appropriate values of parameters (see Chapter 6)
However, parameter values are known to depend on system hydraulics (Kadlec, 2000), as well as on speciation of the BOD (Crites and Tchobanoglous, 1998; Kadlec, 2003a).BOD and COD are water quality parameters measured by procedures that lump individual chemical compounds into an overall, or total, concentration for that class of materials It is clear that the individual components of such mixtures may be degraded or removed at different rates, and that there is a cor-responding difference in removal rate constants (Crites and
Tchobanoglous, 1998; Tchobanoglous et al., 2000; Kadlec,
2003a) There is therefore a distribution of rate constants across the various mass fractions of the mixture As water con-taining such a mixture passes through the wetland, its compo-sition changes because different fractions of the mixture are
reduced at different rates The mixture becomes weathered, a
term coined to describe the selective stripping of light volatile materials upon exposure to outdoor environments In the case
of BOD and COD, the easy-to-degrade substances are lost first; more recalcitrant compounds persist for longer times
The BOD test itself reflects only a fraction of the naceous mixture, because it is terminated before all compo-nents are oxidized For municipal wastewater, the five-day BOD test typically measures about two thirds of the ultimate BOD (UOD) (Metcalf and Eddy, Inc., 1991; Crites and Tcho-banoglous, 1998)
carbo-Effects of Lumping on Removal Models
The potential effects of speciation in lumped contaminant measures, particularly BOD, as manifested in changing rates, have been known for several years (Tchobanoglous, 1969;
Crites and Tchobanoglous, 1998; Shepherd et al., 2001)
35 30 25
Time (days) 5
FIGURE 8.5 The progression of BOD concentrations in three
wet-lands operated in the batch mode The plateau is at 11.3 mg/L (Data
from Lakhsman (1981) A Demonstration Project at Humboldt to
Provide Tertiary Treatment to the Municipal Effluent Using Aquatic
Plants SRC Publication No E-820-4-E-81 74 pp Saskatchewan
10 1
0.1 0.1 1 10 100
1,000
Co = Ci
Trend Lower
FIGURE 8.6 Input–output concentration for BOD in FWS
wet-lands Each point represents an annual average for one wetland There are 385 wetland·years of data for 138 wetlands The trend
line is y 1.13 x0.67 (R 2 0.75 logarithmic) The lower bound line is
y 0.6 0.065 x, and includes 98% of the annual averages.
Trang 7Crites and Tchobanoglous (1998) set forth a formulation for
a “retarded rate expression.” However, Kadlec (2003a)
dem-onstrated that this concept was subsumed by a relaxed
tanks-in-series (TIS) model The P-k-C* model is here defined to
be (see Chapter 6):
o i
The parameter P accounts for two effects: the detention time
distribution (DTD) and the k-value distribution (kVD) (see
Chapter 6) The value of P is always less than the number
of tanks determined from a tracer test For broad
distribu-tions of k-values, such as may occur for BOD, a
hydrau-lic TIS number of four (see Table 6.3) will be reduced to a
P-value of one or two However, the C*-value in Equation
8.20 reflects several possible different causes There may be a
real irreducible component of BOD (hard to imagine, because
it all disappears in the lab test), or there may be wetland
eco-system feedback of BOD constituents But in addition, DTDs
and kVDs may create an apparent C* as an artifact of model
parameter fitting These may be considered “bypassing C*”
and “weathering C*”, respectively.
Reasonable data fits may be obtained for specific wetlands
or specific sites Seven Gustine, California, wetlands were
operated at different hydraulic loadings (different detention
times) for a calendar year (Walker and Walker, 1990) The
P-k-C* model parameters determined from that input–output
data were: P 1, k 63 m/yr, and C* 9.7 mg/L (R2 0.60)
Those parameters also provided a reasonable fit to transect
data (Figure 8.7, R2 0.59) However, it is uncommon to
have multiple wetlands and multiple loadings from which to
derive these types of calibrations
Concentration Profiles and Modeling Pitfalls
Difficulties with the P-k-C* first-order model are compounded
by the problem that data sets are very often poorly conditioned
to produce good estimates of both k and C* by any of the
sev-eral methods of parameter estimation This is easily visualized
from Figures 8.4, 8.5, and 8.8, which contain examples of the
early exponential decline (governed by k), together with the
late plateau (governed by C*) There are insufficient data in
the exponential region for Sacramento and Humboldt to get
a good estimate of k, but plenty of data to define C*
Con-versely, the Arcata pilot, Benton, and Gustine data sets never
reach a plateau; all the data is concentrated in the
exponen-tial decline region Thus, for these wetlands, transect data will
provide a good estimate of k, but a very poor estimate of C*
Input–output data for these sites may nonetheless be fitted to the model In addition to the Gustine results given above, Ben-
ton input–output data over a two-year span resulted in P 1,
k 260 m/yr, and C* 5 mg/L At the Arcata pilot, input– output data over a two-year span resulted in P 1, k 53 m/yr, and C* 4 mg/L.
It is tempting to arbitrarily pick some low concentration to
represent C*, but that is counter-indicated by the importance
of C* in wetland sizing, as shall be seen in the following
sec-tions There is not an existing method to make such an estimate with confidence One need look no further than data from two wetlands in the same geographical region: Humboldt, Sas-
katchewan, shows C* 11.3, but not far away, Oak Hammock, Manitoba, shows C* 2.4 Both are batch systems treating
domestic lagoon effluent We shall also see that k-values are
widely variable, both across years for one wetland nual variability) and across wetlands (intersystem variability) Thus, to the dismay of researchers seeking to do THE definitive design model calibration study, no such study can be trusted in and of itself
(interan-1.0 0.9 0.8 0.7 0.6 0.5 0.4 Fractional Distance 0.3
0.2 0.1 0.0 0 100 200
300
400 500 600 700
800
Transect Data
P-k-C* Model
FIGURE 8.7 BOD profile in the flow direction for wetland 1D at
Gustine, California The model curve was derived from independent input–output data for seven wetlands over a calendar year (From
Kadlec and Knight (1996) Treatment Wetlands First Edition, CRC
Press, Boca Raton, Florida.)
12 11 10 9 8 7 6 Nominal HRT (days) 5
4 3 2 1 1
10
100 1,000
0
Gustine Arcata Pilot Benton
FIGURE 8.8 Initial exponential declines in BOD for FWS
wet-lands These systems did not achieve any apparent plateau.
Trang 8Distribution of k-Values
It is instructive to examine multiple data sets that provide a
dis-tribution of k-values and C*-values If all data are considered
together, the inter- and intrasystem effects are compounded
by a shift in the probable mechanisms of BOD reduction, as
detailed in Equations 8.10–8.18 As loadings increase, aerobic
processes become less of a probable factor, and are replaced by
anoxic processes Therefore, four levels of inlet concentration
are considered: tertiary (0 Ci 30 mg/L); secondary (30 Ci
100 mg/L); primary (100 Ci 200 mg/L); and “super” (Ci
200 mg/L) The effect of BOD weathering, which produces
lower k-values as reaction proceeds, is quite strong for BOD
Data fits are better for P-values that are considerably lower
than the tracer-determined number of tanks-in-series (NTIS)
values In general, data fits are best at P 1, as noted earlier for
Gustine, Benton, and Arcata If the annual performance
data-base is used for calibration, a value of P somewhat less than 1
is found, and therefore analysis has been performed using P
1 For purposes of uniformity, the presumptive C*-values are
taken to be those of Equation 8.20, leading to C* 2, 5, 10, and
20 mg/L for the four categories, respectively
The resultant annual average k-values are given in
Table 8.2 The median values are not much different for
ter-tiary, secondary, and primary applications (median 37 o
4 m/yr), but increases for the stronger influents (super) to
189 m/yr The spread of these distributions is quite large,
imply-ing that the characteristics of individual wetlands, or individual
years in the period of record, can have strong influences on
performance
Annual Loading Relations
The BOD concentration produced in treatment wetland
depends upon three primary variables (area, water flow, and
inlet concentration), as well as numerous secondary ables (vegetation type, internal hydraulics, depth, event pat-terns, and others) It is presumed that the area effect may be combined with flow as the hydraulic loading rate (flow per unit area), because two side-by-side wetlands with double the flow should produce the same result as one at nominal flow Therefore, two primary variables are often considered:
vari-hydraulic loading rate (q HLR) and inlet concentration (Ci).Previous performance analyses have been based upon these two variables (Kadlec and Knight, 1996)
An equivalent approach is to rearrange the primary
vari-ables, without loss of generality, by using BLI rate (q·Ci) and
concentration (Ci) Thus it is expected that the outlet
concen-tration produced (Co) will depend upon BLI and Ci A cal display has often been adopted in the literature (Kadlec and Knight, 1996; U.S EPA, 2000a; Wallace and Knight, 2006) In the broad context, multiple data sets are represented by a trend
graphi-that shows decreasing Co with decreasing BLI (Figure 8.9) Scatter is presumably due to secondary variable differences, such as the relative proportions of different vegetation types, hydraulic efficiencies, and other factors The points at lowest loadings are for systems receiving very low BOD
Each point in Figure 8.9 represents the average of one year’s data for a given FWS wetland Both BOD and CBOD data are represented; therefore, it is understood that some of the scatter is due to the difference between these two measures The use of annual averages removes seasonal variability, if any, and precludes the effects of synoptic error (see Chapter 6)
M ODEL C URVES
The data cloud in Figure 8.9 has been reproduced in
various parameter values The hydraulic loading is also an
TABLE 8.2 Distribution of Annual Areal Rate Coefficients
kA (m/yr) for BOD in FWS Wetlands
Trang 9independent parameter in that model It is seen that the data
are bounded by Line 1, which represents high C* and low
HLR and k; and Line 2, which conversely represents low C*
and high HLR and k These correspond to a very wide range
of potential k and C*-values; in fact, so wide that there is little
resolution of the data by the model Lines 3 and 4 represent a central tendency of the data, but do not entirely resolve either
the k or C* variability Thus it is seen that the intersystem data
FIGURE 8.9 Outlet BOD concentration versus BOD loading for FWS wetlands Each of the 383 points represents an annual average for one
of 136 wetlands Data groups are for tertiary (0 C i 30 mg/L); secondary (30 Ci 100 mg/L); primary (100 Ci 200 mg/L); and “super”
Trang 10does not aid in pinpointing narrow ranges of model parameters
In semiquantitative terms, the ranges that span the data are:
15 < < 250 m/yr
2 < < 20 mg/L
1 < < 2
k C P
*
It is noteworthy that the central tendency reported by Kadlec
and Knight (1996), i.e., k 34 m/yr and C* y 3.5 mg/L for
P ∞, is still a good central estimate for the much larger data
set now available
V ARIABILITY IN A NNUAL P ERFORMANCES
Interestingly, the intrasystem interannual variability
(year-to-year variability for one wetland with several (year-to-years’ data) is not
necessarily much smaller than the intersystem variability
(vari-ability among several wetlands) Some single wetlands span
the data cloud from one extreme to the other for different years
of operation As examples, the annual values of a few wetlands
have been identified in Figure 8.11 For some, such as
Poinci-ana, Arcata Enhancement, and Cannon Beach, the interannual
variation is a significant fraction of the intersystem variation at
the same loading (about
annual variability, such as Reedy Creek and Dove Creek, but
still about half of the intersystem variation
In terms of model parameters, the result is a large spread
in k-values This may be illustrated by examining the spread
of k-values (for P 1 and C* 2) for the various years and
systems at Arcata, all working at the same site (Figure 8.12)
Out of this modeling effort, the central messages are that
(1) the P-k-C* model spans the intersystem data (as it should),
but that (2) there is no resolution of the wide range of parameter
values that might be selected Consequently, the P-k-C* model
by itself is insufficient for wetland design This simple model can be fit to a single profile or input–output data set, and repre-sent it very well; but inherent variabilities remain quite large It
is not possible to say with certainty what next year’s k-value will
be, nor what the next wetland’s k-value will be Unfortunately, this is also true for C*-values It is informative to seek further
understanding of the factors that may control performance
E FFECTS OF D ESIGN AND O PERATING C ONDITIONS
Water Depth
were possible as limiting cases of first-order removal models:
FIGURE 8.11 Single system performance within the general milieu of annual data.
Rate Constant (m/yr)
FIGURE 8.12 Rate constants for BOD removal for the aggregate
of Arcata, California, data sets The basis is C* 2 mg/L and P 1
There are 23 annual average points for the pilot cells (12 cells over two years), 12 years for the combined treatment marsh cells, and 12
years for the combined enhancement marsh cells The site k 54 o
39 m/yr (mean o SD).
Trang 11either (1) the contaminant was processed everywhere within
the water column, in proportion to the water volume; or (2)
the contaminant was processed in proportion to the wetland
planar area In terms of model equations, the influence is
exerted through the depth dependence of removal:
The question arises whether kA is constant, or whether kV is
constant In the former case, the extra detention time created
by deeper operation is of no benefit, because kV is reduced
as depth increases; in the latter case, increased depth creates
no penalty in decreased kV-values, and performance can be
increased by increasing the water depth
As one test of the two possibilities, operational data
from a wetland with sequentially varied depths may be
examined The Listowel wetlands were operated at various
depths over a four-year period, with the resulting ability
to examine Equation 8.22 There is a strong increase in kV
-values with (1/hn) for depths above about 5 cm (Figure 8.13),
indicating that kA is more nearly constant than kV It is
pos-sible that the drop in kV for depths less than 5 cm is due to the
incomplete wetting of the wetland surface
A second test is to compare side-by-side wetlands ated at different depths The Arcata pilot wetlands were oper-ated in that fashion for two years Each of three hydraulic loadings was replicated at two depths For each loading, the
oper-value of kV was lower at the larger depth (Table 8.3) Over the entire suite of experiments, a 35% depth increase resulted in
a 35% kV decrease This also indicates that kA is more nearly
constant than kV
Either kA or kV can be used to represent a data set or be
used in design However, the use of kV requires the
accom-panying information on water depth (h) because of the depth
dependence indicated in Equation 8.22 This depth dence also means that more detention time created by deeper water is counteracted by a decrease in the volumetric rate constant The hydraulic loading rate is not depth-dependent,
depen-25 20
15 10
Reciprocal Depth (m –1 ) 5
0 0.0 0.5 1.0
System 4 System 5 3.5
4.0
FIGURE 8.13 Variation of the volumetric rate constant for BOD
removal for Listowel, Ontario, Systems 4 and 5 The parameters P
Note: Twelve pilot cells were operated as duplicates at two depths and three hydraulic loading rates, over a period of two years, beginning one year after
start-up The P-k-C* model parameters were fixed at P 1 and C* 2 mg/L.
Source: From analysis of data in Gearheart et al (1989) In Constructed Wetlands for Wastewater Treatment: Municipal, Industrial, and Agricultural Hammer
(Ed.), Lewis Publishers, Chelsea, Michigan, pp 121–137.
Trang 12and the same data indicate that kA is nearly independent of
depth The use of areal coefficients does not require depth
For many FWS wetlands, especially large ones, depth is not
known to a reasonable degree of accuracy (see Chapter 2)
For these reasons, the parameter k is used herein.
Loading Effect on k-Values
Importantly, both kV and k depend to some degree upon BLI
rate This is the observed trend of the data from a large
num-ber of free water surface wetlands (Figure 8.14) The selected
parameters were P 2 and C* 2 mg/L Although the
cor-relation depends to some extent upon the values of P and C*,
there is no selection of these parameters that removes the
dependence of kV and k on the BLI rate.
The first-order model has increased sensitivity to loading
if the value of C* is chosen to be zero (Kadlec, 2000) Under
that assumption, the values of kV1 are nearly proportional to
BLI, or inversely proportional to the detention time, for low
hydraulic loadings The additional subscript “1” indicates
that the model contains only one parameter, the k-value, as
opposed to two (k and C*) This sensitivity is exacerbated if
the plug flow model is used, i.e., P ∞ The
near-proportional-ity of kV1PF to BLI has been repeatedly recognized (Reed et al.,
1995; Kadlec, 2000; Water Environment Federation, 2001;
Ran et al., 2004) WEF (2001) report the following relation:
k rrate constant withC*0, d-1
This dependence leads to a design paradox The required
wet-land area is inversely proportional to the k-value, whereas the
inlet BLI is inversely proportional to wetland area Suppose a BLI has been chosen as a first estimate, and the correspond-
ing k-value determined (e.g., from Equation 8.23); and the
predicted outlet BOD is too high The obvious correction is to increase area However, that lowers the inlet BLI, and accord-
ing to Equation 8.23, also lowers the k-value Clearly, this is a useless procedure Reed et al (1995) dispose of the difficulty
by ignoring Equation 8.23 This regression is an example of the spurious correlation caused by hydraulic loading appear-ing in both the abscissa and ordinate (see Chapter 6)
Temperature
The first-order model has been reliable for predicting removal rates of organic matter in most wastewater treatment pro-cesses (Metcalf and Eddy Inc., 1991) The modified Arrhe-nius relationship is commonly used to adjust the removal rate coefficient for temperature in traditional wastewater treat-ment processes:
V1 V1,20Q( 20 )
(8.24)where
-1rate constant at 20°C, dwater tempe
The treatment wetland literature is replete with the assertion that a Q-value of about 1.06 applies to FWS wet-
lands (Reed et al., 1988: 1.10; U.S EPA, 1988b: 1.10; Reed
et al., 1995: 1.06; Crites and Tchobanoglous, 1998: 1.06;
Campbell and Ogden, 1999: 1.06; U.S EPA, 2000a: 1.04)
These reports all referred to the plug flow model with C* 0
However, Kadlec and Knight (1996) could not find a perature dependence in wetland BOD data That finding was subsequently supported by analysis of more systems (Kadlec and Reddy, 2001)
tem-The two most closely related companion technologies for BOD reduction are overland flow and stabilization ponds The former involves very shallow (a few centimeters depth
at most) water flow over a vegetated surface, and the latter represent algal-aquatic systems with typical depths of one to two meters Thus, these technologies may be regarded as the shallow- and deepwater extremes of treatment wetlands The
Trang 13data from those systems yield temperature coefficients that
are close to 1.00 for ponds (1.005 o 0.014) and overland flow
(1.01 o 0.01) (Kadlec and Reddy, 2001) U.S EPA (1983a)
suggests several different design approaches for facultative
ponds, including equivalents to the first-order model
pre-sented above The suggested design temperature factors are
Q 1.085 and 1.090 However, U.S EPA (1983a) show a
data basis that produces Q 0.995 The authors explain this
as follows: “The logical explanation for the lack of
influ-ence by temperature is that the pond systems are so large
that the temperature effect is masked by other factors.” No
explanation was offered for rejecting the observed behavior
in the recommended design calculations This lack of a
tem-perature effect in ponds has more recently been reported by
Abis (2002)
Here the temperature effect on performance of
sev-eral wetland systems has been re-analyzed with the P-k-C*
model, with P 1 (Table 8.4) The Q-value is 0.985 o 0.021,
meaning slightly worse performance at higher temperatures
Little or no variance is removed by adding a Q-factor to the
model It is clear that the complex of wetland ecosystem
pro-cesses is masking the known microbial temperature
sensitiv-ity expected for suspended growth systems One candidate
explanation is oxygen transfer, which must be adequate to
justify the first-order approximation However, as seen in the
earlier section on carbon processing, many other processes
can influence BOD removal
The preponderance of evidence suggests that wetland BOD removal is not improved at higher wetland water temperatures
S EASONAL T RENDS
There are typically gentle annual cycles in the effluent BOD from FWS wetlands (Figure 8.15) A maximum is seen in spring or summer, and the amplitude of the annual cycle is
on the order of 30% of the mean (Table 8.5) The trend is described by
concentration, mg/Lmean annual conc
yearday, dyearday fomax
t t
rr maximum concentration, dannual period,
These cycles often do not reflect contemporary influent BOD
or the contemporary hydraulic loading to the wetland This is evidenced in Figure 8.15, where minima of the inlet concen-tration correspond to maxima of the outlet concentration, for relatively uniform hydraulic loading throughout the year
TABLE 8.4
Temperature Factors for the P-k-C* Model for Example FWS Wetlands
Data (years)
Trang 14The considerable scatter in effluent concentrations
con-tributes to low R2-values for the trend lines (Table 8.5) This
behavior is of concern in wetland sizing, if the peak values of
the concentrations are of importance in the regulatory
com-pliance for the project
Variability around Seasonal Trends
Because stochastic behavior is present in moderate amount,
it is necessary to quantify performance variability, and
ulti-mately to modify sizing based upon that understanding
Aver-age effluent BOD values over short time periods are subject
to variation from the annual mean The longer the averaging period, the closer the short-term mean value is to the annual mean value For FWS wetlands, average effluent BOD con-centrations are distributed approximately according to the log normal distribution Examples of these distributions are given
The averaging period has a very strong influence on the higher percentiles, which form the basis for permit require-ments The example given in Figure 8.17 shows that for the Columbia, Missouri, system, the daily maximum is about triple the monthly maximum, and the weekly maximum is about double the monthly maximum These ratios shrink as
13
Cycle In Cycle Out BOD Out
BOD In
Cycle In Cycle Out CBOD Out
CBOD In
Cycle In Cycle Out COD Out
Trang 15Sample Frequency
Averaging Period
Trend Mean (mg/L)
Trend Fractional Amplitude
CBOD
TOC
COD
* POR = period of record
100 10
CBOD (mg/L) 1
FIGURE 8.16 Frequency distributions for monthly BOD
(Can-non Beach, Oregon; Listowel, Ontario) and weekly CBOD (Arcata,
California).
32 28 24
Daily Weekly Monthly
20 16 BOD (mg/L) 12
8 4 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.7 0.8 0.9 1.0
FIGURE 8.17 Frequency distributions at the Columbia, Missouri,
wetlands for daily (five days out of seven), weekly (average of five dailies), and monthly BOD values (average of 22 dailies) The 90th percentile is about 1.6 times the mean However, the maximum daily value is about triple the mean.