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Modeling nitrate removal in a denitrification bed

Ehsan Ghane a,*, Norman R. Fausey b, Larry C. Brown a

a
Department of Food, Agricultural and Biological Engineering, Ohio State University, Columbus, OH 43210, USA
b
USDA Agricultural Research Service, Soil Drainage Research Unit, Columbus, OH 43210, USA

article info abstract

Article history: Denitrification beds are promoted to reduce nitrate load in agricultural subsurface drainage
Received 13 June 2014 water to alleviate the adverse environmental effects associated with nitrate pollution of
Received in revised form surface water. In this system, drainage water flows through a trench filled with a carbon
22 September 2014 media where nitrate is transformed into nitrogen gas under anaerobic conditions. The
Accepted 19 October 2014 main objectives of this study were to model a denitrification bed treating drainage water
Available online 30 January 2015 and evaluate its adverse greenhouse gas emissions. Field experiments were conducted at
an existing denitrification bed. Evaluations showed very low greenhouse gas emissions
Keywords: (mean N2O emission of 0.12 mg N m
2 min
1) from the denitrification bed surface. Field
Arrhenius experiments indicated that nitrate removal rate was described by MichaeliseMenten ki-
Bromide tracer netics with the MichaeliseMenten constant of 7.2 mg N L
1. We developed a novel deni-
Drainage water trification bed model based on the governing equations for water flow and nitrate removal
Forchheimer kinetics. The model evaluation statistics showed satisfactory prediction of bed outflow
Greenhouse gas nitrate concentration during subsurface drainage flow. The model can be used to design
Woodchip bioreactor denitrification beds with efficient nitrate removal which in turn leads to enhanced
drainage water quality.
2014 Elsevier Ltd. All rights reserved.

Bednarek et al., 2014). The bed type, also known as a wood-

1. Introduction
For economic crop production, farmers in humid and semi-
humid regions install subsurface drainage systems to
remove excess water from the soil profile. Farmers also apply
nitrogen fertilizers on fields and some of the nitrate can be
transported with the removal of excess water to surface water
bodies. Consequently, nitrate pollution in downstream water
bodies can cause adverse effects to aquatic ecosystems such
as hypoxia and toxin production by harmful algal blooms
(Horst et al., 2014).
One emerging biotechnology to reduce nitrate in flowing
water is a denitrifying bioreactor of which there are different
types, namely wall, bed, and layer (Schipper et al., 2010b;
chip bioreactor, is well suited for treating agricultural sub-
surface drainage water. This system is a trench filled with a
carbon media (commonly woodchips) that can remove nitrate
by transformation to nitrogen gas. One of the earliest imple-
mentations of denitrification beds was in California, USA,
where drainage water was diverted through a trench filled
with barley straw (Williford et al., 1971). In this system,
denitrification is the main nitrate removal mechanism
(Greenan et al., 2009; Warneke et al., 2011a), so knowledge of
the denitrification process is essential to the modeling of
denitrification beds.
The reaction rate law governing the denitrification process
describes the extent of nitrate removal in a denitrification bed.
Thus, obtaining the correct rate law is important to the

* Corresponding author. Tel.: 1 614 292 7246; fax: 1 614 292 9448.
E-mail addresses: ehsan.ghane@outlook.com, ghane.2@buckeyemail.osu.edu (E. Ghane).
http://dx.doi.org/10.1016/j.watres.2014.10.039
0043-1354/ 2014 Elsevier Ltd. All rights reserved.
 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
success of the model. According to Sparks (2003), the appro-
priate method for determining the reaction rate law is to
employ multiple initial (inflow) nitrate concentrations that
vary considerably (within the range of application) to inves-
tigate whether the nitrate removal rate constant is indepen-
dent of concentration. However, nitrate removal rate law
determination using this method is scarce. Some studies have
determined nitrate removal rate law based on a single inflow
nitrate concentration (Gibert et al., 2008; Leverenz et al., 2010).
Gibert et al. (2008) concluded that a zero-order rate law
described their data, since linear regression fitted most of the
treatment data (i.e., hardwood, mulch, compost, leaves and
soil) rather well when using a single inflow nitrate concen-
tration of 32 mg N L
1. Leverenz et al. (2010) reported a first-
order rate law for nitrate removal in a pilot-scale unplanted
woodchip subsurface flow constructed wetland with a high
single inflow nitrate concentration of about 70 mg N L
1. Other
studies have assumed nitrate removal in denitrifying bio-
reactors to follow a zero-order (Robertson et al., 2000, 2009), or
first-order rate law (Camilo et al., 2013; Moorman et al., 2015).
Literature review revealed that only Robertson (2010) has
evaluated nitrate removal rate law by employing multiple
inflow nitrate concentrations in a small-scale laboratory
experiment with retention times of 1 to 1.3 days. However,
these conditions may not adequately represent natural con-
ditions present in a denitrification bed due to differences in
scale, hydraulic retention time, denitrifying community, etc.
Therefore, there is need for determining the nitrate removal
rate law under natural conditions.
In addition to enhancing drainage water quality, denitri-
fication beds may also have inadvertent adverse effects.
During the biological nitrate removal process, incomplete
denitrification and woodchip decomposition might generate
greenhouse gases. Literature review indicated that only Woli
et al. (2010) have reported surface emissions of nitrous oxide
(N2O), a potent greenhouse gas, from a denitrification bed
treating drainage water. Also, methane (CH4) surface
emission from this system has not been evaluated previ-
ously. Therefore, there is a need to evaluate these potential
adverse effects.
An optimally designed denitrification bed is important for
providing efficient nitrate removal. Since denitrification beds
have recently been re-introduced for treating subsurface
drainage water, optimal design is still under development. A
denitrification bed model can help optimize the design of
these systems by enhancing our understanding of how input
Fig. 1 e Diagram of the trapezoidal denitrification bed at the Waterman Agricultural and Natural Resources Laboratory.
295
design parameters affect nitrate removal. Only Christianson
et al. (2013a) have developed a semi-empirical model of a
denitrification bed, but they did not include the effect of
temperature on nitrate removal. Furthermore, they assumed
that flow is governed by Darcy's law. However, we proved that
Darcy's law is inadequate for describing water flow through
woodchips (Ghane et al., 2014). Therefore, there is a need for a
denitrification bed model that incorporates temperature, and
employs the governing water flow and reaction rate
equations.
The objectives of this study were to (1) evaluate and
quantify greenhouse gas emissions, (2) determine the reaction
rate law of nitrate removal, and (3) model nitrate removal in a
denitrification bed treating drainage water. The applied sig-
nificance of this research is that it provides a mechanistic
model for optimizing denitrification bed design, which in
turn leads to enhanced drainage water quality.
2. Materials and methods
We presented a detailed description of the site in Ghane et al.
(2014). In brief, the polyethylene lined trapezoidal denitrifi-
cation bed, hereafter referred to as bed, was installed in
October 2011 at the Waterman Agricultural and Natural Re-
sources Laboratory, Ohio State University, USA
(Supplementary Image 1). The bed receives subsurface
drainage water from a 1.5 ha rainfed agricultural field planted
in corn and soybean during the 2013 and 2014 growing sea-
sons, respectively. Nitrogen fertilizer was applied for corn
before planting and before flowering at a rate of 13 and
185 kg N ha
1, respectively. Water flows in and out of the bed
via perforated drain pipes placed on the bed bottom at each
end (Fig. 1).
2.1. Tracer test
We conducted a tracer test at the site using potassium bro-
mide (KBr) on September 11, 2013. A total of 500 g of KBr
(335.7 g Br) was dissolved in 10 L of water and instantaneously
poured in the inlet structure at 09:00. Thereafter, samples
were collected from the outlet structure until 20:00. Sampling
was spaced at 10 min intervals during the rise of the hydro-
graph, and then increased to 15, 30, 60, and 120 min after the
peak to capture a high resolution hydrograph rather than
equal interval sampling. Flow rate during the tracer test was
296 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
kept constant using a flow controller (described in section 2.2).
We used a woodchip total porosity of 0.85 in the calculation of
the nominal retention time based on the companion study of
Ghane et al. (2014).
2.1.1. Residence time
The tracer residence time (t) (actual retention time) at con-
stant flow rate is calculated as
P to reach steady-state, except the September 11 run which
ti BCi Dti
ty P
BCi Dti
where ti is the time at the ith sample, BCi is the outlet bromide
concentration, and Dti is the time interval between sampling
(Kadlec and Wallace, 2009).
The nominal (theoretical) retention time (tn) of a bed is
calculated as tn (Vs nt)/Q, where Vs is the saturated volume of
the bed, Q is the flow rate, nt is the total porosity of the
woodchip media (Kadlec and Wallace, 2009). By replacing
Vs L A and Q q A in the equation for tn, another form of the
nominal retention time in hours is derived as
Lnt
tn
3600q
where L is the length (cm) of the water flow path (i.e., bed
length), A is the mean cross-sectional area (cm2) that water
flows through, and q is the specific discharge (cm s
1).
To quantify the extent of non-ideal flow, Thackston et al.
(1987) defined volumetric efficiency (ev) as the ratio of t to tn
where an ev value of 1 would indicate ideal plug flow.
Actual hydraulic retention time (AHRT) in a bed can also be
calculated from the ratio of the water travel time along the
length of a bed (L) at pore water velocity (v) as AHRT L/v. Pore
water velocity (average linear velocity or seepage velocity) is
the actual water velocity in the woodchip media and is
calculated as the ratio of specific discharge (q) to effective
porosity (ne). Effective porosity (drainable porosity or specific
yield) is the portion of the total porosity that contributes to
flow through woodchips (Bear, 1988; Fetter, 2001). Thus, AHRT
in hours is calculated as
Lne
AHRT
3600q
2.2. Reaction rate law experimental setup
To determine the in-situ nitrate removal rate law, we used
groundwater to represent subsurface drainage flow into the
bed during September 2013. A Mazzei Injector model 584
(Mazzei Injector Company, Bakersfield, California) was
employed to inject a potassium nitrate solution into the flow
entering the bed, creating five inflow nitrate concentration
runs of 3.1, 10.1, 14.9, 20.5, and 25.5 mg N L
1 which were
conducted on September 8, 15, 11, 10 and 9, respectively.
These values were chosen since they are within the common
range of nitrate concentrations in agricultural drainage water
(Adeuya et al., 2012). A Kates Flow Controller model GB11T-A
(W.A. Kates Co., Clawson, Michigan) was used to maintain
steady-state flow and in turn a constant inflow nitrate con-
centration during each run.
Following the flow controller, groundwater flowed through
an A1 Series Flow Meter model N100 (Great Plains Industries,
Inc., Wichita, Kansas) where instantaneous flow rate was
recorded before flowing into the inlet structure
(Supplementary Video 1). The flow meter recording was veri-
fied by measuring the time to fill a known volume before
initiation of each run. The duration of each run was from
about 08:00 to 16:00 to allow enough time for nitrate removal
(1) continued until 20:00 for tracer testing. Water flow through
the bed was maintained from about 07:00 to 08:00 each day to
flush the nitrate from the previous run.
2.2.1. Nitrate removal kinetics
Enzyme catalyzed reactions, such as denitrification, can be
described by the MichaeliseMenten equation which has been
used to model denitrification in the soil (Grant, 1991; Laudone
et al., 2011). With nitrate as the substrate, this equation takes
the common form (Fogler, 2011)
Vmax Ci
(2) rNO3 (4)
KM Ci
where rNO3 is the nitrate removal rate (mg N L
1 h
1), Vmax is
the maximum removal rate (mg N L
1 h
1), KM is the
MichaeliseMenten (or affinity) constant (mg N L
1) that is the
nitrate concentration at which nitrate removal rate is half the
maximum rate, and Ci is the inflow (initial) nitrate concen-
tration (mg N L
1). Nitrate removal rate is the difference be-
tween the bed inflow and outflow nitrate concentrations (DC)
divided by the time (AHRT) it takes for the nitrate removal to
occur (i.e., rNO3
DC=AHRT). In the case of water flow
through porous media (e.g., denitrification beds and subsur-
face flow wetlands), including effective porosity and saturated
volume in the calculation of AHRT (Kadlec and Wallace, 2009)
results in nitrate removal rate as rNO3
DC Q=Vs ne .
It is important to note that rNO3 was not calculated for
sampling events where outflow nitrate concentrations were
zero (i.e., below detection limit). This is due to the possibility
of underestimating rNO3 by using a longer AHRT than needed
to get zero outflow nitrate concentration. This situation oc-
(3)
curs when nitrate is completely removed from water before it
reaches the bed outlet.
At high nitrate concentration (Ci >> KM), reaction is
apparent zero-order
rNO3 yVmax (5)
At low nitrate concentration (Ci << KM), reaction is
apparent first-order
Vmax Ci
rNO3 y (6)
KM
To determine the parameters Vmax and KM, Eq. (4) was
inverted to obtain the LineweavereBurk equation as
 
1 1 KM 1
(7)
rNO3 Vmax Vmax Ci
The plot of the inverse nitrate removal rate versus inverse
 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
nitrate concentration will result in a straight line with slope of
KM/Vmax and intercept of 1/Vmax from which the unknown
parameters can be determined.
2.2.2. Temperature effect on reaction rate
It is well known that temperature affects nitrate removal rate,
and is described by the Arrhenius equation which takes the
modified form (Metcalf and Eddy, 2014)
rT r0 qT
T0 (8)
where r0 and rT are the reaction rate constants (or nitrate
removal rates) (mg N L
1 h
1) at the bed outflow temperatures
T0 and T ( C), respectively, and q is the dimensionless tem-
perature coefficient. According to Benefield et al. (1982), ni-
trate removal rates (rT) at various outflow temperatures (TK) in
degrees Kelvin can be used to calculate the temperature co-
efficient as
q e
m=Tmin Tmax  (9)
where m is the slope of the linear regression fitted to the plot
of ln(rT) versus 1/Tk, and Tmin and Tmax are the minimum and
maximum outflow temperatures ( K), respectively.
Furthermore, the factor by which nitrate removal rate in-
creases with 10 C rise in temperature (Q10) can then be
calculated as
Q10 q10 (10)
2.3. Hydraulic gradient
We used the measured water heights in the inlet and outlet
structures (hereafter referred to as inflow (hi) and outflow (ho),
respectively), and inside the bed to calculate hydraulic
gradient which we then used to determine AHRT along the
length of the bed. For this purpose, nine PVC piezometers
(3.5 cm inside diameter) were placed along the bottom center
of the bed in the direction of flow (Fig. 1). A piezometer was
also placed inside the inlet and outlet structures
(Supplementary Video 2). The piezometers had 5 mm holes in
the bottom 3 cm to allow water to flow inside the pipe. Water
heights in the bed inflow and outflow as well as piezometers 1
to 9 were measured using a yardstick and water finding paste
(Kolor Kut Products, Houston, Texas). HOBO U20 water level
data loggers (Onset, Bourne, Massachusetts) were also low-
ered inside each piezometer to continuously record water
height during subsurface drainage flow (Supplementary
Image 2). The relative bottom elevation of the inlet and
outlet structures, and piezometers were determined from a
laser survey.
2.4. Water sampling and analysis
For the nitrate removal rate law experiment, we collected
water samples from the bed inflow and outflow as well as
piezometers 3, 5, 7, and 9 between 15:00 to 15:30 of each run.
After sampling, water temperature was measured using a YSI
Pro Plus Quatro Cable, pH using a 1001 pH sensor, oxidation-
reduction potential (ORP) using a 1002 ORP sensor, and
297
dissolved oxygen (DO) using a 2003 polarographic DO sensor
(YSI Inc., Yellow Springs, Ohio).
During subsurface drainage flow from January 11, 2013 to
August 3, 2014, we collected water samples from the bed
inflow and outflow after the bed peak flow had occurred. This
delay is needed to allow the bed inflow and outflow water
heights to reach a relatively steady-state condition as required
by the denitrification bed model (Section 2.6). For these events,
bed outflow temperature was measured using the YSI Pro Plus
Quatro Cable. Water samples from the rate law experiment
and subsurface drainage flow were stored at 4 C until
analyzed for nitrate using a Lachat QuikChem 8500 series 2
based on the cadmium reduction flow injection method from
section 4500-NO-3 Nitrogen (Nitrate) of Rice et al. (2012).
For the tracer test, water samples were collected from the
bed outflow and were analyzed for bromide using a Dionex
DX-120 ion chromatograph based on section 4110C of Clesceri
et al. (1998). All water samples were analyzed at Ohio State
University Service Testing and Research Laboratory.
2.5. Gas sampling and analysis
Gas emissions were measured using the closed chamber
method (Hutchinson and Mosier, 1981). We inserted PVC gas
chambers (24 cm tall by 15 cm diameter) on the surface of the
woodchips by removing a portion of the woodchip surface
(equal to the chamber diameter) to about a 7 cm depth. Then the
chambers were inserted and woodchips were replaced inside
and around the chambers by gently compacting it with hand.
The gas chambers were placed next to piezometers 1, 3, 5, 7, and
9 on September 5, 2013 to allow woodchips to settle before the
rate law experiment was initiated. Gases were collected be-
tween 15:00 to 16:00 on September 9 and 15, 2013, which corre-
sponds to the 25.5 and 10.1 mg N L
1 runs, respectively.
Samples were collected from each chamber at 0 and 30 min
after the lid had been placed on the chamber. At each time, gas
samples were collected and injected into a pre-evacuated
glass vial using a 10-cc syringe. The chambers were equip-
ped with a rubber septum inserted in the center of the lid to
allow syringe needle insertion. The samples were later
analyzed for N2O, CH4 and CO2 using a gas chromatograph
(GC-2014, Shimadzu, Japan) at Ohio State University South
Centers. The GC was equipped with an electron capture de-
tector for N2O, flame ionization detector for CH4, and thermal
conductivity detector for CO2 measurement. Gas emission
rates were calculated based on the change of concentration
from 0 to 30 min.
2.6. Model development
The denitrification bed model is comprised of two compo-
nents: water flow and nitrate removal kinetics. Regarding the
former, we proved that Forchheimer's equation best describes
water flow through woodchips (Ghane et al., 2014) which is
written as
m

i q uq2 (11)
kin rg
where i is the hydraulic gradient (cm cm
1), m is the water
dynamic viscosity (g cm
1 s
1), kin is the intrinsic permeability
298 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5

Table 1 e Summary of the bromide tracer test on September 11, 2014.

Hydraulic gradient, Specific discharge, Nominal retention Tracer residence Volumetric efficiency,
i (cm cm
1) q (cm s
1)a time, tn (h) time, t (h) ev

0.018 0.075 2.61 4.67 1.79
a
Specific discharge was calculated from Eq. (12) using the in-situ intrinsic permeability and u constant.

(cm2), r is the water density (1 g cm
3), g is the gravity accel- The input parameters are inflow nitrate concentration (Ci),
eration (cm s
2), q is the specific discharge (cm s
1), and u is a maximum removal rate (Vmax), MichaeliseMenten constant
constant (s2 cm
2). Hydraulic gradient was calculated as the (KM), inflow (hi) and outflow (ho) water height, bed outflow
measured head difference between the inflow (hi) and outflow temperature (T), bed length (L) and woodchip media properties
(ho) water heights divided by the bed length (L 825 cm). For (kin, u, and ne). To our knowledge, this is the first denitrifica-
the occasions where water height was not measured, recorded tion bed model that employs the governing Forchheimer,
sensor water levels were used instead. We used bed outflow MichaeliseMenten and Arrhenius equations to predict
temperature to determine water dynamic viscosity. outflow nitrate concentration.
Solving the quadratic Eq. (11), and replacing i (ho
hi)/L We did not include woodchip variety (Cameron and
results in only one practical solution as Schipper, 2010), age (Jaynes et al., 2008; Robertson, 2010), and
r
   particle size (Van Driel et al., 2006; Cameron and Schipper,
2
ho
hi

kinmrg m
kin rg

4u L 2010) in our model, since these parameters have been
q (12) shown to have no significant effect on nitrate removal rate
2u
after the early stages of the bed operation.
Combining Eqs. (3) and (12) results in the actual hydraulic
To evaluate the model, the predicted bed outflow nitrate
retention time in hours as
concentrations were compared to the observed outflow values
2ukin rgLne during subsurface drainage flow. Coefficient of determination
AHRT r
   (13)
3600 m
4u ho
h
2 i
k in rg
2

m (R2), Nash-Sutcliffe efficiency (NSE), and percent bias (PBIAS)
L
were employed as the model evaluation statistics. NSE de-
For the site under investigation, values for in-situ intrinsic termines the goodness of fit of the plot of measured versus
permeability was 5.68  10
5 cm2, u constant was 0.88 s2 cm
2, predicted data to the 1:1 line. PBIAS measures the model bias
and effective porosity was 0.45 based on the companion study for overestimation (PBIAS < 0) or underestimation (PBIAS > 0)
of Ghane et al. (2014). with smaller absolute values indicating accurate model pre-
The rate law experimental runs were conducted at an diction (Moriasi et al., 2007).
average bed outflow temperature (T0) of 23.5 C (Table 3), so Eq.
(4) will yield nitrate removal rate (r23.5) at 23.5 C. To calculate
nitrate removal rate (rT) at temperature T, Eqs. (4) and (8) were 3. Results and discussion
combined as
3.1. Tracer test
Vmax Ci T
23:5
rT q (14)
KM Ci
The normalized residence time distribution (Fig. 2) showed
Combination of Eqs. (13) and (14), and replacing that the tracer test captured about four volume exchanges
rT
(Co
Ci)/AHRT results in the final model as (Martinez and Wise, 2003). Results indicated a percent bro-
mide recovery of 123% at constant flow rate of 9.8 L min
1. The
2ukin rgLne Vmax Ci T
23:5
Co
r
   q Ci greater than 100% recovery may have been due to concen-
KM Ci
m2
4u ho
h
2
3600 L
i
kin rg
m tration measurement error in the laboratory. The largest
measured bromide concentration was 207.5 mg L
1.
(15)
Bromide tracer test showed volumetric efficiency greater
Under steady-state conditions, the denitrification bed than 1 indicating physical (reversible) retardation that could
model can predict the bed outflow nitrate concentration (Co). be explained by bromide adsorption onto organic matter (i.e.,

Table 2 e Linear (zero-order) and exponential (first-order) regressions of nitrate concentration versus actual hydraulic
retention time for the inflow nitrate concentrations.
Inflow nitrate Zero-order First-order
concentration (mg N L
1)
Coefficient of Reaction rate Coefficient of Reaction rate
determination, R2 constant (mg N L
1 h
1) determination, R2 constant (h
1)
3.1 0.64 1.55 0.96 2.00
10.1 0.83 3.55 0.90 0.48
14.9 0.92 3.63 0.95 0.27
20.5 0.93 4.66 0.95 0.26
25.5 0.92 5.11 0.94 0.21
 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5 299

Table 3 e Data from the rate law experimental runs used to determine the MichaeliseMenten parameters.
Inflow nitrate Bed outflow Flow rate Actual hydraulic Nitrate removal
concentration (mg N L
1) temperature ( C) (L min
1) retention time (h)a rate (mg N L
1 h
1)b
3.1 23.7 9.1 1.41 2.16
10.1 22.1 10.8 1.31 4.34
14.9 23.9 9.8 1.35 4.28
20.5 24.0 9.6 1.37 5.55
25.5 23.8 9.5 1.38 5.78
a
(denitrification bed length  effective porosity)/specific discharge.
b

(outflow nitrate concentration e inflow nitrate concentration)/actual hydraulic retention time.

woodchips) (Table 1). Other studies have reported volumetric the bed with an average of 0.12 mg N m
2 min
1. The propor-
efficiency larger than 1 when using bromide tracer in wood- tion of the inflow nitrate transformed into N2O was 0.002% for
chip media (Christianson et al., 2011a; Cameron and Schipper, both experimental runs of September 9 and 15. Woli et al.
2012). Volumetric efficiency greater than 1.0 can also be (2010) also reported low N2O surface emissions ranging from
calculated for all six pilot-scale denitrification beds using data 0.17 to 2.17 mg N m
2 min
1 from beds treating drainage water.
from Christianson et al. (2011b). In contrast, Christianson et al. These values were close to emissions ranging from 0.14 to
(2013b) reported volumetric efficiency lower than 1 using KBr
tracer in an unlined denitrification bed which allows lateral
seepage and deep percolation. The authors reported clear
short-circuiting of flow in the bed that could explain the lower
than 1 volumetric efficiency.
Based on the bromide physical retardation observed in
woodchips, we could not accurately calculate the tracer resi-
dence time (AHRT) that was intended to be used in Eq. (3) to
yield the in-situ effective porosity. Instead, we used effective
porosity presented in the companion study of Ghane et al.
(2014). Therefore, we recommend that other conservative
tracers (e.g., isotope tracers) be investigated so that the hy-
draulic characteristics of denitrification beds could be better
determined.

3.2. Gas emission

A potential adverse effect of denitrification beds is the pro-

duction of greenhouse gases especially N2O since it has a high
global warming potential of 298 for a time horizon of 100 years
(IPCC, 2007). To evaluate and quantify this potential adverse
effect, we measured surface emission rates of greenhouse
gases (i.e., N2O, CH4 and CO2) along the length of the bed
(Fig. 3).
Measurements showed very low N2O surface emissions
ranging from 0.01 to 0.29 mg N m
2 min
1 along the length of

Fig. 3 e (a) N2O, (b) CH4, and (c) CO2 emissions from the
denitrification bed surface along its length (i.e.,
piezometers 1, 3, 5, 7, and 9) on September 9 and 15, 2013
Fig. 2 e Normalized residence time distribution of the corresponding with 10.1 and 25.5 mg N L1 inflow nitrate
bromide tracer test. concentration runs, respectively.
300 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5

4.75 mg N m
2 min
1 from agricultural soils (Han et al., 2014).

On the other hand, surface emissions from our bed were
smaller than the average emission of 78.58 mg N m
2 min
1
from a bed treating greenhouse effluent with high nitrate
concentrations (Warneke et al., 2011b). The abundance of ni-
trate for denitrification in the greenhouse effluent can explain
the greater N2O emissions from the bed surface (Regina et al.,
1996). In summary, we found very low N2O surface emissions
from the bed. We recommend measuring dissolved N2O in the
bed outflow to evaluate the export of this gas via this path.
Methane (CH4) surface emissions along the length of the
bed ranged from 0.59 to 5.15 mg m
2 min
1 with an average of Fig. 4 e Nitrate concentration versus actual hydraulic
2.42 mg m
2 min
1. Methane emission is expected at redox retention time for the applied inflow nitrate concentrations
potentials less than
150 mV (Masscheleyn et al., 1993), but (Ci) from the rate law experimental runs.
we measured emissions at positive redox potentials (Fig. 7b).
Boon et al. (1997) found similar results for sediments which
resulted from the difference between the redox potential
since reaction rate constants did not remain relatively con-
measured and values in anaerobic microsites within the
stant with varying inflow nitrate concentrations.
media where methanogens are active. Our reported methane
Schmidt and Clark (2013) reported a zero-order rate law for
emissions were less than the mean CH4 emission of
nitrate removal in a column study with nitrate concentrations
2227 mg m
2 min
1 during summer from a river-floodplain
ranging from 1.0 to 9.1 mg N L
1. Their conclusion was based
edge (Sha et al., 2011). A CH4 surface emission of
on the lack of significant difference and trend in nitrate
0.51 mg m
2 min
1 was reported during summer from a bed
removal rate along flow distance, but they did not consider the
treating greenhouse effluent (Warneke et al., 2011b). This CH4
effect of change in temperature on nitrate removal rate along
emission was lower than the emissions measured in our study
flow distance. Also, the lack of significant difference and trend
possibly resulting from a larger nitrate concentration that
could be the result of pooling all the treatments. Therefore, a
resulted in the denitrifiers outcompeting the methanogens for
valid conclusion can be made when nitrate removal rate for
carbon (Warneke et al., 2011b). It has been shown that CH4
each treatment is evaluated at a relatively constant temper-
emission increases with rise in temperature (Sha et al., 2011).
ature along flow distance. Chun et al. (2009) reported a first-
In our study, CH4 emissions were present at high bed outflow
order rate law for nitrate removal in a laboratory study
temperatures (22.1 C and 23.8 C), so smaller surface emis-
based on model predictions that assume Darcy's law applies,
sions from the bed are expected for the majority of the season
but their model's linear flow assumption was not validated.
when bed outflow temperature is lower (Fig. 9).
Regarding water flow through woodchips, we proved that flow
CO2 surface emissions along the length of the bed ranged
is dominantly non-Darcian (Ghane et al., 2014).
from 9.14 to 26.23 mg m
2 min
1, which is expected due to
As neither the zero- nor the first-order rate law explained
organic matter (i.e., woodchips) decomposition. Warneke
our data, we employed the MichaeliseMenten equation to
et al. (2011b) reported similar CO2 bed surface emissions
describe the nitrate removal reaction. To determine the pa-
ranging from 5.48 to 25.82 mg m
2 min
1. Woli et al. (2010)
rameters Vmax and KM, nitrate removal rate was calculated
measured CO2 bed surface emissions ranging from 269 to
for each experimental run (Table 3), and subsequently we
458 mg m
2 min
1 during spring. Collins et al. (2011) reported
fitted the LineweavereBurk equation (Eq. (7)) to the data
CO2 emissions from agricultural soils ranging from 1.88 to
(Fig. 5). Results indicated that the MichaeliseMenten equa-
7.84 mg m
2 min
1. Although, our CO2 emissions were slightly
tion was appropriate for describing denitrification because
larger than those reported for agricultural soils, the surface
area of a bed is much smaller, leading to a smaller total CO2
emission. In addition, CO2 is naturally released from organic
matter decomposition.

3.3. Nitrate removal rate law

Nitrate concentration as a function of actual hydraulic

retention time is presented in Fig. 4. To determine the reaction
order, we fitted both linear (zero-order) and exponential (first-
order) regressions to the concentration profiles. Comparison
of the coefficient of determination (R2) values showed that the
first-order rate law provided a better fit (Table 2). However, it is
required that the reaction rate constant not change substan-
tially with varying inflow nitrate concentrations as well as Fig. 5 e LineweavereBurk plot of the inverse of nitrate
providing a good fit (Sparks, 2003). Consequently, neither the removal rate versus the inverse of inflow nitrate
zero- nor the first-order rate law described nitrate removal concentration from the rate law experimental runs.
 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5 301

(Cameron and Schipper, 2010; Warneke et al., 2011c; Healy et

al., 2015). In contrast, Healy et al. (2012) calculated nitrate
removal rate of a woodchip column using the same method
presented in our study. For bed modeling and comparison
purposes, we recommend calculating nitrate removal rate
based on the effective water-filled pore volume of the
porous media where the reaction occurs as
rNO3
DC=AHRT
DC Q =Vs ne .

3.4. Denitrification bed pH, ORP and DO

Results of the pH, ORP and DO measurements along the length

Fig. 6 e MichaeliseMenten plot identifying the parameters
Vmax and KM from the rate law experimental runs.
of the bed are illustrated in Fig. 7. Measurements of pH
showed an overall decrease along the length of the bed in all
experimental runs. Warneke et al. (2011c) also reported a
slight decrease in pH in a laboratory column test. In contrast,
Warneke et al. (2011b) reported increase of pH along the length

98% of the variation was explained by the linear relationship.

Consequently, KM of 7.2 mg N L
1 and Vmax of
7.1 mg N L
1 h
1 were determined at an average bed outflow
temperature of 23.5 C. These parameters were determined
from nitrate removal rates of woodchips after 2 years and 11
months of operation, so they are expected to be valid for the
subsequent years. This is because nitrate removal rate re-
mains consistent for long periods of time after the release of
soluble carbon in the early stages (Jaynes et al., 2008;
Robertson, 2010). Therefore, the values of the model inputs
of KM and Vmax are appropriate for predicting nitrate removal
under field conditions.
The MichaeliseMenten constant of 7.2 mg N L
1 is the ni-
trate concentration at which nitrate removal rate is
3.6 mg N L
1 h
1 (Vmax/2). We calculated a KM value similar to
that reported for intact sediment cores ranging from 7.4 to
30.7 mg N L
1 (Laverman et al., 2010) and from 0.2 to
9.0 mg N L
1 (Garcia-Ruiz et al., 1998). Stringfellow et al. (2013)
also reported a KM of 43.8 mg N L
1 for a wetland microcosm
filled with on-site sediments and plants. These relatively large
KM values indicate a weak affinity of enzymes to nitrate under
natural conditions (Laverman et al., 2010).
The MichaeliseMenten plot (Fig. 6) illustrates the change in
nitrate removal rate as a function of inflow nitrate concen-
tration. This plot shows that at abundant nitrate concentra-
tion (Ci >> 7.2 mg N L
1), reaction is apparent zero-order and
nitrate removal rate is equal to Vmax (rNO3 y7:1 mg N L
1 h
1 at
23.5 C). Similarly, Warneke et al. (2011b) reported a zero-order
rate law for nitrate removal in a denitrification bed at abun-
dant nitrate concentrations.
Since Vmax is temperature dependent and has been calcu-
lated in different units, it is difficult to compare among
studies. This is also true regarding nitrate removal rate in
denitrification beds since it has been calculated differently.
Some studies have calculated nitrate removal rate using the Fig. 7 e (a) pH, (b) oxidation-reduction potential, and (c)
total bed volume that includes the unsaturated woodchip dissolved oxygen along the length of the denitrification
volume (Schipper et al., 2010a; Warneke et al., 2011a, 2011b; bed (i.e., inflow, piezometers 3, 5, 7, and outflow) from the
Christianson et al., 2013b). Others have used the saturated rate law experimental runs. The parameter Ci is inflow
woodchip volume but without porosity consideration nitrate concentration in mg N L1.
302 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
of a denitrification bed. Nonetheless, pH in this study
remained within the optimum range of 6.0 to 8.0 for deni-
trifying organisms (Pierzynski et al., 2005).
Average inflow ORP of 136 mV declined as water entered
the bed because of reducing conditions. Nitrate reduction
occurred in the bed at ORP ranging from
38 to 96 mV. The
ORP values in our study were within the redox window of
150
to 180 mV where low greenhouse gas emissions were reported
for rice soils (Yu and Patrick, 2004).
Average inflow DO of 7.3 mg L
1 decreased to an average
outflow value of 3.1 mg L
1 because of oxygen consumption by
aerobic microorganisms during woodchip decomposition in
the bed. In our study, nitrate removal was observed at a bed
average DO concentration of 3.4 mg L
1.
3.5. Temperature coefficient
Davidson and Janssens (2006) state that the Arrhenius equa-
tion and Q10 are valid when nitrate concentration is abundant
(Ci >> KM). However, inflow nitrate concentrations (ranging
from 5 to 31 mg N L
1) during subsurface drainage flow were
not abundant (Fig. 10). Consequently, we used the Arrhenius
equation at constant inflow nitrate concentrations to deter-
mine solely the temperature effect on nitrate removal rate. For
this purpose, we chose the largest group of available samples
with relatively similar inflow nitrate concentrations from the
subsurface drainage flow where outflow nitrate concentration
was non-zero (Supplementary File 1). These samples had
inflow nitrate concentrations ranging from 10.2 to
10.9 mg N L
1 and outflow temperatures (TK) ranging from
284.9 K to 295.5 K. The linear relationship in Fig. 8 accounted
for 98% of the variability in the data and resulted in a slope of

8705. Consequently, Eq. (9) resulted in a temperature coef-
ficient of 1.109 and in turn a Q10 of 2.8. This temperature co-
efficient was used in Eq. (15) to predict bed outflow nitrate
concentration during subsurface drainage flow.
Our Q10 value was greater than the Q10 value of 2.0 reported
for a denitrification bed at temperatures ranging from 15.5 C
to 23.7 C (Warneke et al., 2011b), and 1.7 reported for a labo-
ratory woodchip column at temperatures ranging from 14.0 C
to 23.5 C (Cameron and Schipper, 2010), both measured at
abundant nitrate concentrations. The greater Q10 value from
our study possibly resulted from the differences in nitrate
Fig. 8 e Plot of the natural logarithm of nitrate removal rate
versus inverse of bed outflow temperature.
removal rate calculations and/or temperature ranges.
Warneke et al. (2011c) reported Q10 of 1.2 for inflow nitrate
concentrations of 14.4 and 17.2 mg N L
1 at temperatures
between 17 C and 27 C. Elgood et al. (2010) determined Q10 of
2.0 based on bed inflow and outflow nitrate concentrations
ranging from 1 to 5.8 mg N L
1, and <0.01 to 3.9 mg N L
1,
respectively, at temperatures between 5 C and 15 C. Caution
is advised in determining values of Q10 when nitrate is not
abundant.
3.6. Seasonal nitrate removal rate
Fig. 9 presents nitrate removal rates and their respective bed
outflow temperatures during subsurface drainage flow. Ni-
trate removal rates in the bed ranged from 0.01 to
4.64 mg N L
1 h
1 with temperatures ranging from 4.4 C to
24.1 C. Healy et al. (2012) reported nitrate removal rate ranging
from 0.06 to 0.08 mg N L
1 h
1 for lodgepole pine woodchips in
a column experiment at a constant temperature of 10 C and
inflow nitrate concentrations ranging from 19.5 to
32.5 mg N L
1. The difference between their nitrate removal
rates and our study can be explained by differences in tem-
perature, inflow nitrate concentration, scale, and denitrifying
community.
As evident from Fig. 9, nitrate removal rate was smallest
during late fall and winter due to lower temperatures and/or
smaller inflow nitrate concentrations. A strategy to enhance
nitrate removal from drainage water during this colder period
is to implement controlled drainage in conjunction with the
bed. Controlled drainage is a practice in which the drainage
discharge from the field is reduced (Woli et al., 2010). The
smaller drainage discharge with controlled drainage induces
longer bed hydraulic retention times that lead to greater ni-
trate removal. In the Midwest USA, a three-chamber inlet
control structure is commonly used in bed installations to
provide the means to implement controlled drainage which
may provide an incentive of increased crop yield over the long
term (Ghane et al., 2012; Poole et al., 2013). Woli et al. (2010)
found integration of controlled drainage with a denitrifica-
tion bed to be very effective in nitrate removal. Therefore, we
recommend implementing controlled drainage with denitri-
fication beds to enhance nitrate removal from drainage water
during colder months.
Nitrate removal rate (mg N L-1 h-1)
Bed oulow temperature (C)
Month
Fig. 9 e Nitrate removal rate and bed outflow temperature
during subsurface drainage flow. Note: There are no data
for May, September and October, 2013, and February, 2014.
 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
Fig. 10 e Nitrate concentrations measured in the denitrification bed inflow and outflow during subsurface drainage flow,
and predicted outflow nitrate concentration (n 35).
3.7. Model evaluation
During subsurface drainage flow, predicted bed outflow ni-
trate concentrations were compared to the actual measured
values (Fig. 10). The model evaluation resulted in R2 of 0.86,
NSE of 0.85 (optimum NSE 1), and PBIAS of 5.98 (optimum
PBIAS 0). Therefore, with appropriate input values, this
model can predict nitrate load removal with good accuracy.
Overall, the model's predictions were in good agreement with
the measured values except on February 11, 2013 where pre-
diction was far from actual measurement likely due to error in
water height measurement, or the measured value.
The practical implication of this model is to provide better
insight into nitrate removal under different conditions. As a
result, a denitrification bed can be designed to efficiently
remove nitrate, and at the same time reduce the potential for
strongly reducing conditions that promote methylation of
inorganic mercury. An example of using the model
(Supplementary File 2) to reduce outflow nitrate concentration
is to increase the bed length to create a longer hydraulic
retention time. Furthermore, this model could be integrated
into field-scale hydrological models such as DRAINMOD
(Skaggs et al., 2012).
4. Conclusions
Our tracer test showed physical retardation of bromide in the
denitrification bed. We recommend that other conservative
tracers (e.g., isotope tracers) be investigated so that the in-
ternal hydraulics of denitrification beds could be more accu-
rately studied. Greenhouse gas surface emissions from the
denitrification bed treating drainage water were very low. We
recommend measuring dissolved N2O in the bed outflow to
evaluate the export of this gas via this path.
Nitrate removal rate law experiments based on multiple
inflow nitrate concentrations (within the common range
observed for drainage water) indicated that denitrification did
not follow either the zero- or the first-order rate law. Instead,
nitrate removal rate was described MichaeliseMenten
303
kinetics with MichaeliseMenten constant (KM) of 7.2 mg N L
1
and a maximum nitrate removal rate (Vmax) of
7.1 mg N L
1 h
1 at 23.5 C bed outflow temperature. Results
indicated a temperature coefficient of 1.109 and Q10 of 2.8,
considering the effect of inflow nitrate concentration on ni-
trate removal rate. Furthermore, seasonal nitrate removal
rates were smallest during late fall and winter. Thus, we
recommend implementing controlled drainage with denitri-
fication beds to enhance nitrate removal from drainage water.
We used Forchheimer's equation and nitrate removal ki-
netics to develop a novel mechanistic model of a denitrifica-
tion bed. As evident from the model evaluation statistics, the
model prediction of bed outflow nitrate concentration was
statisfactory. The practical implication of this model is to
enhance our understanding of denitrification beds so it could
lead to designs with optimal nitrate removal. We recommend
that this model be validated at other denitrification bed sites,
and be used to develop optimal design guidelines.
Role of funding source
Funding of this research was provided in part by Ohio Agri-
cultural and Research Development Center grant number
2013-098; Ohio State University Graduate School Presidential
Fellowship to lead author; Overholt Drainage Education and
Research Program; Department of Food, Agricultural and
Biological Engineering; College of Food, Agricultural, and
Environmental Sciences; and USDA-Natural Resources Con-
servation Service CIG grant number 69-5E34-10-053. The
funding sources were not involved in the study design,
collection, analysis, interpretation of data, and preparation of
the manuscript.
Acknowledgments
The authors thank Mozhgan Foroughi and Scott Schwieter-
man for their assistance. We also express gratitude to Dr.
304 w a t e r r e s e a r c h 7 1 ( 2 0 1 5 ) 2 9 4 e3 0 5
Khandakar Rafiq Islam and Yogendra Raut at Ohio State Uni-
versity South Centers, Waterman Laboratory Manager Glenn
Mills, and USDA-ARS Soil Drainage Research Unit.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.watres.2014.10.039. These data
include videos, a Google map, files, and images.
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