Investigation into the kinetics of constructed wetland degradation

processes as a precursor to biomimetic design

Lara Aylward1,2, Uwe Kappelmeyer3*, Ricky Bonner1,2, Philipp Hecht4 and Craig Sheridan1,2
1
Industrial and Mining Water Research Unit (IMWaRU), School of Chemical and Metallurgical Engineering, University of the Witwatersrand,
Private Bag X3, PO Wits, Johannesburg, 2050, South Africa
2
Centre in Water Research and Development (CiWaRD), University of the Witwatersrand, Private Bag X3, PO Wits, Johannesburg, 2050, South Africa
3
Helmholtz Centre for Environmental Research GmbH - UFZ, Dept. of Environmental Biotechnology, Permoserstraße 15, 04318, Leipzig, Germany
4
University of Dresden, Technische Universität Dresden, Institute of Food Technology and Bioprocess Engineering, Bergstraße 120, 01609,
Dresden, Germany

ABSTRACT
In this study, biomimetic principles were incorporated into a kinetic study of a pilot-scale, horizontal subsurface-flow
constructed wetland (6.0 m ×  1.0 m ×  0.5 m) in Leipzig, Germany. The bed contained glacial gravel (4–8 mm) planted with
Phragmites australis. Construction was completed in October 2013 and experiments commenced in August 2015. During
establishment, the system was fed with only municipal tap water (165 L·d−1). The Phragmites root system had penetrated to
the bottom of the wetland within 18 months. To break into the constructed wetland ‘black box’, the system was divided into
a three-dimensional grid of sample ports. Initially, the wetland was physicochemically characterized (prior to addition of
nutrients from an external source) in order to quantify the natural, baseline state. Thereafter, an impulse-response tracer
test was conducted, using a fluorometer, for continual measurement of uranine concentration. 100% tracer recovery was
achieved. The RTD was multi-modal – indicating by-pass flow – and showed long tailing due to mixing, diffusive effects
and dead zones. Kinetic performance was investigated via monitoring total organic carbon and total nitrogen degradation,
with a continual feed of artificial domestic wastewater (110 mg·L−1 COD). 93% reduction in TOC and TN was achieved for
5 weeks (11 November – 08 December 2015), despite high inflow loading (69.9 g·m−3·d−1 TOC; 28.1 g·m−3·d−1 TN) and colder
temperatures. There was a general decline in reaction rate and rate constant from late October to early December. The average
rates of TOC and TN removal were 65.08 ± 2.16 g·m−3·d−1 and 26.22 ± 0.68 g·m−3·d−1, respectively (Tanks-In-Series model).
These results are the first set in a series. Continual observation and repetition of these experiments into long-term operation
will deepen understanding of the internal development and performance of constructed wetlands, as is in line with the
biomimetic approach, and provide the basis of a framework for improved wetland design.

Keywords: constructed wetlands, baseline analysis, hydraulics, kinetics, biomimicry

INTRODUCTION South Africa’s water resources are governed by the Water

Services Act of 1997 (RSA, 1997) and the National Water
South Africa is a water-scarce country – ranked 30th driest Act of 1998 (RSA, 1998). In line with the requirements of
globally (Greencape, 2016) – with an annual rainfall of just the two water acts and Government’s National Development
50% of the world average. The country relies predominantly Plan (NDP), the South African Department of Water and
on water from catchments, rivers, wetlands and aquifers Sanitation (DWS) issued the National Water Resource
(WWF-SA, 2016). Poor water quality has a major negative Strategy 2 (NWRS2). The NWRS2 covers security of water
impact on the livelihood of all South African citizens, as well supply, managing environmental degradation and curb-
as the surrounding ecosystem. Water quality in South Africa’s ing pollution of water resources (DWS, 2013). The DWS, in
natural resources has declined over the past two decades, in conjunction with the South African National Biodiversity
some cases to such an extent that the water has become a seri- Institute (SANBI), has proposed a 19 th Strategic Integrated
ous health threat. The primary contributors to the pollution of Project (SIP) which will use the ‘Investment in Ecological
the country’s water resources are: Infrastructure (IEI)’ model to find joint ecological and engi-
• Release of raw sewage neering solutions to South Africa’s water treatment challenges
• Acid mine drainage (AMD) (SANBI, 2014). As South Africa works towards developing its
• Release of untreated industrial effluent ecological infrastructure, the opportunity arises to move from
• Excess nutrients from agricultural runoff centralized to decentralized water and wastewater treatment
• Poor service delivery from municipal Water Service facilities, examples of which include point-of-use household
Authorities technologies, rainwater harvesting installations, grey-water
Without urgent attention, South Africa could be faced with a green roofs and water recycling and reclamation systems
serious water quality crisis (WWF-SA, 2016). (Greencape, 2016).
Constructed wetlands (CWs) are engineered systems,
designed to utilize the soil, vegetative and microbial processes
This paper was originally presented at the 2016 Water Institute of
Southern Africa (WISA) Biennial Conference, Durban, 15–19 May 2016. of natural wetlands in the treatment of wastewater of different
* To whom all correspondence should be addressed. origins, including domestic and municipal sewage, industrial
 49 341 235 1679; e-mail: [email protected] and agricultural wastewater, landfill leachate, AMD, storm-
Received 6 March 2017; accepted in revised form 6 October 2017 water run-off and mining wastewater (Reed, 1993; Vymazal,

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2005). CWs typically consist of a soil-, gravel- or sand-filled habitats for biodiversity (Dama-Fakir et al., 2015).
bed planted with various types of macrophyte (most com- There is real scope for CWs to provide a valuable addition
monly Phragmites australis) (Brix, 1994). Table 1 summarizes to South Africa’s ecological infrastructure. They offer all of the
the primary contaminants and their mechanisms of removal advantages of decentralized systems (Greencape, 2016) and,
from CW systems (Vymazal, 2005). when designed using biomimetic principles, can offer benefits
In the past, CWs have most often been used as polishing beyond just water remediation. A case in point is the success-
systems following the primary and secondary water treatment ful prototype in the Langrug informal settlement close to
stages (Brix, 1994), but have more recently been identified as a Franschhoek, South Africa (WWF-SA, 2016). Langrug has been
viable, green technology solution to water management in the converted into an ‘eco-machine’ (USEPA, 2002; Jted, 2014),
following areas: which uses biomimicry to address water purification, stormwa-
• Regulation of water supply ter and solid waste management, as well as provide potential for
• Drought alleviation revenue generation (WWF-SA, 2016).
• Regulation of water quality (particularly for biological and Although the use of CWs for wastewater treatment was
temperature control) (Greencape, 2016) documented as early as 1904 (Brix, 1994), much of the pioneer-
Biomimicry is defined as ‘the practice of learning from and ing literature views CWs as ‘black boxes’, and understanding
then emulating nature’s genius to solve human problems of how these systems operate internally is limited (Albertson,
and create more sustainable solutions’ (Biomimicrysa, 2015). 1998; Haberl et al., 2003; Garcia et al., 2010; Rengers et al.,
Throughout the process of evolution, living organisms have 2016). This research focuses on an overall hydraulic characteri-
survived and adapted to changing conditions in such a way as zation of a newly established pilot-scale CW and an in-depth
to ensure continual access to water. For this reason, natural physico-chemical baseline description to act as points of refer-
ecosystems and their inhabitants provide many examples of ence. This is followed by 2 months of feeding artificial domestic
successful water purification processes (Dama-Fakir et al., wastewater into the wetland and continually monitoring the
2015). For example: chemical and physical changes. The chemical characterization
• The ability of the Namibian Fog Beetle to capture water will provide insight into the kinetics of total carbon and total
from the air (Kenny et al., 2012) nitrogen transformation. The analytical procedure involves
• The ability of ‘curly-whirlies’ (desert plants of the dividing the CW into a grid of sample ports: 7 ports down
Namaqualand) to capture fog from the air with modified the length of the bed, each of which is divided into 3 depths.
leaves and stems (Vogel and Müller-Doblies, 2001) The multitude of sampling locations and samples will provide
• The action of worms, beetles and micro-organisms in decom- insight into the internal development and operation of the
posing forest litter into humus, thereby creating a mat for wetland system. This preliminary data is to form the basis of
water filtration on the forest floor (the chemical-free Biolytix a long-term study into the internal behaviour of CWs, from
water filtration system mimics this process) (Kenny et al., start-up into steady operation, and will provide the start of a
2012) framework to inform improved biomimetic design.
• The ability of natural wetland ecosystems to filter sediments
and nutrients from surface water (Kenny et al., 2012) MATERIALS AND METHODS
Natural wetlands have a number of important functions,
namely, water purification, water capture and storage, flow reg- Pilot-scale CWs at the Helmholtz Centre for
ulation, flood attenuation, shoreline stabilization and protec- Environmental Research GmbH – UFZ
tion, carbon sequestration, air quality regulation, temperature
regulation and habitats to support biodiversity (Dama-Fakir et The pilot-scale wetlands at the UFZ are planted, horizontal
al., 2015). Without their variety of vegetation, micro-organisms, subsurface flow (HSSF) CWs. The system is filled with glacial
aquatic species and wildlife, wetland ecosystems would not gravel (particle size 4–8 mm; voidage 36%; bed height 0.50 m)
support these functions (Kivaisi, 2001). and planted with Phragmites australis. A schematic diagram
As the types of wastewater to be treated become more of the wetland is given in Fig. 1. The boundary structure is
diverse, so the need for more economical, efficient and an approximately rectangular, stainless-steel container (6 m
robust systems to cope with the treatment demands emerges. length x  0.70 m height). One side down the length of the wet-
Biomimetic principles (Benyus, 2017; Todd and Josephson, land is constructed at 16° from the vertical, such that the width
1996) could provide valuable tools to inform the design of at the top and base of the container is 1.2 m and 1.0 m, respec-
improved CW systems. Biomimetic CWs are self-contained, tively. Three fully removable, stainless-steel baskets (height
ecologically engineered systems in which waste streams are 0.7 m; diameter 0.30 m) have been inserted into the central flow
recycled wherever practicable. In addition, they can be a source path. Each basket contains glacial gravel and has been planted
of nutrient-rich fertilizers and renewable energy and can act as with Phragmites australis, just as in the surrounding wetland
carbon sinks, air quality regulators, temperature regulators and system. The basket cages have evenly distributed pores of the

Table 1
Primary contaminants and mechanisms of removal from CW systems
Contaminant Mechanism of removal
Organic matter Aerobic and anaerobic degradation by bacteria attached to plant roots, rhizomes and media surfaces
Suspended solids Filtration and sedimentation
Nitrogen (ammonia or nitrate) Nitrification/denitrification process and adsorption (if soil grain is sufficiently fine)
Phosphorus (phosphate) Ligand exchange reaction in the presence of iron, aluminium or calcium hydrous oxides

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same diameter as the average gravel particle size to minimize Collection of baseline samples
disruptions to the flow of water. The purpose of the baskets is to
be able to transport a predominantly undisturbed section of the From October 2013 to July 2015, the wetland was allowed
CW to the laboratory for more detailed analysis. to establish naturally, without any external nutrient source.
The wetland is fed by 3 evenly-spaced inlet valves, which Municipal tap water was fed into the system during spring,
are positioned 5 cm above the base of the container. The dis- summer and autumn and shut off during the coldest winter
charge is removed via a single, centred outlet valve, also 5 cm months. In order to determine the baseline characteristics of
above the wetland base. The flow rate of water into and out the newly constructed CW, a set of samples, hereafter referred
of the wetland is regulated via a gear pump (VGS120, Verder to as baseline samples, were taken before the commencement
Pump, Germany), motor (SEV6324, SEVA Tec, Germany) and of any other experiments. The samples were taken from 24 cm
frequency controller (DF51-322-025, MOELLER, Germany) below the gravel surface. Sampling devices, hereafter referred to
and data is logged to allow for continual monitoring of as samplers, were inserted into the bed at the locations indi-
the flow rates. The water level within the wetland is main- cated in Fig. 1a, but not at the system outlet (Port 7) where black
tained at 0.5 m by means of a siphon at the wetland outlet. norprene tubing was connected directly to the discharge valve.
Construction was completed in October 2013. Figure 2a The samplers were L-shaped, stainless steel tubes (Fig. 1b), open
shows a photograph of the wetlands at the UFZ taken in July at both ends, to allow for the easy movement of water. The long
2015. The wetland has been dug into the ground, such that end was inserted into the gravel bed and contained several
the upper rim and 20 cm of the boundary walls are visible. pore-like holes at the base. These holes were too small to allow
Figure 2b shows a photograph of the middle basket when it for gravel to enter the hollow interior. The short end sat above
was removed from the wetland in September 2015. the surface of the gravel bed and contained a single opening.

Figure 1
Aerial view of the CW showing (a) sample port and inlet valve locations (outlet valve is Port 7) and (b) cross-sectional view showing one
stainless-steel sampling tube

Figure 2
Photographs of (a) the pilot-scale, horizontal subsurface flow CWs at the Helmholtz UFZ (July 2015) and (b) the stainless-steel basket removed
from the centre of the wetland showing a well-developed root system (September 2015)

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 The short ends of each sampler were connected, one at a
time, to a small peristaltic pump (REGLO MS 2/6, ISMATEC
SA, Switzerland) via 1.2 m of black, norprene tubing. Water was
pumped continually through flow-through cells for the meas-
urement of dissolved oxygen (DO) (Fibox 3, Presens, Germany),
oxidation-reduction (redox) potential (Multi-i340, WTW,
Germany), pH (Multi-i340, WTW, Germany) and temperature,
after which 20  mL aliquots were collected, through 0.45 μm
syringe filters, and submitted to the analytical laboratory for
total organic carbon (TOC) and total nitrogen (TN) analysis
(Multi N/C 21005, Analytikjena, Germany). Figure 3
A schematic diagram of the sampling device, pump, flow cell and
Impulse-response tracer tests fluorometer configuration for the tracer flow tests

For the hydraulic investigation, samplers were inserted

into the bed at each internal port (Fig. 1a); 24 cm below the Table 2
gravel surface. The samplers were connected in pairs. One Legal limits on environmental discharges for a treatment
plant of Class 2 in Germany
sampler was the outlet tube, from which water was removed
(based on an inflow of 300–600 kg·d−1 BOD5)
from the wetland, and the second was the return tube.
The return tube was fixed to the outlet tube such that the Component Concentration (mg·L−1)
holes at the base of its long end were positioned 6 cm above a
COD 110.0
those of the outlet tube. Both short ends of the samplers a
BOD5 20.0
making up each pair were connected to a peristaltic pump
(BVP_Z, ISMATEC SA, Switzerland), a stainless-steel flow
b
TOC 22.80
cell (Schnegg, 2002) and a fluorometer (GGUN-FL, Albillia, b
TN 9.14
Switzerland), using black norprene tubing. This configura- a
legal standard
tion is shown in Fig. 3. b
measured in analytical laboratory (UFZ, Leipzig) from AWW
A known mass of uranine fluorescent tracer dye was concentrate
dissolved in 1 L of distilled water and injected into the wet-
land inlet as a single pulse. For the duration of each flow test,
water was pumped out of the wetland and through the flow entry into the wetland. The individual feed water and AWW
cell, which was connected to the fluorometer, before being loading rates are presented in Table 3. The AWW flow rate was
returned to the bed at the same location (Fig. 3). The return monitored regularly via the ‘bucket and stopwatch’ method.
flow ensured that the total system volume was maintained. Weekly sampling commenced 1 week after the introduction of
The fluorometer was programmed to record data at 10 s the wastewater and continued for 7 weeks. Samples were taken
intervals and provided a potential (mV) reading, which was from 24 cm below the gravel surface at each sample port, as
converted to uranine concentration after calibration with feed described previously.
water from the site (baseline) and a standard uranine solution
(70 ppb). RESULTS AND DISCUSSION

Introduction of artificial wastewater It was desired that the pilot-scale CWs at the Helmholtz UFZ
resemble a natural wetland ecosystem as closely as possible.
An artificial wastewater (AWW) concentrate containing For this reason, the CWs were allowed to establish naturally,
37.50 g·L−1 casein peptone, 25.78 g·L−1 meat extract, 7.03 g·L−1 without any external nutrient source, from October 2013 until
urea and 6.56 g·L−1 dipotassium hydrogen phosphate was summer 2015, when these first experiments were scheduled
prepared, autoclaved and introduced into the CW system via a to commence. The results to follow represent the baseline and
metering pump (Gamma L GALA1000, ProMinent, Germany). the very first set of measured data. Due to the complexity and
The concentrate was formulated from a published standard continual internal development of these systems, such experi-
based on the average composition of the water released from a ments will be repeated seasonally and annually into long-
treatment plant of Class 2 in Germany; representing between 1 term operation of these wetlands. Knowledge and resources
000 and 5 000 inhabitant equivalents (FMJC, 2001). A typical from several disciplines in the sciences will be drawn upon to
analysis of German Class 2 effluent is given in Table 2. develop a databank of information, to gain a deeper under-
The separate feed water and AWW feed lines were com- standing of the operation and continual fluxes within wetland
bined into a single pipe and the two fluid streams mixed before systems and, ultimately, to recommend a methodology and a

Table 3
Feed water and artificial wastewater inflow loading rates
HLR (L·m −2·d−1) HLR (L·m−3·d−1) Flow ratio
Week Date (2015)
Inflow AWW Inflow AWW (inflow:AWW)
1 21 Oct–28 Oct 76.14 0.0982 452.4 0.583 776
2 28 Oct–4 Nov 76.95 0.0899 457.2 0.534 856
3–7 4 Nov–8 Dec 20.54 0.0806 122.0 0.479 255

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set of design parameters for engineering scale-up. of the wetland before reaching a minimum and then increasing
until the water was oxygen saturated again close to the outlet
Wetland baseline characterization (Fig. 4a, ‘◊’). The plant roots are a source of oxygen to the rhizo-
sphere (Kadlec and Wallace, 2009), but it cannot be confirmed
Samples for the baseline characterization were taken in August, that this is the reason for this re-introduction of oxygen into the
September and October of 2015, at which time the wetland was wetland. The September trend in DO close to the wetland outlet is
a working system with unknown flux, no additional carbon dissimilar to that in both August and October and, due to the lack
source and low organic load. The bed temperature, pH, TOC of confirmatory experimental data, should be treated with cau-
and TN concentration were measured down the length of the tion. In contrast, the oxygen level decreased progressively down
wetland and are presented in Table 4. the bed in October (Fig. 4a, ‘□’). This indicated that plant activ-
The pH of the wetland was found to remain relatively ity decreased down the bed (it was observed that the vegetation
constant (Table 4) and within the physiological range of natural density also decreased down the bed) but that the plants were still
fens and freshwater wetland ecosystems (Kadlec and Wallace, active although not at the same high level as at the height of the
2009). The TOC and TN concentrations reported in Table 4 summer.
give the average natural background levels, below which the In summary, Figs 4a and b suggest a seasonal influence on
measured outlet concentrations are not expected to fall (Kadlec
and Knight, 1996). This residual carbon and nitrogen can be
accounted for by inherent production of organic substances and
carbonaceous material (root exudates), which contribute to the
biological oxygen demand (BOD) and decaying plant matter
(Bavor et al., 1988; IWA, 2000; Reed, 1993).
The variation in DO and potential within the wetland are
plotted in Figs 4a and b, respectively. For clarity, the DO and
redox potential at Sample Port 3, located inside the middle
basket (Fig. 1a), has been plotted as individual points. In gen-
eral, the wetland microcosm within the basket does not show
behaviour markedly different to that in the surrounding sys-
tem, except during October when the DO and potential aligned
with the data obtained in August (Fig. 4, ‘x’).
There was a clear consumption of oxygen during August
(Fig. 4a, ‘o’), accompanied by a lower potential (Fig. 4b, ‘o’)
and a general increase in both wetland DO and potential from
August to October. August was the warmest month during the
summer of 2015 with high levels of solar radiation. The average
daily air temperature and global radiation maxima were meas-
ured to be 28.4°C and 716 W·m-2, respectively, at the weather
station on-site. These were measured between 11 am and 2 pm.
The plants were green and their growth rate and level of activity
would have been at a maximum under these climatic condi-
tions (Kadlec and Wallace, 2009); hence the greater consump-
tion of oxygen during August.
In the autumn months of September and October, when the
average ambient and bed temperatures had begun to decrease
(Table 4), there was a reduction in oxygen consumption (Fig. 4a, ‘◊’
& ‘□’) and a more positive potential (Fig. 4b, ‘◊’ & ‘□’). Overall, this
would be expected because plant activity should have decreased
in the autumn period. Also evident is that the oxygen concen-
trations were closer to the saturation values. In both September
Figure 4
and October, approximately 9 mg·L−1 of O2 was measured in the
Baseline characterization showing (a) the dissolved oxygen
feed water. The water remained oxygen-saturated within the first concentration and (b) the oxidation-reduction potential, prior to the
100 cm of the wetland (Fig. 4a, ‘◊’ & ‘□’), which would suggest no introduction of artificial wastewater. Data was obtained from 24 cm
oxidative processes or exudate transformation up to 100 cm. In below the gravel bed surface and at increasing distance along the flow
September, oxygen was consumed faster within the second 100 cm path during August, September and October 2015.

Table 4
Average bed temperature, pH, TOC and TN concentration with the saturated oxygen concentration (fresh water, 760 mm Hg)
at the time of the baseline measurements
Average bed temp Saturated oxygen
Period pH TOC (mg·L−1) TN (mg·L−1)
(°C) (mg·L−1)
Aug 2015 24.1 ± 2.1 8.5 6.85 ± 0.14 3.11 ± 0.24 0.54 ± 0.05
Sept 2015 20.5 ± 0.3 9.0 7.50 ± 0.21 3.60 ± 0.30 0.44 ± 0.02
Oct 2015 16.8 ± 1.1 9.7 7.44 ± 0.19 2.39 ± 0.11 0.72 ± 0.06

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 𝑚𝑚
0
𝑉𝑉
𝜏𝜏 =
𝑣𝑣0 𝑉𝑉
𝜏𝜏 =
𝑉𝑉 𝑣𝑣0
the DO concentration and redox potential, but it cannot be said calculated according to: 𝜏𝜏 =
𝑣𝑣0
with certainty whether this is due to changes in the plants or
∞
changes in microbial activity in the root zone. However, model
2 ∞
experiments have indicated that oxygen input from the plants is 𝜎𝜎 = ∫ (𝑡𝑡 − 𝑡𝑡𝑚𝑚 ̅ )2 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑 (5)
dependent on the light intensity and the redox state of the root 𝜎𝜎 20=∞∫ (𝑡𝑡 − 𝑡𝑡𝑚𝑚 ̅ )2 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑
zone (Kadlec and Wallace, 2009). 𝜎𝜎 2 = ∫ (𝑡𝑡
0 − 𝑡𝑡𝑚𝑚 ̅ )2 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑
Owing to the fact that flow 0 was laminar and, thus, com-
Hydraulic characterization pletely reversible, the RTD function could be normalized
𝑡𝑡
against the mean residence time θ =according to:
A gravel HSSF CW can be considered to be a type of packed- θ=𝑡𝑡 ̅ 𝑡𝑡
𝑚𝑚
𝑡𝑡
𝑡𝑡 𝑚𝑚̅
bed reactor (Sheridan et al., 2014a; Sheridan et al., 2014b; θ= (6)
̅
𝑡𝑡𝑚𝑚
Vymazal and Kröpfelová, 2009). An understanding of wetland
hydraulics is a pre-requisite for an investigation into the kinet-
𝐸𝐸(θ) = 𝐸𝐸(𝑡𝑡)𝑡𝑡𝑚𝑚 ̅
ics of contaminant degradation (Headley and Kadlec, 2007), 𝐸𝐸(θ) = 𝐸𝐸(𝑡𝑡)𝑡𝑡 ̅ (7)
𝑚𝑚
(Fogler, 2006). The hydraulic investigation of the pilot CW 𝐸𝐸(θ) = 𝐸𝐸(𝑡𝑡)𝑡𝑡𝑚𝑚 ̅
at the UFZ was performed by means of an impulse-response Equations 2, 6 and 7 were employed to produce the normal-
tracer test according to the methodology described by Headley ized RTD function for the reactor𝜏𝜏outlet 2 in Fig. 5. The shape
2
and Kadlec (2007). of the RTD in Fig. 5 suggests𝑛𝑛that = that 𝜏𝜏 this system displays
𝑛𝑛𝜎𝜎=22 2
Tracer studies should be conducted under laminar, or behaviour intermediate between plug 𝜏𝜏 𝜎𝜎flow and complete mix-
reversible flow, conditions (Sheridan et al., 2014a; Sheridan ing (Headley and Kadlec, 2007). 𝑛𝑛 =There
𝜎𝜎 2 are two main features
et al., 2014b). Before commencing the flow test, the Reynolds in Fig. 5. Firstly, the distribution is multi-modal. There are
number was calculated for the wetland system (Subramanian, two distinct peaks prior to t = tm (θ = 1.0). 1 This is typical of
1
2004) and verified to be less than 10, which confirmed that flow a reactor in which there𝑋𝑋is=channelling
1−
𝑋𝑋 = 1(1 − + 𝜏𝜏𝑖𝑖or 𝑘𝑘)by-pass
𝑛𝑛 and dead
was well within the laminar region (Miller and Clesceri, 2002). zones (Headley and Kadlec, 2007). (1
The +
1 𝜏𝜏𝑖𝑖 𝑘𝑘)𝑛𝑛peaks after t = t
small
𝑋𝑋 = 1 − 𝑛𝑛
m
Subsequent to the completion of the tracer test, the recovery (θ = 1.0) could indicate hold-up in(1densely + 𝜏𝜏𝑖𝑖 𝑘𝑘)vegetated areas or
of tracer material was calculated, according to Eq. 1, as the first possibly adsorption and desorption of the tracer material onto
check on the reliability of the experimental data. Data obtained the gravel (Headley and Kadlec, 2007; 𝑉𝑉 Smart and Laidlaw,
from a tracer test with a low percentage recovery of material at 𝜏𝜏𝑖𝑖 =𝜏𝜏 = 𝑉𝑉
1977). Secondly, there is long tailing evident. This can be the
𝑖𝑖𝑣𝑣0 𝑛𝑛
𝑉𝑉𝑣𝑣0 𝑛𝑛
the system outlet should be treated with caution (Headley and result of mixing between the pore 𝜏𝜏𝑖𝑖 =spaces, diffusion between
Kadlec, 2007). regions of faster and slower flow and, 𝑣𝑣0 𝑛𝑛again, dead zones (Fogler,
2006).
∞
𝑣𝑣0 ∫0 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑 Various hydraulic parameters, calculated from Eqs 1, 3,
𝑅𝑅 = × 100 (1) 4, 5 and the RTD, are summarized in Table 5. The mean resi-
𝑀𝑀
∞
𝑣𝑣0 ∫0 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑 dence time, or time taken for the bulk of the injected pulse of
𝑅𝑅 = in Fogler (2006),
The method outlined × 100and summarized uranine to reach the outlet, was 2.89 days. Ninety-nine percent
𝑀𝑀
below, was used to calculate the residence time distribution (99%) of the injected mass of tracer had exited the wetland after
(RTD) function for the𝐸𝐸(𝑡𝑡)
reactor, 𝐶𝐶(𝑡𝑡) by:
defined
= ∞ 6.54 days. In general, it takes at least 3 retention times for mate-
∫0∞𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑 rial to be flushed from the system. Making this assumption, it
𝑣𝑣0 ∫ 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑
𝐶𝐶(𝑡𝑡)
= =0 ∞
𝑅𝑅 𝐸𝐸(𝑡𝑡) × 100 would take an additional 2 days (2.89 d x  3 = 8.67 d) for the tail
∫0𝑀𝑀 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑 (2) of the RTD curve to reach baseline concentration again.
∞
𝑣𝑣0 ∫0 ∞ 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑
𝑅𝑅 =
C(t) is the time-variant concentration × 100 data collected
̅𝑡𝑡𝑚𝑚 = 𝑀𝑀 ∫ 𝑡𝑡𝑡𝑡(𝑡𝑡)𝑑𝑑𝑑𝑑 Contaminant transformation indicators
during the flow test and the denominator represents the area
under the C(t) curve. The RTD 0 ∞ 𝐶𝐶(𝑡𝑡) because it visually
𝐸𝐸(𝑡𝑡) is = important ∞ Various physicochemical parameters provide information about
describes dynamic wetland 𝑡𝑡 ̅ =
𝑚𝑚 behaviour∫ 𝑡𝑡𝑡𝑡(𝑡𝑡)𝑑𝑑𝑑𝑑
∫0 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑
and fluid flow patterns water quality. DO is essential for aerobic degradation processes.
and is the basis for the calculation 0 𝐶𝐶(𝑡𝑡) of many important hydrau-
𝐸𝐸(𝑡𝑡) = 𝑉𝑉∞ The ammonium ion is a by-product of the decomposition of a
lic parameters, one of which is the mean residence time, tm, or wide range of nitrogen-containing organic matter and high levels
𝜏𝜏 =∫0 𝐶𝐶(𝑡𝑡)𝑑𝑑𝑑𝑑
first moment: 𝑣𝑣0 of NH4+ can produce an environment which is toxic to aquatic
∞
𝑉𝑉 organisms. A positive redox potential indicates an oxidizing
̅ 𝜏𝜏 =
𝑡𝑡𝑚𝑚 = ∫ 𝑡𝑡𝑡𝑡(𝑡𝑡)𝑑𝑑𝑑𝑑
𝑣𝑣0 solution and many pollutants require strong oxidants to facilitate
∞ ∞ 0 (3) their decomposition (Bellingham, 2012). Organic carbon and the
𝜎𝜎 2𝑡𝑡=̅ ∫
𝑚𝑚 =(𝑡𝑡∫−𝑡𝑡𝑡𝑡(𝑡𝑡)𝑑𝑑𝑑𝑑
̅ )2 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑
𝑡𝑡𝑚𝑚 chemical oxygen demand (COD) are important water quality indi-
The mean residence time, 0 ∞ 0 tm, was compared to the nominal cators (Kadlec and Wallace, 2009), for which maximum allowable
residence time, τ, which is the hypothetical time taken for a pulse limits are commonly published in environmental legislation.
𝜎𝜎 2inlet
= ∫to(𝑡𝑡outlet ̅ 𝑉𝑉 2
)assuming
of tracer to move from 𝜏𝜏−= 𝑡𝑡𝑚𝑚 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑 ideal plug flow: For the purpose of this very first investigation into the
𝑣𝑣0
0
𝑡𝑡 behaviour of this CW system, the TOC and TN concentra-
θ =𝑉𝑉 tions were measured. TOC was chosen because it is a more
𝜏𝜏 = 𝑡𝑡 ̅
𝑣𝑣0𝑚𝑚 (4) accurate measure of the degradation of carbon in the system, as
∞ 𝑡𝑡 opposed to COD which is a cumulative measure of all oxidiz-
V is the reactor volume and θ =accounts2for the porosity of the
𝜎𝜎 2
= ∫ (𝑡𝑡 𝑡𝑡
− ̅ 𝑡𝑡𝑚𝑚 ̅ ) 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑 able components. Similarly, TN, which is the sum parameter
packing material, and 𝐸𝐸(θ) v0 is the system
= 𝐸𝐸(𝑡𝑡)𝑡𝑡
𝑚𝑚
̅ the volumetric flow rate.
𝑚𝑚 of the nitrogen contributions from ammonium (NH4+), nitrate
tm = τ for a closed, steady-state ∞ 0 system with no dead volume.
(NO3-), nitrite (NO2-) and organic nitrogen, was considered for
The variance, σ𝜎𝜎2,2or= second
∫ (𝑡𝑡 − moment 𝑡𝑡𝑚𝑚̅ )2 𝐸𝐸(𝑡𝑡)𝑑𝑑𝑑𝑑 of the RTD, is an
this preliminary set of results. The next set of experiments will
indication of the spread 𝐸𝐸(θ) of the data
= 𝐸𝐸(𝑡𝑡)𝑡𝑡 about
̅ the mean and was
0
𝜏𝜏 2
𝑚𝑚 involve more detailed analysis of the species making up these
𝑛𝑛 = 2
𝑡𝑡
𝜎𝜎θ =
̅
𝑡𝑡𝑚𝑚
http://dx.doi.org/10.4314/wsa.v43i4.13𝑡𝑡
𝜏𝜏 2
θ𝑛𝑛==
̅ 21
𝑡𝑡𝑚𝑚
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𝜎𝜎
ISSN 1816-7950 (Online)𝑋𝑋==Water
1 − SA Vol. 43𝑛𝑛No. 4 October 2017
(1=
𝐸𝐸(θ) 𝜏𝜏𝑖𝑖 𝑘𝑘) 𝑚𝑚
+ 𝐸𝐸(𝑡𝑡)𝑡𝑡 ̅ 660
Published under a Creative Commons Attribution Licence

𝐸𝐸(θ)
𝑋𝑋 = =
1− ̅1
𝐸𝐸(𝑡𝑡)𝑡𝑡𝑚𝑚
𝑉𝑉 + 𝜏𝜏2𝑖𝑖 𝑘𝑘)𝑛𝑛
(1
 Figure 5
The normalized RTD function for the pilot CW determined from an
impulse-response tracer test, with τ = 2.16 d (θ = 0.78), tm = 2.89 d (θ = 1.0)
and a peak time at maximum concentration of 2.31 d (θ = 0.80)

Table 5
Various hydraulic parameters describing the behaviour
of the pilot CW as determined from the impulse-response
tracer test and system RTD
Hydraulic parameter Value
Mean volumetric flow rate (L·d ) −1
534.7
Reynold’s no. (Re) 0.11
Reactor volume (L) 1 156.2
Mean residence time, tm (d) 2.89
Nominal residence time, τ (d) 2.16
Variance, σ (s )
2 2
1.116 x 1010
Figure 6
Peak time at max. concentration
2.31 (a) Total organic carbon concentration (avg. inlet [TOC] =
(days after injection) 573 ± 62 mg·L−1; baseline TOC = ± 3.0 mg·L−1 ) and (b) total nitrogen
t99 (d) 6.54 concentration (ave. inlet [TN] = 230 ± 21 mg·L−1; baseline TN
= ± 0.57 mg·L−1), as a function of time at the wetland outlet up to
Recovery (%) 100 7 weeks after the introduction of artificial wastewater into the system

sum parameters. that this is not the case in reality and increases and decreases
The TOC and TN concentrations at the system outlet over in flow rate from inlet to outlet were observed. A decrease in
the 7-week experimental period are shown in Figs 6a and flow was the general trend, unless a large rain event produced
6b. The inlet and outlet concentration data for Weeks 1 and an increase in flow from inlet to outlet. However, due to data
2 is plotted as individual points because the system was yet from the outlet pump being unavailable over the full 7-week
to achieve a state of steady operation. Fig. 6a indicates TOC duration of the experiment and the fluctuation in flow being in
degradation and Fig. 6b shows TN transformation. There is a the vicinity of 15%, the steady flow assumption was deemed to
general decrease in TOC and TN removal from late October be reasonable. In future, it will be beneficial to conduct a more
to early December, indicated by the increasing outlet TOC and detailed investigation into the fluctuations in the inlet and
TN concentrations over this period. The change of season and outlet volumetric flow rates.
the resultant colder ambient temperatures would have lowered When the inflow loads (Table 6) are considered and the
microbial activity and any decomposition of dead bio-matter inlet concentrations (Fig. 6) are compared to the typical Class 2
could have introduced additional nitrogen into the system German effluent composition (Table 2), it is evident that the sys-
(Kadlec and Wallace, 2009). tem was receiving a noticeably higher load of carbon and nitrogen.
The TOC and TN loading rates, per unit surface area, are The minimum capacity of the metering pump meant that the flow
given in Table 6. The calculations were performed on a weekly rate of AWW had to be maintained at a higher setting; resulting
basis and coinciding with each sampling day. For the purpose in a larger ratio of AWW to feed water than initially desired. In
of these calculations, it was assumed that the inlet and outlet addition, the inflow instability experienced over the first 2 weeks
concentrations of TOC and TN (measured weekly) were the reduced the quantity of utilizable data. Due to the limited experi-
average values for the preceding week. The volumetric flow rate mental time available and the 3-week period required to attain
was monitored on a daily basis and the weekly average was cal- steady operation after adjustments to the pump settings, it was
culated. It was further assumed that the system was operating decided to continue with a higher inflow load.
at approximately steady-state (Qin ≈ Qout). It is acknowledged Table 6 shows the percentage of TOC and TN removal,

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calculated on a weekly basis and taking into account the Kinetics of contaminant degradation
average hydraulic residence time during each week. From
Week 3 onwards, once the flow had stabilized, an average of For the purposes of this paper, the rates of transformation of TOC
93.05 ± 3.09% removal of TOC and 93.42 ± 2.42% removal and TN (from urea) were considered. The RTD was used to guide
of TN were achieved; despite the high inflow loading and the the choice of a reactor model to describe the system so that the
lower temperatures. rate constants for these transformations could be calculated. The
Figure 7b shows the DO concentration of the outlet stream tanks-in-series (T-I-S) model, along with a first-order rate law,
over the duration of the experiment. Each week, the DO was was chosen for this preliminary investigation. According to the
found to be below 0.75 mg·L−1, which indicates high oxygen T-I-S model, a packed bed reactor can be described by a number
consumption when compared to the 11.158 ± 1.208 mg·L−1 DO of continuously stirred tank reactors (CSTRs) of equal volume in
at the wetland inlet. This is thought to be due to the action of
micro-organisms in degrading organic carbon (Kadlec and
Wallace, 2009). To support this hypothesis, the general trend
in TOC concentration as a function of distance along the flow
path is also plotted in Fig. 7a and shows that organic carbon is
degraded in the first half of the bed. In general, oxygen con-
sumption appears to be higher in the first 300 cm of the bed,
where the largest reduction in TOC is also observed. It is also
noted that the standard deviation at each sample port increases
with distance down the wetland bed. This spread of data points
is most pronounced at the wetland outlet (600 cm). In general,
the DO concentration is greater at the start of the experi-
ment (28 October) and lower towards the end of the sampling
campaign (8 December). In the autumn (October/November
2015), the plants could still have been contributing oxygen to
the system (Kadlec and Wallace, 2009); hence the higher DO
data on 28 October, 11 and 17 November in the sample ports
after 300 cm, where TOC degradation had largely ceased.
As the experiment proceeded into the beginning of winter
(December 2015), oxygen input by the plants should have been
much less, but the plants were still observed to be active up
until 8 December. The continued activity, even if slower at this
time, coupled with reduced oxygen input from the roots, could
explain the lower DO data on 2 and 8 December in the sample
ports after 300 cm and the larger spread of data points for these
latter sample ports.
The redox potential as a function of time at the wetland
outlet is plotted in Fig. 8 and a progressive decrease in poten-
tial can be seen over the 7-week experiment. This decrease in
potential indicates that the system became more anoxic, as
would be expected if oxidative degradation processes were tak-
ing place. Oxidative degradation may have produced a number
of reduced species, such as nitrate (NO3-) and nitrite (NO2-). The Figure 7
(a) The general trend in TOC concentration (ave. inlet
presence of these reduced species would have contributed to the
[TOC] = 573 ± 62 mg·L−1) and (b) the dissolved oxygen concentration
observed decline in redox potential (Kadlec and Wallace, 2009). at increasing distance from the wetland inlet over the 7-week
experimental period (ave. inlet [DO] = 11.158 ± 1.208 mg·L−1; ave. inlet
temp = 10.9 ± 2.6°C)

Table 6
Total organic carbon and total nitrogen average weekly hydraulic loading rate and percentage removal
TOC TN
Ave. bed HLR (g·m −3·d−1) )g/m3·d) HLR (g·m −3·d−1)
Week a
Date (2015)
temp. (°C) % removal % removal
Inflow Outflow Inflow Outflow
1 21 Oct–28 Oct 8.8 34.7 8.68 75.01 13.3 2.68 79.86
2 28 Oct–04 Nov 8.5 92.0 7.54 91.81 43.5 2.73 93.71
3 04 Nov–11 Nov 13.0 69.9 3.17 95.47 28.1 0.97 96.56
4 11 Nov–17 Nov 10.6 69.9 1.67 97.62 28.1 1.09 96.12
5 17 Nov–25 Nov 3.3 69.9 7.73 88.95 28.1 2.39 91.47
6 25 Nov–02 Dec 7.4 69.9 5.97 91.47 28.1 2.55 90.93
7 02 Dec–08 Dec 6.6 69.9 5.76 91.77 28.1 2.25 92.00
2 mentioned date in each row is the day on which samples were taken and analysed
a nd

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 𝑡𝑡
θθ== 𝑡𝑡
̅̅
𝑡𝑡𝑡𝑡𝑚𝑚
𝑚𝑚
̅
𝐸𝐸(θ) = 𝐸𝐸(𝑡𝑡)𝑡𝑡𝑚𝑚

series. The number of𝐸𝐸(θ)

tanks
𝐸𝐸(θ)=in series,𝑚𝑚
=𝐸𝐸(𝑡𝑡)𝑡𝑡
𝐸𝐸(𝑡𝑡)𝑡𝑡 ̅ ̅ n, was calculated by: Figure 9 shows the rate constants for the degradation of
𝑚𝑚
TOC and the transformation of TN from Week 3 onwards
𝜏𝜏 2 when the system was operating more stably, with the calcu-
𝑛𝑛 = (8) lated values presented in Table 7. A similar trend of variation
𝜎𝜎 2 𝜏𝜏22
𝑛𝑛 = 𝜏𝜏 2 in rate constants, with regards to both carbon and nitrogen,
= 𝜎𝜎2 inflow concentration and
This method requires 𝑛𝑛a constant can be seen. A certain degree of variation in the rate constants
𝜎𝜎
volumetric flow rate. The conversion, X, of the reacting spe- may be expected because TOC and TN are sum parameters
cies was related to the mean residence time and reaction rate and dependent on multiple chemical processes. In addition,
constant by:
11 the temperature dependence of the rate constant should also
𝑋𝑋 = 1𝑋𝑋 −
=1−
(1 𝑛𝑛
𝑖𝑖 𝑘𝑘)𝑛𝑛
(1 + +𝜏𝜏𝑖𝑖1𝜏𝜏𝑘𝑘) be considered. The reaction rate constant of most chemi-
𝑋𝑋 = 1 − cal reactions is directly related to the reaction temperature
(1 + 𝜏𝜏𝑖𝑖 𝑘𝑘)𝑛𝑛 (9)
and increases with an increase in temperature, or vice versa
𝑉𝑉 (Atkins and De Paula, 2006). The temperature in the wet-
where 𝜏𝜏𝑖𝑖 = (10)
𝑉𝑉 0 𝑛𝑛
𝑣𝑣 land decreased as the weeks progressed from autumn into
𝜏𝜏𝑖𝑖 = by the
where conversion is defined
𝑉𝑉 the beginning of winter (Fig. 9), and this could account for
𝑣𝑣0 𝑛𝑛 quotient of the number of
𝜏𝜏𝑖𝑖 = the general decline in the reaction rate constant, particularly
moles of the species reacted to the 𝑣𝑣0 𝑛𝑛number of moles of the same
species fed into the system. Hence, in terms of concentration: beyond the third week of the experiment. As the micro-
organisms acclimatize to the different types and quantities of
𝐶𝐶𝐴𝐴𝐶𝐶 nutrients available and plant activity increases significantly
𝐶𝐶 = 𝐶𝐶 (1 − 𝑋𝑋) 𝑜𝑜𝑜𝑜 𝐴𝐴= (1 − 𝑋𝑋) (11)
𝐶𝐶𝐴𝐴 = 𝐶𝐶𝐴𝐴0 (1 − 𝑋𝑋) 𝑜𝑜𝑜𝑜𝐶𝐶𝐴𝐴0 = (1 − 𝑋𝑋)
𝐴𝐴 𝐴𝐴0
with the onset of spring in 2016, it is expected that the rate
𝐶𝐶𝐴𝐴0
constants will change. Thus, the values calculated here should
Substituting Eq. 11 into Eq. 9 yields: be treated as a point of reference.
The rates of TOC and TN removal over the same
𝐶𝐶𝐴𝐴0 period (Weeks 3–7) are also presented in Table 7. The
𝐶𝐶𝐴𝐴 = 𝐶𝐶𝐴𝐴0 𝑛𝑛
𝐶𝐶𝐴𝐴 =(1 + 𝜏𝜏𝑖𝑖 𝑘𝑘) rates have been calculated on a weekly basis. It is difficult
(1 + 𝜏𝜏𝑖𝑖 𝑘𝑘)𝑛𝑛 (12)
to compare the rate of TOC degradation with the rate of
Equation 12 was used to solve for the reaction rate constants TN transformation directly because the wetland was sub-
(Fogler, 2006). ject to different inlet loading rates (the system received
2.5 times more organic carbon than nitrogen). For direct

Figure 8
The change in oxidation-reduction potential as a function of time at Figure 9
the wetland outlet up to 7 weeks after the introduction of artificial The variability in the rate of decomposition of total organic carbon,
wastewater into the system (ave. inlet potential = 336.1 ± 30.1 mV). kTOC, and the rate of transformation of total nitrogen, kTN

Table 7
Reaction rate constant and rate of removal of total organic carbon, r TOC, and total nitrogen, r TN
(inlet load: TOC = 69.9 g·m−3·d−1 and TN = 28.1 g·m−3·d−1)
Week a
Date (2015) Ave. bed temp (°C) kTOC (d-1) r TOC (g·m −3·d−1) kTN (d-1) r TN (g·m −3·d−1)
3 04 Nov–11 Nov 13.0 0.494 66.77 0.552 27.10
4 11 Nov–17 Nov 10.6 0.633 68.27 0.526 26.98
5 17 Nov–25 Nov 3.3 0.325 62.21 0.371 25.67
6 25 Nov–02 Dec 7.4 0.371 63.96 0.360 25.52
7 02 Dec–08 Dec 6.6 0.378 64.18 0.383 25.82

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comparison, the percentage removal is more meaningful • The National Research Foundation (NRF)
(approximately 93% reduction in both TOC and TN was • The German Academic Exchange Service (DAAD)
achieved). The rate of removal is relatively constant, but • Water4Crops (an EU initiative)
there is a greater variation in the rate of TOC degradation
( = 65.08 ± 2.16 g·m−3 ·d−1) than in the rate of TN transforma- REFERENCES
tion ( = 26.22 ± 0.68 g·m−3 ·d−1). The temperature dependence
of the reaction rate can also be observed. The reaction rate ALBERTSON ML (1998) Constructed wetlands for wastewater treat-
is higher in Weeks 3 and 4, when the temperature was above ment: a proposed research program. Wetlands Engineering and
10°C. There was a sudden drop in temperature in Week 5, River Restoration Conference 1998, 22-27 March 1998, Denver,
Colorado. American Society of Civil Engineers. https://doi.
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org/10.1061/40382(1998)121
pronounced for TOC. ATKINS P and DE PAULA J (2006) Atkins’ Physical Chemistry. Oxford
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Waters. Stevens Water Monitoring Systems Inc., Portland, Oregon.
newly established CW. A better understanding of the natural
BENYUS JM (2017) Biomimicry 3.8 Resource Handbook. URL: http://
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loadings were high and the experimental period spanned the BRIX H (1994) Use of Constructed wetlands in water pollution control:
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APPENDIX

Abbreviations Nomenclature

AMD acid mine drainage CA0 concentration of Species A in the feed

AWW artificial wastewater CA concentration of Species A at the system outlet
BOD5 5-day biological oxygen demand C(t) time variant tracer concentration
COD chemical oxygen demand E(t) residence time distribution function
CSTR continuous stirred tank reactor E(θ) normalized residence time distribution function
CW constructed wetland kTOC reaction rate constant for the decomposition of TOC
DO dissolved oxygen kTN reaction rate constant for the transformation of TN
HSSF horizontal subsurface flow M mass of tracer injected
RTD residence time distribution n number of tanks in series
T-I-S tanks-in-series model R percentage recovery
TN total nitrogen tm mean residence/retention time
TOC total organic carbon V system fluid volume
v0 system volumetric flow rate
Greek characters X conversion or extent of reaction

σ standard deviation
σ2 variance
τ nominal residence time or hydraulic retention time
θ normalized time

http://dx.doi.org/10.4314/wsa.v43i4.13
Available on website http://www.wrc.org.za
ISSN 1816-7950 (Online) = Water SA Vol. 43 No. 4 October 2017
Published under a Creative Commons Attribution Licence 665