Ecological Engineering 37 (2011) 70–89

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Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Filter materials for phosphorus removal from wastewater in treatment

wetlands—A review
Christina Vohla a , Margit Kõiv a , H. John Bavor b , Florent Chazarenc c , Ülo Mander a,∗
a
Department of Geography, Institute of Ecology and Earth Sciences, University of Tartu, 46 Vanemuise St., Tartu 51014, Estonia
b
Water Research Laboratory, University of Western Sydney-Hawkesbury, Locked Bag 1797, Penrith South DC, NSW 1797, Australia
c
Ecole des Mines de Nantes, GEPEA UMR CNRS 6144, 4, rue Alfred Kastler, B.P. 20722, F-44307 Nantes Cedex 3, France

a r t i c l e i n f o a b s t r a c t

Article history: This paper aims to collect and analyse existing information on different filter media used for phosphorus
Received 18 November 2008 (P) removal from wastewater in constructed wetlands. The most commonly used materials are catego-
Received in revised form 4 August 2009 rized as natural materials (considered in 39 papers), industrial byproducts (25 papers) and man-made
Accepted 12 August 2009
products (10 papers). A majority of studies on sorbents have been carried out in lab-scale systems as batch
experiments, and only very few studies have highlighted results on full-scale systems. Among the great
variety of filter media studied, most of materials had a pH level >7 and high Ca (CaO) content. The highest
Keywords:
P-removal capacities were reported for various industrial byproducts (up to 420 g P kg−1 for some furnace
Ash
Bauxite
slags), followed by natural materials (maximum 40 g P kg−1 for heated opoka) and man-made filter media
Constructed wetlands (maximum 12 g P kg−1 for Filtralite). We found a significant positive Spearman Rank Order Correlation
Freundlich equation between the P retention and CaO and Ca content of filter materials (R2 = 0.51 and 0.43, respectively),
Langmuir equation whereas the relation of P retention to pH level was weak (R2 = 0.22) but significant. There is probably an
LECA optimal level of hydraulic loading rate at which the P removal is the highest. Additional important factors
Limestone determining the applicability of filter materials in treatment wetlands such as saturation time, availability
Peat at a local level, content of heavy metals, and the recyclability of saturated filter media as fertilizer should
Saturation
be taken into consideration.
Slags
© 2009 Elsevier B.V. All rights reserved.

1. Introduction In Europe, the supplementary treatment of wastewater from

Phosphorus (P) is an important nutrient that is critically
needed for the normal functioning of ecosystems. Nevertheless,
excess P and nitrogen (N) is the main cause of euthrophication
(Vollenweider, 1968; Schindler, 1977; Tiessen, 1995). The main
input of P into nature occurs through its use in agriculture and from
domestic wastewater (Soranno et al., 1996; Bennett et al., 2001).
Whereas P can be regulated by balanced fertilization in agricultural
use (Sharpley and Tunney, 2000), wastewater needs proper treat-
ment for the removal of P to levels that are acceptable for natural
systems (Kadlec and Knight, 1996).
Phosphorus removal in conventional small-scale wastewater
treatment systems is a critical issue that has not yet been suffi-
ciently solved. Moreover, continuing eutrophication, especially in
freshwater ecosystems, has led to increasing governmental reg-
ulatory pressure for the lowering of P concentrations through
enhanced P removal from wastewater (Kadlec and Wallace, 2008).
∗ Corresponding author.
E-mail address: ulo.mander@ut.ee (Ü. Mander).
houses and small rural communities specifically designed for P
removal is becoming important for the improvement of environ-
mental quality in streams and lakes (Brix et al., 2001).
Subsurface flow constructed wetlands (SSF CW) function very
effectively in the treatment of the wastewater of small settlements
and rural areas. SSF CWs are known to be efficient in the removal of
both biological oxygen demand (BOD5 ) and total suspended solids
(TSS) from wastewater. However, nitrogen (N) and phosphorus (P)
removal is known to be somewhat problematic (Brix et al., 2001;
Vymazal et al., 1998).
Subsurface flow and other treatment wetlands have been used
for the purification of industrial wastewater (agroindustry produc-
tion, paper industry, etc.), mine water, agricultural runoff water
and also landfill leachate purification, and most often for domestic
wastewater (Kadlec and Knight, 1996).
Phosphorus removal in subsurface flow CWs is closely associ-
ated with the physical–chemical and hydrological properties of the
filter material, because P is mainly sorbed by or precipitated in filter
media (Faulkner and Richardson, 1989; Kadlec and Knight, 1996;
Sakadevan and Bavor, 1998; Vymazal et al., 2000). The removal of
P in constructed treatment wetlands is a complicated and difficult

0925-8574/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ecoleng.2009.08.003
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
to sustain process. The life expectancy of sub-surface flow CWs,
especially as concerns phosphorous removal, depends on the fil-
ter media that are used for the construction (Grüneberg and Kern,
2001; Sakadevan and Bavor, 1998). A medium with a high phos-
phorus binding capacity is an important component of treatment
wetlands (Arias et al., 2001).
The search for efficient and long-lasting filter media has been
a key issue for more than a decade. However, the longevity of the
sorption capacity of phosphorous is still a main focus for research
(Johansson Westholm, 2006). In addition to good hydraulic con-
ductivity, the chemical composition of the adsorption media is a
critical factor in CW design. Because phosphorus is removed via
sorption and precipitation processes, Ca, Fe and Al content is impor-
tant in efficient P removal. Thus filter media should be selected very
carefully. Even if a medium with high P binding capacity has been
selected, it may be saturated after a few years (Arias et al., 2001).
An obvious and sustainable solution would also be a separate filter
unit containing replaceable material with a high P binding capacity
(Brix et al., 2001). In such systems, appropriate pre-treatment will
also allow for a longer lifetime of the filter media, by decreasing the
risk of clogging and allowing one to use finer reactive filter media
with higher sorption capacity (Hedström, 2006).
1.1. Sorbents for phosphorus removal
A great variety of different types of materials for P retention in
CWs have been described. Traditionally, locally available sands and
soils have been used as filter media in sub-surface flow wetlands
for retaining P, even without any data about P-removal efficiency
(Johansson Westholm, 2006), for example sand filters or gravel
(Rustige et al., 2003). Studies performed during the last decade have
demonstrated the importance of finding locally available materials
with high P retention capacity. Johansson Westholm (2006) also
emphasised the fact that regardless of the great amount of existing
scientific data, the potential and efficiencies of different materials
and studies are very difficult to directly be compared and general-
ized.
There are many studies that use the special treatment of filter
media to enhance P retention capacity (Brogowski and Renman,
2004; Kwon et al., 2004; Li et al., 2006). Usually heating Ca-rich
media at high temperatures is a common way to perform material
improvement. During heating, CaO will probably form, which has
a more reactive Ca-phase than commonly existing CaCO3 .
The objectives of this paper are to (1) summarize existing infor-
mation on different filter media used for phosphorus removal from
wastewater that could be applied to one database, with the advan-
tages and disadvantages of each amendment and (2) to clarify
relationship between P retention capacity, pH level, Ca(CaO) con-
tent, and the hydraulic parameters of the filter media.
2. Methods
Data about various filter materials have been collected to give
an overview of advantages, but also to emphasise the critical condi-
tions and possible limiting factors for the usage of these materials.
A preliminary screening of available data showed that majority of
filter materials studied have high Ca and/or CaO content. Based on
these data, analysis of the influence of Ca(CaO) content and pH on
the P retention capacity was performed. However, to give a bet-
ter overview of the different types of materials and their potential
as a filter media, articles where only P-removal effectiveness or
retention capacity were also presented, have been included in our
analysis. Some literature sources provided with information on the
hydraulic loading rate (HLR) and hydrologic retention time (HRT).
71
These data were taken into account and analysed in combination
with P retention values.
A valuable overview of sorbents that have been used for phos-
phorus removal was presented in Johansson Westholm (2006). In
our work we have considered many additional data for substrates
and special sorbents. Analyses of the impact of pH and sorbents
such as Ca and CaO are also included.
Three basic databases are used for this overview: the ISI Web of
Science, Scopus, and ISI Proceedings. The main topics used for the
database search were as follows: “phosphorus removal”, “phospho-
rus retention”, “phosphorus sorption”, “phosphorus adsorption”,
and “phosphorus precipitation”. An analogous search was carried
out using the terms “phosphorous” and “phosphate(s)” instead of
“phosphorus” in these word combinations. All of the term combi-
nations mentioned above were also analysed adding the following
terms: “constructed wetland(s)”, “soil filter(s)”, “sand filter(s)”, and
“filter material(s)”. In addition, the following names indicating var-
ious filter materials were analysed in combination with the terms
“phosphor(o)us” and “phosphate(s)”: “ash”, “bentonite”, “blast fur-
nace slag”, “calcite”, “ceramic”, “clay”, “coal”, “Filtralite”, “gravel”,
“LECA”, “limestone”, “LWA”, “oil shale ash”, “Opoka”, “peat”, “sand”,
“shellsand”, “slag(s)”, and “wollastonite”.
The most commonly used materials can be broadly categorized
as natural materials (Table 1 ), industrial by-products (Table 2 )
and man-made products (Table 3). A total of 64 papers were used in
our analysis, and in 39 of the papers natural materials were studied,
whereas in 25 and 10 papers, industrial byproducts and man-made
materials were considered, respectively. We gathered data on Ca
and CaO content and the pH level of the filter media in relation
to P retention capacity. Data lacking one of the above-mentioned
characteristics were excluded. Considering both the lack of data
and the wide range of experimental conditions for full-scale and
bench-scale experiments, all of the data considering Ca and CaO
content of filter materials came from batch/sorption tests alone.
Among the gathered data, very few data were provided about
pH and CaO. That is why in the CaO analyses, only 37 data points
from 9 papers were used, compared to Ca analyses (78 data points
available from 22 papers).
All of the data were analysed for the normality of distribu-
tion using the Lillefors test and the programme STATISTICA 7.0.
Spearman Rank Order Correlations were provided to describe the
relationships between the P removal, pH, and Ca and/or CaO con-
tent of the filter media. The level of significance of ˛ = 0.05 was
accepted in all cases.
3. Results and discussion
3.1. Filter materials used for phosphorus removal
3.1.1. Natural products
3.1.1.1. Apatite. Is a group of phosphate minerals, usually referring
to hydroxylapatite, fluorapatite, and chlorapatite, containing OH− ,
F− , or Cl− ions, respectively, in the crystal. Sedimentary apatites
are charactarezied by high Ca and P content (31.4% Ca and 11.3%
P in Bellier et al., 2006; 37.3% Ca and 16.8% P in Molle et al., 2005;
37.6% Ca and 15.2% P in Joko, 1984). Presence of P-crystal in apatite
is believed to act like a catalyst which lowers the activation energy
barrier between the crystal and precipitated P. The distinction
between adsorption and crystallization is not clear in P-sorption
mechanisms on natural apatites, considering that their concomi-
tant action is expected to occur. P sorption from 0.4 up to 4.8 g
P kg−1 apatite have been measured in batch experiments (Bellier
et al., 2006; Molle et al., 2005; Joko, 1984). Full-scale experiments
showed promising results (enough to reduce P-level to reach 2 mg
 72
Table 1
Natural materials used as filter media for P removal.

Material Study type Description of the study Retention calculation P retention Ca (CaO) References pH

Alunite Batch Adsorption: 1 g of material
(calcinated) with 1 L of phosphate
solution (25–150 mg L−1 ),
contact time 29.1 min
Apatite Batch KH2 PO4 solution of
(sedimentary) 0–500 mg P L−1 with
contact time of 1–48 h
Column Synthetic solution 20 mg P
L−1 with hydraulic loading
rate (HLR) 1.35 L d−1 in 550
days (hydraulic retention
time (HRT) 5.6 h)
Apatite Batch/column 35 g of material in a 1 L
(igneous and glass flask filled with
Calculated Average of over 80% – Özacar (2006) 5
removal
Langmuir Langmuir b = 4.76 mg P 37.3 Molle et al. (2005) 7.0
g−1 , K = 0.15
Saturation value after
550 d 13.9 mg P g−1 ;
<2 mg P L−1 in the
outlet
Langmuir/Freundlich 0.28–1.09 g P kg−1 7–31.4% Bellier et al. (2006) 8
material in 24 h

C. Vohla et al. / Ecological Engineering 37 (2011) 70–89

sedimentary) 700 mL of solution isotherms
(5–150 mg P L−1 ) 24 and
96 h isotherms
Bauxite Batch 2.5–40 mg P L−1 , 20 g and Langmuir Adsorption 0.612 g – Drizo et al. (1999) 5.9
24 h and column study kg−1 . Column: 160 mg
(40d + 40d); HLR 3 L d−1 P kg−1 , longer study:
355 mg P kg−1
Bauxite Batch 1 g substrate and 100 dm−3 Calculated Maximal PO4 3− – Altundoğan and Tümen (2002)
solution, 10 mg P dm−3 and removal 67.3% at pH
shaken for 2 h 4.45
Bauxites (raw Batch 1 g substrate and 100 dm−3 Calculated Adsorption for raw and – Altundoğan and Tümen (2003) 4.5–5.2
and activated) solution, 10 mg P dm−3 and activated bauxite: 0.82
shaken for 2 h and 2.95 mg P g−1 ,
removal >95% for
activated bauxite
Dolomite Batch 0.2 g in 100 mL solution Calculated Sorption 21.7% Karaca et al. (2004) Highest adsorption at pH 11
10–60 mg PO4 -P L−1 , 7.34–52.02 mg P g−1
different adsorption times,
temperature, pH 1–11,
material from Turkey
Dolomite and Batch 10 g sorbate in 50 mL Langmuir 0.168 g P kg−1 28.7% Prochaska and Zouboulis (2006) 7.8
sand solution with 0–100 mg
L−1 , 24 h
0.121 g P kg−1 2.5% 6.9

Gravel Full-scale CW, Batch 3 gravel based CWs
investigated, secondary
sewage effluent, 2 years.
Laboratory P adsorption
study
Gravel Full-scale CW Gravel filled wetland, dairy
farm wastewater, mean
influent concentration
15 mg P L−1 , 5 years; HLR
21.4–71.7 mm d−1 , HRT
1.95–6.54 d
Langmuir and Freundlich P removal from −40% – Mann and Bavor (1993)
to 40%. Adsorption
capacity ranged
25.8–47.5 mg P g−1
Determined Total P (TP) removal 1.07% Tanner et al. (1999)
184–296 g m−2 ,
substratum TP
accumulation
115–128 g m−2
Gravel Full-scale CW VSSF planted gravel filter
in Turkey, HLR 3 m3 d −1
(0.1 m d−1 )
Gravel Pilot-scale CW HSSF CW, planted, 2 years,
HRT 6–20 days; HLR
16–55 L d−1
Gravels (South- Batch 3 g sorbate, 75 mL solution
Estonian) with 5–1000 mg PO4 -P L−1 ,
24 h
Laterite Batch, pilot-scale Sorption test with leachate
(10 g granular laterite,
solution with 5–50 mg
PO4 -P− L−1 ) and pilot CW
about 2 years
Limerock Meso-scale CW Experimental wetland
system received effluent
from a treatment wetland
for 19 months; HLR 11 cm
d−1
Limestone Batch 1 g substrate, P-solutions
(5–25 mg PO4 –P L−1 ),
limestone from Sweden
Limestone Batch 2.5–40 mg P L−1 , 20 g and
24 h, material from a
quarry; HLR 3 L d−1
Limestone Full-scale CW SSF wetland cell treating
wastewater from dairy
farm. HRT 13.4 d, 1.5 years
Maerl Pilot-scale CW, batch Pilot-scale wetlands in the
laboratory, 9 weeks, 21 L.
HLR 2.3 L d−1 ; HRT 5 d.
Batch: 4 g, 100 mL of P
solution (0–5000 mg L−1 ).
72 h
Marl gravel Full-scale CW Filter treating swine
wastewater after anaerobic
lagoon treatment
Opoka Batch 1 g substrate, P-solutions
(5–25 mg PO4 -P L−1 )
Opoka (heated) Batch Artificial P solutions
(K2 HPO4 ), distilled water
Oyster shell Batch, column P solution 0–320 mg P L−1 .
(burnt) Column, 100–g medium (1
month), 50 mg P L−1 , HRT
4 h, HLR 300 mL d−1
material from Korea
Peat Lab-scale biofilter Domestic wastewater (1
month) lab-scale filters
300, 600, 1200 L m−2 d−1 ,
household biofilter
70–258 L m−2 d−1
Calculated PO4 3− -P removal – Korkusuz et al. (2005)
efficiency of the gravel
system 4.33%
Calculated Medium gravel 43.9%, 27.2% Akratos and Tsihrintzis (2007)
with cobbles and
cattail up to 67%
Calculated Removal 33–50%, 2–14% (3.6%) Vohla et al. (2005)
sorption 3–3.6 g P kg−1
(fine gravel: 88.6%)
Calculated 99% removal of – Wood and McAtamney (1996)
phosphates in lab and
96% in pilot CW
Calculated TP removal for the – DeBusk et al. (2004)
filter system was 0.32 g
P m−2 year−1 and 46%
C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Calculated Sorption 0.25–0.3 mg P 21.2% Johansson (1999a) 8.9
g−1
Langmuir Maximal adsorption – Drizo et al. (1999) 7.8
capacity 0.682 g kg−1 .
Calculated P retention on average – Hill et al. (2000) 7.2
4.3%. Mean reduction
14.5%
Calculated TP removal 98%. Batch 32.04% Gray et al. (2000) pH out of tank 7.6
removal 32–99%,
capacity
39.5–7490 mg kg−1
Calculated Removal efficiency of 12% Szögi et al. (1997)
TP 37–52%
Calculated P-sorption capacity 20.0% Johansson (1999a) 8.3
<20%, sorption
0–0.1 mg P g−1 .
Calculated Maximum sorption 30.1 (42.1)% Brogowski and Renman (2004) 12.6
capacity was 119.6 g
PO4 -P kg−1
Langmuir Adsorption 37.80% Seo et al. (2005)
833.3 mg kg−1 , column
(unsaturated media)
7925 mg kg−1
Calculated P removal in lab-scale – Talbot et al. (1996)
filters 44%. Biofilter:
12% for TP
73

Table 1 (Continued).
Material Study type Description of the study
Peat Small-scale CW in field Filters treated landfill
leachate from activated
sludge treatment plant (12
months) and from biopond
(6 months), volume
0.11 m3 , loaded 36–41 mm
d−1 and 82 mm d−1
Peat Pilot-scaleCW VF peat filters and HF
filters treated municipal
wastewater and landfill
leachate, VF 0.86 m3 ,
76 mm d−1 and HF 1.24 m3 ,
53 mm d−1 (HLR 60 L d−1 ),
6 months
Polonite Column Columns: 20 ◦ C,
water-saturated
conditions. PO4 -P and
NH4 -N (5.30 mg dm3 ), tap
water, HLR 530 L m−2 d−1 ,
68 weeks
Sand Column Columns with upflow
hydraulic regime, load
0.5–2.0 mg L−1 , filled with
sand; HRT 2 h; HLR
7.2–86.4 L d−1
Sand Full-scale CW HSSF sand filter, 8 years;
HLR 3.2–5.5 m3 d−1
Sand, dolomite Batch, column Sorption experiment: 1 g
sand and shale 20 mL (0–100 mg P L−1 )
24 h. Column: SSF study at
loading of P 330 mg m−2
d−1 . Loading: 105 mg P m−2
d−1 , HLR 60–120 L m−2 d−1 ,
33 months
Sands (Danish) Batch, column Solution 320 mg P L−1 by
calculated retention and
0–10 mg P L−1 by
Langmuir. Columns 12
weeks; HLR 0.24–L d−1 ;
HRT 12–14 h
Sands (South- Batch 3 g sorbate and 75 mL
Estonian) solution (5–1000 mg PO4
L−1 ), 24 h
Full-scale CW HSSF sand filter, 5 years;
HLR 1.0–6.3 m3 d−1
74
Retention calculation P retention Ca (CaO) References pH
Calculated Reduction of TP during 5.1% Kõiv et al. (2009a) 7.2
the first 6 months 77%
from sludge water, 93%
from biopond water
Determined Removal in VF peat 5.1% Kõiv et al. (2009b) 7.2
filters was 58% and
63%, P binding capacity
0.081 g kg−1
Calculated Retained P 96.7% 24.5% Gustafsson et al. (2008) pH decreased from 11.7 to 9.5
C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Calculated P removal at low load 1.2% Farahbakhshazad and Morrison (2003)
(0.5–2.0 mg L−1 )
increased from 40% to
75% with 12
recirculations
Determined P in soil after 8 years 4.15% Vohla et al. (2007) Outflow, pH 7.4
0.117 g P kg−1 , 72%
Langmuir, determined Sorption 0.417 g P kg−1 , 5.1–7.5% Pant et al. (2001) 7.9–9.1
columns 0.7–1.0 g P
kg−1 ; 95%. Sand is
sensitive to P loading
Sorption 0.303 g P kg−1 , 26.4–26.6% 9.3–9.4
columns 0.2 g P kg−1 ;
44% removal
Sorption 0.192 g P kg−1 , 3–10.5% 8.1–8.9
columns 0.7–0.8 g P
kg−1 ; 37% removal
Calculated, Langmuir, determined Calculated removal 0.02–7% Arias et al. (2001) 8.2–8.7
0.272–3.941 g P kg−1 ;
Langmuir 0.02–0.129 g
P kg−1 ; determined
0.052–0.165 g P kg−1 .
Calculated P removal between 8.6 0.33–11% Vohla et al. (2005) –
and 27.2% or 2.45 g P
kg−1
Purification efficiency 4.15% Outflow, pH 7.4
78.4%. P in sand
52.8 mg kg−1
Shellsand Batch 3 g in 75 mL, 0–1000 mg P Calculated First batch 14–17 g P 28–30% Roseth (2000)
L−1 in 24 h, and also 3 g in kg−1 , second batch
5–1000 mg P L−1 in 48 h, 3–4 g P kg−1
Norwegian sand
Column Column, HLR 10 cm d−1 ; 32 Determined Adsorption capacity
d 3.5 g P kg−1
Shellsand Batch 5–1500 mg L−1 , 24 h Langmuir 0.8–8 g P kg−1 31.8% Søvik and Kløve (2005) 8.6
Meso-scale CW in field HSSF filter in greenhouse Determined 335 g P kg−1 , saturated
for household, 1 year, before 2 years, Ca-P
Norwegian sand, HLR (37–57%), Al-P (8–23%)
85 mm d−1
Shellsand Batch 3 g material for 24 h in Langmuir 9.6 g P kg−1 0.033% Àdàm et al. (2007) 8.8

C. Vohla et al. / Ecological Engineering 37 (2011) 70–89

90 mL solution (0–480 ppm
PO4 3− )
Column Vertical upflow columns Calculated 0.497 g P kg−1 , P
(330 d), HRT 4.1 d, HLR removal 97%
4.5 L d−1
Soils (sub-, top- Batch 3 g and 30 mL solution Langmuir Adsorption 0.006–0.3% Sakadevan and Bavor (1998) 4.2–7.2
and wetland (500–10,000 mg P L−1 ), 0.001–0.005 g P kg−1 .
soils) shaken for 48 h
Spodosol Batch Filter medium treated with Calculated P-removal 1 mg g−1 (1.5) Johansson (1999a) 6.3
artificial P solutions when P load 15 mg L−1 ,
(5–20 mg PO4 –P L−1 ). decline in removal
Sorption isotherm studies with higher load
Wollastonite Batch 5 g adsorbent and 75 mL Calculated PO4 -P reduction 32.9% Hedström (2006)
solution varying from 0.8 90–93%. P sorbed
to 1700 mg PO4 3− L−1 , for 0.1–12,000 mg kg−1
20 h
Wollastonite Column At 20 ◦ C, under Calculated 51.1% of P was 15.1% Gustafsson et al. (2008) 8.0
water-saturated removed
conditions. PO4 -P and
NH4 -N (5 and 30 mg dm−3 ),
tap water, HLR 610 L m−2
d−1 , 68 weeks
Wollastonite Column Vertical upflow columns Calculated >80% removal (up to – Brooks et al. (2000)
with HRT from 15 to 180 h, 96%), when the
secondary wastewater, 411 residence time was
d >40 h
Wollastonite Full-scale CW SSF wetland cell, Calculated Soluble P retention – Hill et al. (2000)
tailings wastewater from dairy 12.8%. Mean reduction
farm, HRT 13 d, 1.5 years was 27.5%.
Zeolite Batch 3 g and 30 mL solution Langmuir Adsorption 2.15 g P – Sakadevan and Bavor (1998)
500–10,000 mg P L−1 , 48 h kg−1

75
 76
Table 2
Industrial by-products used as filter media for P removal.

Material Study type Description of the Retention calculation P retention Ca (CaO)% References Particle size (mm) pH
study

Coal ash Batch, column (2.5–40 mg P L−1 , 20 g Langmuir Sorption for fly ash – Drizo et al. (1999) 8.2
and 24 h) and column 0.862 g P kg−1 . Column
study, furnace bottom 300 mg P kg−1
ash (40 days); HLR 3 L
d−1
Coal ash Batch Bottom ashes: 5–40 mg Langmuir 0.081–29.5 g P kg−1 2.4–11.7 (5–16.5) Yan et al. (2007) 0.1–2 9.5–11.6
HPO4 2− L−1 , fly ashes
200–1500 mg L−1 , 72 h
Fly ash Batch 5 g adsorbate and Langmuir 3.08 g P kg−1 2.6 (0.41) Cheug and 7.7
(lagoon), 25 mL solution with Venkitachalam (2000)
precipitator fly different P
ash and sand concentration, shaken
24 h

C. Vohla et al. / Ecological Engineering 37 (2011) 70–89

13.77 g P kg−1 5.0 (4.3) 12.4
0.04 g P kg−1 0.2 (0.01) 6.4

Fly ash (acidic) Batch, column Batch equilibration Calculated PO4 3− immobilization – Grubb et al. (2000) 4.5
experiments using a 75–100%. Column:
low Ca 1% as CaO and removed 10 mg L−1
50–100 mg P L−1 , 24 h. over 85 pv
A column, 10 mg L−1
Initial pH 8.5
−1
Fly ash Batch Laboratory P Langmuir, Freundlich 160–420 mg P g – Mann and Bavor (1993) 0.08–4.75 slag 1
adsorption study
260 mg P g−1 9.5–19 slag 2
<0.5 Fly Ash

Fly ash (Red Batch 20 mL of 155 mg L−1 Langmuir 113.9–345.5 g P kg−1 32–33 (45.2–46) Li et al. (2006) 10.1–11.9
mud) KH2 PO4 , materials
heated at various T
8.9–78.4 g P kg−1 1.5–1.9 (2.1–2.7) 8.3–10.0
−1
Fly ash Batch 25–1000 mg P L , at Langmuir Retention: from 5.5 to 1.8–18 (0.07–5.6) Chen et al. (2007) 5
adjusted pH 5, 40 mL 42.6 g P kg−1
PO4 2− solution;
reaction time 24 h, fly
ash from coal power
plant, China
Fly ash Full-scale CW CWs for the treatment Calculated Majority of the TP was – He et al. (2007)
of eutrophic river adsorbed by fly ash
water, 3 stage system, stage, TP removal
one filled with fly ash, about 83%
HLR 60 m3 d−1 ; 14
weeks
Iron ore 67% (aerated) and 53% 0.04
(anaerobic), working
area 140 ␮g P g−1
Quartz sand 70% (aerated) and 43% 0.01
(anaerobic)
Ochre Batch P solutions (1500 and Langmuir 0.026 g P kg−1 . 90% of 7 Heal et al. (2003, 2005) 7.2
3000 mg P L−1 ) were all P forms were
added until P was no removed after 5 and
longer removed from 15 min shaking
the solution. Between
additions stand 48 h,
dried. high saturated
hydraulic conductivity
26–32 m d−1
Oil shale Batch 2.5–40 mg P L−1 , 20 g, Langmuir Adsorption 0.582 g P – Drizo et al. (1999)
(burnt) 24 h; HLR 3 L d−1 kg−1
Sediment of oil Batch Batch experiments, Calculated 25 g PO4 3− kg−1 or 8.2 g 20.9 (29.2) Vohla et al. (2005) <0.063 12.32
shale ash 5–1000 mg PO4 3− L−1 , P kg−1
24 h
Pilot-scale CW Experimental filter in First 4 months removal 20.9 (29.2) Vohla et al. (2005) <0.15 Outflow pH 7.6

C. Vohla et al. / Ecological Engineering 37 (2011) 70–89

saturated conditions, 71%, after average 52%
tertiary treatment for
P, HRT 1.5–2 d−1 , 1 year
Sediment of oil Batch Batch experiments, Calculated P-binding capacity up Kaasik et al. (2008) 1–2 and 0.01 (weathered) 12.32
shale ash 5–300 mg PO4 3− L−1 , to 65 mg P g−1 ,
48 h, 9 d (67–85%). P sorption
due to Ca-minerals
(ettringite, portlandite)
Slags
Basic oxygen Column Synthetic aqueous Calculated Average PO4 -P removal 25.45 Kim et al. (2006) Adjusted pH 6–9
furnace slag solutions of P and Ca 90.4%
ions 40–80 mg L−1
Basic oxygen Column Soil, the mixture of Calculated After 1 day 100% 22.97 Cha et al. (2007) 1–2 11
furnace slag Korean soil from river
and slag were studied,
unsaturated columns
for 4 day 18 mL h−1 and
3 d brake, saturated
8–9.8 mL cm−2 d−1
Natural soil Unsaturated columns: 0.57
after 1 day 86%, after
4th day 58.6, saturated
columns 97.8%
Blast furnace Batch 0–320 mg L−1 , raw Langmuir P-sorption capacity up 23.97 Korkusuz et al. (2007) <3 7.7
slag domestic wastewater, to 9150 mg P kg−1
HLR 100 mm d−1 ,
10 mg P L−1 , 8 g
Blast furnace Column Water-saturated, Calculated WCBFS removed >95% 21.60 Gustafsson et al. (2008) 0–4 Effluent pH decreased from 11.4 to 8.8
slag PO4 -P and NH4 -N (5 P first 300 pvs, after P
and 30 mg dm−3 ), tap retention 85.6%
water, HRT 340 L m−2
day−1 , 68 weeks. BFS
from steel industry

77
 78
Table 2 (Continued)

Material Study type Description of the Retention calculation P retention Ca (CaO)% References Particle size (mm) pH
study

Blast furnace Small-scale CW Small-scale SSF CW, Calculated Up to 72% of P was 27.6 Grüneberg and Kern (2001) 0.3–1
slag dairy farm wastewater, retained, working area
planted, 9 L, load 200 ␮g P g−1
15 L m−2 d−1 ; hydraulic
conductivity: quartz
sand 1.4 × 10−3 m s−1 ,
slag 5 × 10−3 m s−1 ,
iron-ore 2.5 × 10−3 s−1 ;
4 months
Blast furnace Full-scale CW The CW system with Calculated Slag filters reduced TP – Cameron et al. (2003) 0.45–2.6 Up to 11.52
slag slag filters in Canada. up to 99%
Slag filters (trickling),
ca. 60 m3 day−1 , 7
months
Blast furnace Batch 180 ppm PO4 3− , 50 mL Freundlich 6.37 mg g−1 (500 ppm), 26.93 (37.7) Oguz (2004) 0.02–0.03
slag of solution, at 25–65◦C, during 60 min,
(Iskenderun) different pH values. Jar phosphate removal

C. Vohla et al. / Ecological Engineering 37 (2011) 70–89

tests: removal time of 99%
PO4 3− (150–500 ppm,
BFS 60 g L−1 ). Slag from
steel factory
Blast furnace Full-scale CW VSSF reed bed, Determined Average removal of TP 24.30 Korkusuz et al. (2005) 7.11–8.56
slag from granulated BFS, HRT 45%.
Turkey 3 m3 d−1 , HLR mm d−1 ,
11 months, slag from
iron and steel company
Electric arc Full-scale CW Detention time 3 day, Determined Slag maintained its 10.48 Shilton et al. (2005) N.A.
furnace loading 2000 m3 day−1 , maximum removal,
(melter) slag 1.5 years, slag from reaching TP retention
Steel Mill. of 1.23 kg T−1
Electric arc Column Columns, 20 mg P L−1 Determined Slag was nearly 100% – Drizo et al. (2006) 2.5–10 10.6–11
furnace slag (114 d) than 400 mg P efficient, removed
L−1 (21 d); HLR 2.2 mg P g−1
3.0–4.0 L d−1 ; HRTv
12–24 h
Fly ash Blast Batch Adsorbent (from Fumkin 32 mgPO4 g−1 2.9 Agyei et al. (2002) 0.026
furnace slag S-Africa) 0.5–5 g were
Portland used in 200 mL 100 mg
cement PO4 3− L−1 , pH 9 for 16 h
60 mg PO4 g−1 23.8 0.031
83 mg PO4 g−1 45.2

Soils, Sands, Batch KH2 PO4 at P Langmuir 0.29–0.97 g P kg−1 Xu et al. (2006) 4.4–4.9
Fly ash, Blast concentrations (pH 7.0)
furnace slag of 10–100 mg P L−1 for
sands and soils from
China, and of
100–1000 mg P L−1 for
fly ash and furnace slag
(24 h)
0.13–0.26 g P kg−1 3.3–5.6 6.7–8.1
8.89 g P kg−1 , 100% 12.3
removal
8.81 g P kg−1 , 100% 22.4 (3.1) N.A. 12.1
removal
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89 79

Table 3
Man-made products used as filter media for P removal.

Material Study type Description of the Retention P retention Ca% References pH

study calculation

Filtra P Column At room Calculated Retained P 98.2%, 3.10 Gustafsson et al. (2008)
temperature under effluent pH fell
water-saturated from 12.9 to 11.6,
conditions. PO4 -P clogged after 971
and NH4 -N (5 and pv
30 mg dm3 ), tap
water, HLR
7–10 L m−2 day−1 ,
68 weeks
Filtralite PTM Small-, meso- and Small-scale Determined Small-scale: – Àdàm et al. (2006) >10
full-scale CW systems (953 g): extracted P
HLR 5.0 and 1.25 L 3887 mg P kg−1 .
d−1 , HRT 0.21 and Meso-scale:
0.83 d. Meso-scale 4500 mg P kg−1 .
filter (359 kg): HLR Full-scale: 52 mg P
∼71 L d−1 , HRT kg−1
3.6–4.3 d. Full-scale
system: VF and HF
filter (180 m3 ); HLR
1.6 m3 d−1 ; HRT 18
d
Filtralite PTM Full-scale CW The upflow filter, Calculated Reduction in the – Heistad et al. (2006) 12.5 (after 3 years 10)
6 m3 , HLR filter system is
450–864 L d−1 ; 3 99.4%
years
Filtralite PTM Batch 3 g, 24 h in 90 mL Calculated 2.5 g P kg−1 0.003 Àdàm et al. (2007) 10.7
solution with
phosphates
0–480 ppm
Column 2 vertical upflow Calculated and By mass balance
columns up to 330 extracted calculations
d, HRT 3.65 d; HLR 497 mg P kg−1 , by
4.9–5.5 L d−1 extraction up to
635 mg P kg−1 ,
removal 54%
Leca (Estonian) Batch 3 g and 75 mL Calculated Bounding capacity 0.1 Vohla et al. (2005)
solution with 0–10 mg P g−1 .
5–1000 mg PO4 Sorption of up to
L−1 , 24 h 7.98 mg P g−1
Leca (Estonian) Full-scale CW VSSF + HSSF filter Calculated TP removal 89% 2.1 Öövel et al. (2007) Outflow pH 7.4
bed, 64 PE, HRT
7.4 m3 d−1 , 2 years
LWA Batch, Full-scale HF CW, HRT 4 Calculated >95% 3.1 Zhu et al. (2003) 10
CW weeks, households,
4 years, Norsk Leca
LWA Batch Batch: 3 g in 75 mL, Calculated Sorption 12 g P Jenssen and Krogstad (2003) 12.3
(lab-made) 320–480 mg L−1 , kg−1 , higher
24 h. Laboratory dolomite content
made LWA and pH guarantees
sorption
LWA (USA) Batch Test Calculated 3465 mg P kg−1 46.5 Zhu et al. (1997) 10.1
(0–320 mg L−1 ), 8 g
substrate, 200 mL
solution, 24 h
Filtralite TM 209–2210 mg P 31.0 10.3
kg−1
Leca (Swedish) 46–565–mg P kg−1 8.5 10.5
Norlite Full-scale CW SSF wetland cell, Calculated Norlite removed 1.43 Hill et al. (2000) Outflow pH 7.7
wastewater from 34%
dairy farm

P L−1 ) but the long-term stability remains to be established (Bellier
et al., 2006).
3.1.1.2. Bauxite. Bauxite, a naturally occurring mixture of miner-
als rich in hydrated Al oxides and Fe oxides and low in alkali
metals, alkaline earths and silicates, obtained from Alcan Chem-
icals Europe, Burntisland. Phosphate removal efficiency of more
than 95% for activated bauxites has been reported (Altundoğan
and Tümen, 2003). Adsorption of different P forms by raw bauxite
was 16.1–67.3%, and 48.3–97.9% in the case of activated bauxite.
Batch tests with bauxite (Altundoğan and Tümen, 2002) showed
that orthophosphate removal was higher at pH 4.5 (67.3% of 10 mg
P L−1 initial solution).
3.1.1.3. Dolomite. Dolomite (CaMg(CO3 )2 ) is a common sedimen-
tary rock-forming mineral that can be found in massive beds several
hundred feet thick. These are found throughout the world and are
quite common in sedimentary rock sequences. These rocks are
appropriately enough referred to as dolomite or dolomitic lime-
80 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
stone. The P removal efficiency of dolomite was 44% of the influent
P (Pant et al., 2001). Karaca et al. (2004) showed that the P adsorp-
tion capacity for dolomite fluctuated from 9.7 to 52.9 g P kg−1 , with
an increase in initial phosphate concentration from 10 to 60 mg L−1 .
The amount of phosphate adsorbed also increased with the increase
in pH from 1 to 11.
3.1.1.4. Gravels. In the gravel systems, the main P-removal mech-
anisms are adsorption and precipitation reactions with Ca, Al, and
Fe but also, like in all media, biological assimilation and plant
uptake can play a remarkable role (Korkusuz et al., 2005). Tanner
et al. (1999) showed that over 5 years, P accumulation decreased
and substratum P-sorption capacity became saturated. Mann and
Bavor (1993) described testing the phosphorus removal efficiency
gravel based constructed wetland system in a 2-year study in which
removal ranged from −40% to 40%. Korkusuz et al. (2005) showed
that many substrates in subsurface constructed wetlands (e.g. pea
gravel, crushed stones, sand, etc.) usually do not contain high con-
centrations of Ca, Al, Mg and Fe, and thus the removal of phosphate
is, generally, low and varies widely among systems due to the
different materials used. For domestic wastewater treatment in
Turkey, vertical subsurface flow constructed wetlands showed TP
removal efficiency for gravel wetland cells of only 4%. He et al.
(2007) reported TP removal during a 14-weeks experiment in a
gravel wetland from 6.8% to 54%, on average 22.44%. In pilot-scale
units containing medium gravel obtained from a quarry, Akratos
and Tsihrintzis (2007) found greater removal efficiency for fine
gravel (89%), followed by medium gravel with cattail (67%) and
cobbles (57%). The removal efficiencies of the other two units
were significantly lower (medium gravel with reed 28.2%; medium
gravel alone 43.9%). PO4 3− and TP removal efficiency was predom-
inantly affected by porous media size and type.
3.1.1.5. Laterite. Laterite is a hydrated mixture of Al, Fe and Ti
derived from the decomposition of aluminium-rich silicate, baux-
ite rocks and subsequent loss of alkalis, lime, magnesia and silica.
Wood and McAtamney (1996) has found 99% removal of phos-
phates from leachate in lab and 96% in pilot CW for laterite.
Probably P ions are chemically adsorbed onto surfaces of hydrous
oxides of Fe and Al by ligand exchange.
3.1.1.6. Limestone. Limestone is a very common sedimentary rock
of biochemical origin. It is composed mostly of the mineral calcite
(CaCO3 ). Sometimes it is almost pure calcite, but most limestones
are filled with lots of other minerals and sand, and they are termed
“dirty limestones”. Calcite is derived mostly from the remains of
organisms such as clams, brachiopods, bryozoa, crinoids and corals.
Some limestones may have been derived from non-biogenic calcite
formation. Although some limestones can be nearly pure calcite,
there is often a large amount of sand or silt that is included in the
shelly debris. DeBusk et al. (2004) showed that in mesocosm-scale
experimental wetland system, the TP removal for the limerock filter
system was 46%. Strang and Wareham (2006) described a removal
of only 20% in limestone filters. Johansson (1999a) found a retention
capacity from 0.3 up to 20 g P kg−1 for limestone.
3.1.1.7. Maerl. Maerl are the dead deposits of calcareous red algae
(Corallinaceae) found growing in shallow waters around the coast
of north-western Europe and the western Mediterranean. Upon
death, the algae accumulate to form large shoals, providing an
important habitat for benthic communities (Hall-Spencer, 1998).
The use of maerl exploits its high mineral content; in addition
to high percentages of calcium carbonate (80%) and magnesium
carbonate (10%), it contains small amounts of 25 different trace
elements such as sulphur (0.6%), phosphorus (0.35%), potassium
(0.2%), sodium (0.17%), iron (2500 ppm), aluminium (500 ppm) and
copper (15 ppm) (Inglethorpe, 1992). The removal of phosphorus
in the experiments conducted by Gray et al. (2000) was one of the
highest found in the literature. This study noted that maerl had
great potential as a constructed wetland substrate, due to its high
phosphorus-adsorbing capacity (0.12–39 g P kg−1 , according to the
initial P concentration in solution: 5–5000 mg P L−1 ).
3.1.1.8. Marble. Marble is a nonfoliated metamorphic rock result-
ing from the metamorphism of limestone, composed mostly of
calcite (a crystalline form of calcium carbonate, CaCO3 ). Gervin
and Brix (2001) tested a planted vertical flow wetland system to
reduce the phosphorus discharge from combined sewer overflows.
The bed medium consists of a mixture of calcareous gravel and
crushed marble, which has a high binding capacity for phosphorus
(up to 25 kg P m−3 ; Brix et al., 2001). During the initial two years of
operation. P removal was consistently high (94–99% of 1.3–1.8 mg
P L−1 inflow concentrations). When loaded with lake water, the
phosphorus removal was high during summer (71–97%) and lower
during winter (53–75%), suggested to have been partly because of
lower inlet concentrations.
3.1.1.9. Sands. In sand or gravel substrates, phosphorus is bound
to the media mainly as a consequence of adsorption and precipita-
tion reactions with calcium (Ca), aluminium (Al) and iron (Fe). At
pH levels greater than 6, the reactions are a combination of physical
adsorption to iron and aluminium oxides and precipitation as spar-
ingly soluble calcium phosphates. At lower pH levels, precipitation
as iron and aluminium phosphates (strengite, variscite) becomes
increasingly important (Gerritse, 1993). The capacity of filter media
to remove P may therefore be dependent on the contents of these
minerals in the substrate. This hypothesis is supported by the
observation that P-removal has been found to be particularly effi-
cient in constructed reed beds containing ferruginous sand (Netter,
1992). However, P-removal efficiency is often high initially and
then decreases after some time as the P-sorption capacity of the
sand is exhausted (Ciupa, 1996). Arias et al. (2001) found that the
P-removal capacity of some sands would be used up after only a few
months in full-scale systems, whereas that of others would persist
upnto several years. The most important characteristic of the sands
that determined their P-removal capacity was their Ca content. In
situations where the wastewater to be treated is more acid, the
contents of Fe and Al may be more important, as the precipitation
reactions with these ions are favoured at lower pH levels (Stumm
and Morgan, 1981). Pant et al. (2001) showed that some local sands
from Canada with elevated contents of Fe, Al and P have high P-
sorption capacity. Sand filters are also known as efficient units for
complex wastewater purification (BOD, COD, NH4 -N, and also in
some cases PO4 -P and faecal coliforms). Long-term purification,
however, has only been demonstrated in a few studies (Mander
et al., 2003; Vohla et al., 2007).
3.1.1.10. Opoka. Siliceous sedimentary rock Opoka was deposited
in the Mesozoic era. In contrast to limestone that is crystalline,
Opoka is amorphous in its structure, making it highly porous. This
material, from south-eastern Poland, is composed of 50% CaCO3 ,
40% SiO2 and 10% Al-, Fe- and other oxides. Opoka samples in
the study performed by Johansson and Gustafsson (2000) did not
retain phosphorus efficiently, although these extracts were super-
saturated with respect to hydroxyapatite, and supersaturation was
probably too low to initiate Ca-P precipitation. Renman et al. (2004)
describes the high efficiency of heated Opoka.
3.1.1.11. Peat. Compared to mineral soils, peat has a high organic
matter content and large surface area (more then 200 m2 /g), and
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
is highly porous (80–90%; Brown et al., 2000). The reduction of P
in mineralized peat may occur through the sorption, sedimenta-
tion and combination of complex compounds (Mann, 1990; Kadlec
and Knight, 1996; Richardson et al., 1996). Alternatively, some
P may be bound to the biofilm (Mann, 1990; Richardson et al.,
1996), but this can be quite irreversible such as the phosphorus
can easily be transformed from organic to inorganic form. Impor-
tantly, the phosphorus forms chemical complexes with organic
and inorganic ligands, which can be adsorbed into the soil or
will be removed by precipitation (Mæhlum, 1998). Interestingly,
Kõiv et al. (2009b) results show that the phosphorus removal
by HF peat filters (well-mineralized peat) did not occur if the P
concentration was lower than ∼1.5 mg L−1 . The nature of this phe-
nomenon remains unclear, but this may suggest that the phosphate
molecules need to be bound to complexes (through formation of
larger molecular aggregates) to be adsorbed to peat surfaces. In
aerobic wetland conditions, phosphorus appears in dissolved com-
plexes together with Ca and Mg ions in alkaline conditions, and
with Fe or Al ions in soil with acidic to neutral pH (Nieminen
and Jarva, 1996; Mæhlum, 1999), which can then be chemically
adsorbed by peat particles. Talbot et al. (1996) showed in a lab-
scale experiment that the efficiency of P removal from initial 14 mg
P L−1 was 44%. Average effluent parameters over a 2-year study for
the septic tank and peat filter system demonstrated no removal of
PO4 -P and 12% for total P. Rizzuti et al. (2002) found that peats with
higher N and P retention capacities also have humic acid contents
between 5 and 7%. Bulc et al. (1997) demonstrated that phospho-
rus removal efficiency from leachate over a 5-year study was on
average 63%.
3.1.1.12. Shale. Shale, an argillaceous rock, is derived from the
lower limestone group of the carboniferous system, which is highly
fissile and readily splits into very thin laminae. It is a readily avail-
able material in Scotland (Drizo et al., 1997; Drizo, 1998). Drizo
et al. (1999) found that X-ray fluorescence measurements showed
that substantial precipitation of P had occurred on the shale sur-
faces. Shale shows promise as a substrate for constructed wetland
systems, using low loading rates. Results from batch and column
tests suggest it may have a potential lifetime of 20 years in such
systems; however, data from pilot-scale and full-scale CWS would
be needed to confirm that the lifetime is of this order of magnitude.
3.1.1.13. Shellsand. Shellsand is a natural carbonatic material
mainly sourced from shells, snails and coral algae with a grain con-
sistently similar to sand or gravel. The quality varies and can be
separated according to its origin and weathering (Erstad, 1982).
One million tonnes are annually harvested on the Norwegian coast-
line (Roseth, 2000). Shellsand has shown a maximum P-sorption
capacity of 9.6 g P kg−1 . The find for shellsand is consistent with
earlier findings by Roseth (2000) and Søvik and Kløve (2005): in
vertical upflow columns the mass balance calculations showed that
the column sorbed an average of 0.5 g P kg−1 of material. Àdàm et al.
(2006) found the overall P-removal rate by shellsand of 92% (Àdàm
et al., 2006). Roseth (2000) demonstrated calculated phosphorus
adsorption for shellsand 14–17 g P kg−1 and 3.5 g P kg−1 for the
column. Søvik and Kløve (2005) found retention capacity in accor-
dance with the Langmuir equation for shellsand up to 8 g P kg−1 .
3.1.1.14. Soils. P retention by mineral soil, humus and peat
is related to the content of iron and aluminium compounds
(Hartikainen, 1982; Heikkinen et al., 1995; Nieminen and Jarva,
1996; Giesler et al., 2005). These Al and Fe compounds are abundant
in upland soils with podzolised B horizons, but are scarce in peat
soils (Nieminen and Jarva, 1996). For instance, fine loamy soil beds
removed the highest average amount of P, i.e. 53% (Hill et al., 2000.)
81
Loamy soils were probably from the E horizon and extended into
the argillic (top of the Bt) horizon. The E horizon refers to depleted
clay and Fe oxides; the parental material is rich in calcium, except
for the top meter, due to leaching. Problems with soil SSF wetlands
that might appear: declining hydraulic conductivity leads to lower
retention time; during subfreezing temperatures unpredictable; to
avoid clogging, SS should be kept out of the media (wetland owner,
farmer), and it is not usable in vertical flow beds. The spodic B
horizon of podzolised forest soil described by Johansson (1999a)
is rich in Al and F and is effective in removing As, but also P
(85–92%), whereas P was mainly sorbed to the Al- and Fe- com-
pounds. Sakadevan and Bavor (1998) demonstrated that soils from
experimental and former wetlands removed P 100% if the loading
remained under the 100 mg P L−1 . Phosphorus sorption by the soils
was strongly correlated with oxalate extractable Al and Fe. Organic
matter content rather had a negative effect, probably due to the
competition with P ions for the adsorption sites.
3.1.1.15. Wollastonite. This calcium metasilicate is a mineral
mined for several purposes (primarily in ceramics, friction prod-
ucts, paint filler and metalmaking) in upstate New York. Calcium
metasilicate deposits exist in China, India, Finland, California and
Mexico as well (Hare, 1993). It has been used as a substrate for
constructed wetland ecosystems for the removal of soluble phos-
phorus from secondary wastewater. Brooks et al. (2000) studied
vertical upflow columns with hydraulic residence times varying
from 0.6 to 7.5 d. Removal higher than 80% (up to 96%) was achieved
when the residence time was >1.7 d. A relationship was established
between residence time and soluble phosphorus removal. Hill et
al. (2000) tested wollastonite tailings, which were a by-product of
mining activities that produced wollastonite and garnet (a ferrous
metasilicate). The tailings were approximately 15% wollastonite
and 70–80% garnet, so they provide both calcium and iron as poten-
tial adsorption sites for P. Lab experiments showed high (90%) P
removal. A retention time at least 62 h is necessary for optimal
removal (Brooks et al., 2000). Mean reduction in P concentrations
was 28%. Hedström (2006) studied wollastonite from China. Phos-
phate removal was minor when the initial P concentration was low.
Thus this material may not be suitable for wastewater treatment,
due to its low removal capacity at low concentrations. For PO4 -P
concentration as low as 0.8 mg L−1 , the sorption of phosphate was
negligible. The results also indicated that possible precipitates are
hydroxyapatite and calcium phosphate.
3.1.1.16. Zeolite. Zeolite is a hydrated aluminium-silicate mineral
in which the aluminium and silicon polyhedra are linked by the
sharing of oxygen atoms. Drizo et al. (1999) described that zeo-
lite achieved an adsorption maximum of 0.462 kg−1 . Chen et al.
(2006) has found the maximum P retention for different zeolites
at different pH ranges, defined by Langmuir adsorption, to be only
0.01–0.05 g P kg−1 .
3.1.2. By-products that are used for phosphorus removal
3.1.2.1. BauxsolTM . BauxsolTM , is a neutralised bauxite residues, i.e.
seawater-neutralized red mud, and consists in a complex mixture
composed primarily of Fe and Al oxides from the Queensland alu-
mina refinery in Australia. According to batch tests (Akhurst et
al., 2006), adsorption of phosphates increased with decreasing pH,
with maximum adsorption capacities at pH 5.2 (the lowest pH
investigated), increased BauxsolTM to initial phosphate concentra-
tion ratios and increased time.
3.1.2.2. Burnt oil shale (BOS). Burnt oil shale is widely available in
central Scotland as a waste product that results from heating oil
shale to produce mineral oil. Data found about burned oil shale
82 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
by Drizo et al. (1999) showed the adsorption maximum for that
material to be 0.582 g P kg−1 , on the basis of the Langmuir equation.
3.1.2.3. Coal fly ashes. Coals are composed of aluminium silicate
clays, carbonates, sulphides, chlorides and quartz that are oxidized
at high temperatures (>1500 ◦ C), which melts almost all of the
inorganic components with the exception of quartz. Coal fly ash
is an inorganic waste product from coal combustion, consisting
mainly of spherical glassy particles of silica (SiO2 ), alumina (Al2 O3 )
and iron oxides. Fly ashes are widely used on agricultural land to
improve the physical and chemical properties of soil (Kukier et
al., 1994). In addition, fly ashes are used in effluent treatment to
remove various pollutants (COD, suspended solids, organic com-
ponents, chrome dye, heavy metals, phenolic compounds, fluoride
and also P (Eye and Basu, 1970; Gray et al., 1988; Banerjee et al.,
1997; Gupta et al., 1990; Piekos and Paslawska, 1999; Kao et al.,
2000; Diamadopoulos et al., 1993; Tsitouridou and Georgiou, 1988;
Gray and Schwab, 1993).
Chen et al. (2007) found that high Ca, medium Ca and low Ca fly
ashes from coal-using power plants in China showed retention at
different pH ranges to be up to 42.6 g P kg−1 .
Yan et al. (2007) described retention capacity as defined by
Langmuir as being up to 29.5 g P kg−1 , while the initial pH in slurry
was alkaline (9.7–11.6).
He et al. (2007) studied constructed wetlands for the treatment
of low-concentration polluted eutrophic landscape river water
with a three-stage system filled with fly ash. The TP adsorbed by
the last 7 m of the fly ash stage was about 83%.
3.1.2.4. Ochre. The flooding of abandoned mines frequently results
in the formation of acidic, Fe rich water due to the oxidation of
pyrite during mining operations. In treatment plants, atmospheric
oxidation and precipitation are harnessed, and thus large quanti-
ties of Fe(OH)3 and FeO(OH) precipitate accumulates, collectively
known as ‘ochre’. Heal et al. (2003, 2005) demonstrated maximal
sorption capacity for ochre of 0.026 g P kg−1 . It was found that 75%
and 90% of all P forms were removed after 5 and 15 min shaking,
and pH differing from 4 to 10 did not influence P removal. Ochre
was also tested in the field, but due to the hydraulic conditions, the
results remained moderate (27% of P was removed from a initial
solution of 20 mg P L−1 ).
3.1.2.5. Red mud. Red mud is the by-product associated to alumina
production from bauxite using the Bayer Process. It causes serious
environmental problems due to its high alkalinity and large quan-
tities. Environmental and economical concerns have led to ongoing
research to find effective ways to utilize the abundant and widely
available red mud (Shannon and Verghese, 1976) to remove phos-
phate. Li et al. (2006) found a very high maximal sorption capacity
of 345.5 g P kg−1 of extra heated red mud in batch-scale experi-
ments. Treated red mud also had alkaline pH and high Ca content.
For raw red mud, the maximum sorption capacity using Langmuir
was 113.9 g P kg−1 .
3.1.2.6. Sediment of oil shale ash. Kerogenous oil shale used in Esto-
nian thermal power plants is a solid fuel of low energetic value,
which after combustion leaves large amounts of ash (45–48% of
dry mass of shale). Estonian oil shale is highly calcareous (average
calcite and dolomite content is 40–60% of the mineral matter), and
the ash remaining after combustion is due to the thermal decom-
position (peak temperatures 1500 ◦ C) of carbonate minerals and
subsequent reactions with flue gases rich in free lime (CaO) and
anhydrite (CaSO4). The ash is transported to waste heaps (plateaus)
through a pipe system in water slurry at an ash–water ratio of
1:20. The lime and anhydrite already begin to react with water in
the ash removal system, and the hydration processes continue in
open plateaus, resulting in different secondary Ca-minerals. Batch
experiments by Kaasik et al. (2008) indicated the good (up to 65 mg
P g−1 ) P-binding capacity of the hydrated oil shale ash sediment,
with a removal effectiveness of 67–85%. This is the highest reten-
tion capacity, and is found by calculating the sorbed P amount from
the difference between initial and final P concentrations per gram
of material. The high phosphorus sorption potential of hydrated oil
shale ash is considered to be due to the high content of reactive
Ca-minerals, of which ettringite Ca6 Al2 (SO4 )3 (OH)12 × 26H2 O and
portlandite Ca(OH)2 are the most important (Kaasik et al., 2008).
Treatment with a P-containing solution causes partial-to-complete
dissolution of ettringite and portlandite, and precipitation of Ca-
carbonate and Ca-phosphate phases, which was confirmed by X-ray
diffraction (XRD) and scanning electron microscope (SEM)-EDS
studies. Vohla et al. (2005) found retention capacity of 8.2 g P
kg−1 , which is a lower capacity value, probably due to a different
methodology and calculation techniques. Hydrated oil shale ash
has also been shown to have quite an effective removal capacity in
field studies, showing removal efficiency in hydraulically saturated
experimental filter treating domestic wastewater up to 71% and in
small-scale vertical flow filters (Kõiv et al., 2009a) treating leachate
up to 68%.
3.1.2.7. Slag. Slag is a porous non-metallic co-product produced
in the iron and steel industry. In steelmaking industry, materials
including iron ore, scrap metal, and fluxing agents such as lime, are
heated beyond their melting points. Two main liquids are formed
the metal in fusion and a liquid with a lowest specific gravity forms
a layer on the surface of the melt that is called slag (Proctor et al.,
2000). Four main slag are identified including blast furnace slag (BF-
slag, is associated with iron production), basic oxygen furnace slag
(BOF-slag, produced in a furnace supplied with oxygen to remove
carbon), electric furnace slag (EAF-slag in steel production, pro-
duced in an electric arc furnace, a furnace adapted for scrap metal
recycling) and melter slag (specific production in New Zealand
from sands rich in iron). A large range of sorption capacities were
reported from batch experiments using slag ranging from 0.1 up
to 50 g P kg−1 slag (Mann and Bavor, 1993; Sakadevan and Bavor,
1998; Grüneberg and Kern, 2001). Apparently, the large scatter of
results of phosphorus sorption on slag relates to the fact that these
substances are not fully and unambiguously defined by their chem-
ical, mineralogical and phase compositions. The problem has now
been studied for nearly 20 years (Yamada et al., 1986), and it is
still evident that more detailed research is needed to elucidate the
sorption of phosphates. As P is known to bind with Ca at high pH,
the formation of calcium phosphates was believed to be a major
mechanism of P removal by slag systems (Baker et al., 1998). Sim-
ilarly, calcium-containing alkaline slag has proven to have a high
P-sorption capacity as shown earlier in batch, column experiments,
but also in some field investigations (Yamada et al., 1986; Mann and
Bavor, 1993; Johansson, 1999b; Sakadevan and Bavor, 1998).
To determine if P-loaded slags might be efficient as agricultural
fertilizers, Johansson and Hylander (1998) showed, in pot experi-
ments with barley, that P retained by slag was available for uptake
by plants. However, further investigations are required to under-
stand the uptake mechanisms. Cameron et al. (2003) reported that
during research conducted on slag column filters for the removal
of PO4 from wastewater, the pH of the effluent of the slag columns
reached a maximum of 11.5. It is therefore recommended that
the pH of the pilot-scale slag filters be measured and corrected
if required before discharge to surface waters. Drizo et al. (2006)
reported that electric arc furnace (EAF) steel slag was nearly 100%
efficient due to specific P adsorption onto metal hydroxides and the
precipitation of hydroxyapatite. The void hydraulic retention time
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
(HRTv) was a key factor for growing hydroxyapatite crystals and
had a significant effect on P-removal efficiency using EAF steel slag.
Shilton et al. (2006) presents a decade of experience of P removal
by active slag filters at a full-scale treatment plant. The average
total phosphorus (TP) removal efficiency of slag was 77% during
the 5-year period.
3.1.3. Man-made products that are used for phosphorus removal
3.1.3.1. Alunite. Alunite, KAl3 (SO4 )2 (OH)6 , is a mineral that in its
original form is not soluble in water. It is formed by the hydrother-
mal alteration of tuff. It contains approximately 50% SiO2 . The
alunite used in the study revealed by Özacar (2006) was obtained
from Turkey. Alunite samples were calcined in a muffle furnace at
1000 ◦ C for 30 min. Using a two-stage adsorber lab scale, an average
of over 80% removal was achieved from a contact time of 29.1 min
at pH 5.
3.1.3.2. Filtra P. Filtra P is produced after heating a mixture of
limestone, gypsum and Fe oxides. The product, which is strongly
alkaline because of its content of Ca(OH)2 (about 20%), is gran-
ulated to a particle size of 2–13 mm for use as a filter material
in wastewater treatment. Samples of Filtra P were obtained from
Nordkalk Oy Abp (Pargas, Finland). Gustafsson et al. (2008) studied
Filtra P in subsurface wetlands cell treating dairy wastewater for 68
weeks. They found 98.2% removal of P. The pH of the effluent water
remained alkaline, dropping from 12.9 to 11.6. Nevertheless, the
material clogged after 971 pore volumes.
3.1.3.3. Filtralite PTM . Filtralite PTM , a new generation of
Norwegian-produced LWA, has been especially developed for
P sorption (Zhu et al., 2003; Àdàm et al., 2005). This new LWA
is made of natural mineral clay illite with natural additives, and
is manufactured by running palletized clay aggregates through a
rotary kiln at 1200 ◦ C. Filtralite PTM has high pH (10) and high Ca
and Mg content (Jenssen and Krogstad, 2003). After saturation,
this material can be used as an alternative fertilizer in agriculture.
Àdàm et al. (2005) showed in the study with Filtralite PTM at lab
scale that the removal rate was dependent on the inlet P concen-
tration, but was not correlated with the hydraulic loading rate. It
was also noted that resting periods regenerated the P-sorption
capacity.
The retention capacity results from the batch study were quite
consistent with those reported by Zhu (1998) (0.4–3.5 g P kg−1 ),
although Zhu used the very first generation of Filtralite without
dolomite addition. The founded P retention capacity was, how-
ever, much lower than that shown in earlier studies revealed by
Jenssen et al., 2003 (8–12 g P kg−1 ) for Filtralite P. Àdàm et al.
(2006) described the P-sorption capacity found in a batch study of
Filtralite-PTM 8 g P kg−1 . Results from the small and meso-scale sys-
tem showed that it was difficult to extrapolate the results obtained
from model studies to full-scale constructed wetland systems.
Jenssen and Krogstad (2003) analysed the horizontal subsurface
flow LWA bed and found still effluent P concentrations of less than
0.5 mg L−1 after 6.5 years. The system was loaded with wastewater
having and average concentration of 11 mg L−1 . Heistad et al. (2006)
studied a wastewater treatment system for use in single houses
(aerobic biofilter and an upflow saturated filter) for 3 years. The
system performed excellent total phosphorus removal through-
out the experiment. The average reduction in the filter system was
99.4%. Over 3 years, the pH value from the upflow filter, which is
problematic using such alkaline materials, dropped from 12.5 to
10.
Due to high P-removal capacity Filtralite-PTM has been reported
to be an effective filter media used in CW systems (Jenssen and
Krogstad, 2003; Àdàm et al., 2005; 2006, 2007; Heistad et al., 2006),
83
but is often criticized for the high energy demand that the pro-
duction processes consume, along with the high pH generated in
effluents. An effective design could include a peat filter after the
filters with calcareous materials to reduce the high pH to meet the
permitted discharge values (pH 9.0) and even afford an additional
P-removal effect (Kõiv et al., 2009b; Mayes et al., 2009). In Filtralite-
PTM systems, the initial pH can be up to 12.7 and a decrease to 11
is generally observed after several months. Other filter materials
(slags, fly ashes etc.) with alkaline components would also cause
a high effluent pH. Possible solutions in addition to the polishing
filter are aeration and dilution (Saltnes and Føllesdal, 2005).
3.1.3.4. Lightweight aggregates (LWA) or light-expanded clay aggre-
gates (LECA). Lightweight aggregates or light-expanded clay aggre-
gates have shown both good water permeability and phosphorus
sorption capability (Mæhlum et al., 1995; Johansson, 1997a; Zhu
et al., 1997; Drizo et al., 1999; Harris and Mæhlum, 2003; Jenssen
and Krogstad, 2003; Öövel et al., 2007). LWA is manufactured by
running palletized clay aggregates through a rotary kiln at 1200 ◦ C;
the chemical compositions differ according to whether their parent
material is clay or shale. These filter substrates must be available
in large quantities at low cost, but with long-lasting phospho-
rus sorption capacity (Johansson, 1997b). Kvarnstrom et al. (2004)
demonstrated that all inorganic P that was accumulated in the LWA
was easily soluble, mobile, and available to plants. Mæhlum et al.
(1995) described the P removal in the landfill leachate system with
two parallel horizontal subsurface flow LECA filters during mon-
itoring, on average 88% a year. Johansson (1997a,b) conducted a
column study with Leca and found that sorption of P by Leca was
low (8–13%). Jenssen et al. (1991) reported 10 times higher sorp-
tion in batch experiments, but the reason was probably that lime
was added to the Norwegian Leca to avoid aggregation. Zhu et al.
(1997) tested 3 types of LWA and founded the US LWA to be most
effective in comparison with Norwegian and Swedish LWAs. The
US LWA also had the highest Ca content. Vohla et al. (2005) tested
an Estonian LWA (Ca 0.1%), but found retention capacity of up to
3.2 g P kg−1 . Öövel et al. (2007) analysed the subsurface flow CW
treating schoolhouse wastewater with an Estonian LWA for about
2 years. The purification effect for total P was on average 89%.
3.1.3.5. Norlite. Norlite is a lightweight coarse aggregate of fired
shale. It is a construction material that is classified as a lightweight
aggregate. Norlite may be compared with LECA. It consists of 4.7%
iron oxide, 3.6% magnesium oxide, 3.2% alkalis, 2.0% calcium oxide,
20.2 aluminium and 64.2% silica (Hill et al., 2000). Hill et al. (2000)
has shown that Norlite removed 33.7% of TP during the 1.5-year
study in a subsurface wetland cell treating dairy wastewater. Based
on these data, Norlite is recommended for use in agricultural
systems. The author recommended this material, as it had good
hydraulic conductivity and low risk of clogging when SS in water
was higher.
3.1.3.6. Oyster shell. Oyster shell, in Korea, a large quantity of oys-
ter shell is generated as a by-product of the oyster culture on
the south coast. The amount of oyster shell was about 0.25 mil-
lion tonnes/year as of late 2003, of which only 10% was treated
for oyster spat attachment (2000 tonnes/year) and fertilizer (2000
tonnes/year). Kwon et al. (2004) found that raw material removed
no P in plastic jars, stirred with a deionized P solution. Heated oys-
ter shell, however, removed up to 68%, and pyrolized oyster shell
up to 98% of P.
3.1.3.7. Polonite. Polonite is manufactured from siliceous sedimen-
tary Opoka rock in Poland that is heated to 900 ◦ C. The material
consists mainly of reactive lime and wollastonite phases, which
84 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Fig. 1. Relationship of P retention capacity (g P kg−1 ), Ca content (%) and pH level
of various filter materials.
contribute to the strongly alkaline conditions. The Ca content in
Polonite averages 24.5%. Gustafsson et al. (2008) conducted a col-
umn study with Polonite and found the removed amount of P to be
96.7%. During the 68-week study period, the pH remained alkaline.
Effluent pH decreased from 11.7 to 9.5.
3.2. Phosphorus retention capacity related to pH level and Ca
and/or CaO content of filter media
As calcium ions can form stable and insoluble products with
phosphate, calcium-based materials are considered to be one of
the potential sorbents for phosphorus removal. Ca-bound P is also
more available for plants than Al- or Fe-bound P (Tisdale et al., 1993;
Krogstad et al., 2005). Willadsen et al. (1990) and Johansson and
Hylander (1998) showed that substrates containing CaCO3 sorbed
less P than substrates with more aggressive CaO or Ca(OH)2 con-
tent.
The retention capacity of the analysed materials was from 0.001
(soil, Sakadevan and Bavor, 1998) to 345.5 g P kg−1 (heated red
mud, Li et al., 2006). Most of the inserted data remained between
P retention capacities of 0–25 g P kg−1 . The Ca content ranged
from 0.03 (Filtralite-PTM , Àdàm et al., 2007) to 46.5% (USA LWA-
UTELITETM , Zhu et al., 1997) (average content 9.3%). The pH of the
selected filter materials ranged from 3 (bentonite, Xu et al., 2006)
to 12.6 (heated Opoka, Brogowski and Renman, 2004) (average pH
was 8). As shown by Fig. 1, pH did not influence retention capac-
ity. Based on the three-dimensional figures, we can see a slightly
increasing trend for P retention capacity with increasing Ca con-
tent over 15% (Fig. 1). We can also see that most of the materials
with high pH also have higher Ca content (>15%). However, the high
Ca content does not guarantee higher P retention capacity. Several
reasons for that phenomenon can be mentioned:
1. Different study conditions: P load, substrate amount, reaction
time, the method of calculating P retention (Langmuir or using
water data). Arias et al. (2001) showed that if one uses Langmuir,
the retention capacity was lower than if retention was calculated
from the difference of P concentration before and after the test.
Many authors have claimed that if one uses a higher initial P
Fig. 2. Relationship of P retention capacity (g P kg−1 ), CaO content (%), and pH level
of various filter materials.
load, P retention is also higher (Àdàm et al., 2005; Akhurst et
al., 2006). In addition, the greater amount of sorbent can also
influence the higher sorption, especially when one uses natural
materials like sands and gravels. That is due to the way the P is
bound. In natural materials the P is usually bound by adsorption
or sorption, and thus the greater the specific area of the material
in which the P can be bound, the higher the retention.
2. Different chemical composition of material. The high Ca content
does not always guarantee a rapid reaction between Ca and P.
For instance, the reaction is many times easier if the Ca in the
material is in the form of CaO instead of CaCO3 , which has much
lower dissolving ability. For instance, Kaasik et al. (2008) showed
that hydrated sediment of oil shale ash consists of both CaCO3
and Ca6 Al2 (SO4 )3 (OH)12 ·26H2 O (ettringite) and Ca(OH)2 (port-
landite). After the sorption test, the calcite content remained the
same, but the ettringite and portlandite content declined drasti-
cally or was even lost in the material. Brogowski and Renman
(2004) demonstrated that after the heating of Opoka, which
naturally contain Ca as CaCO3 , the sorption capacity increased
significantly, from 0.1 g P kg−1 (Johansson, 1999a) to 39.0 g P
kg−1 . After heating Opoka, the CaCO3 in the material was trans-
formed to CaO. The higher is the temperature (up to 1000 ◦ C), the
higher is the CaO content and P retention capacity. Kwon et al.
(2004) showed that heating (pyrolizing) oyster shell above the
650 ◦ C, the CaCO3 content fell and P-removal efficiency increased
to 98% in the material. Untreated material showed no P removal.
In some cases the Ca content was probably too low, and the Ca
species were not reactive compared to other elements such as Al
and Fe. In addition, adjusted acidic pH could influence the sorption
capacity, favouring P binding reactions between Fe and Al more
than with Ca. Thus the removal mechanism was related more to
the reaction with Al and Fe (Grubb et al., 2000).
Most of the P retention capacities used for the analyses
against Ca/CaO content remained between 0 and 50 g P kg−1
(Figs. 1 and 2). The CaO content ranged from 0.01% (sand, Cheug
and Venkitachalam, 2000) to 46.0% (acid-treated red mud, Li et al.,
2006) (average content 13%). The pH range remained the same as
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Table 4
Determination coefficients (R2 ) of Spearman Rank Correlation between the P reten-
tion capacity, pH level and Ca and CaO content of all of the filter material studied.
P retention Ca (%)
P retention
Ca (%) 0.43
CaO (%) 0.51 –a
pH 0.22 0.34
a
The correlation between Ca and CaO was not counted.
in previous Ca analyses, and it did not influence the P retention
capacity. Fig. 2 shows a slightly increasing trend for the P reten-
tion capacity with increasing CaO content over 15%. In these terms
it is similar to Ca content analyses (Fig. 1). Likewise, most of the
materials with high pH have higher CaO content (>15%) (Fig. 2).
The determination coefficient (R2 ) between the Ca content and
P retention capacity was only 0.43. However, the correlation was
stronger between the CaO and P retention (R2 = 0.51) and between
the CaO and pH (R2 = 0.42) (Table 4).
The highest P retention capacities for various filter materials
were detected in studies in which batch analyses were used. It is
evident that the highest numbers are described when industrial
by-products such as blast furnace slag studied by Mann and Bavor
(1993) and heated red mud from the study by Li et al. (2006) are
used (Table 5). P retention capacities for natural and man-made
products are from ten to a hundred times smaller. We also included
heated Opoka as a natural product, regardless of the fact that Opoka
was extra treated.
The difference between the maximum retention capacity of
industrial by-products and man-made products might arise from
the different calculation of P-sorption capacity. For the above-
mentioned by-products, the Langmuir equation was used to
determine the maximum retention capacity, but in the case of
man-made products, the retention capacity was calculated from
the difference between the initial and final P concentration of the
solution per gram.
The smallest P retention capacity was detected when using soils,
sands and fly ashes with low Ca content (0.001 and 0.02 g P kg−1 ).
The smallest values of P retention capacity for man-made prod-
ucts have been 10–100 times higher (0.42 and 0.57 g P kg−1 ) than
natural and by-products (0.002 and 0.003 g P kg−1 ) (Table 5). One
reason for this may be the higher Ca, but also Mg, Fe and Al content
in the material.
Substrates such as pea gravel, crushed stones, sand, etc. in the
subsurface constructed wetlands do not usually contain high con-
centrations of Ca, Mg, Al and Fe, the removal of phosphate is
generally low, and varies extensively among systems due to the
different materials used. Korkusuz et al. (2005) reported in the
results of the 1-year study that average removal efficiencies for the
gravel SSF vertical flow wetland cells were only recorded as PO4 3− -
P (1%) and total phosphorus (4%). Studies with shellsand (Àdàm
et al., 2007; Søvik and Kløve, 2005; Roseth, 2000), which con-
tains 10 times more Ca (327.6 mg kg−1 ) than Filtralite P, reported a
Table 5
Maximum phosphorus retention capacities (two for each group) of natural materials, industrial by-products and man-made products.
Maximum P retention, g P kg−1
40
Natural materials
5.2
420
Industrial by-products
65
12
Man-made products
3.5
Only materials with reliable hydraulic conductivity and useful for constructed wetlands are shown.
85
maximum P-sorption capacity of 9.6 g P kg−1 . The overall removal
capacity of P during the column study was 92%. That is similar to
the P-removal efficiency found in the Kodijärve sand (Ca content
CaO (%) 41.5 g kg−1 ) filter in the first years of operation.
On the other hand, the studies with limestone, which consisted
mainly of calcium carbonate (CaCO3 ) in the form of calcite, have
not been as effective as expected. Strang and Wareham (2006)
0.42
demonstrated only about 20% of the total reduction achieved in
the limestone wetland system. Hence the chemical form of Ca in
the filter media is also important characteristic when choosing a
potential filter media for P removal. Opoka (bedrock material from
south-eastern Poland) also mainly contains CaCO3 (50%), but low
retention of P was detected in the material, even in batch tests
(20%). Low P-sorption capacity was probably due to the type of Ca
in the material. CaCO3 is less active than CaO (Johansson, 1999a).
Heating the Opoka (CaO is augmented in that process) markedly
increased P sorption (average removal 96–99%). Maximum sorp-
tion capacity for heated Opoka was detected to be 119.6 g PO4 -P
kg−1 (Brogowski and Renman, 2004).
Wollastonite tailings are also an example of Ca rich sorbent,
which consist of approximately 15% wollastonite and 70–80% gar-
net, and provide both calcium and iron as potential adsorption
sites for P. Lab experiments showed high (90%) P removal. In the
SSF wetland cells, the soluble P retention in wollastonite over 1.5
years averaged only 12.8 ± 9.5%. The mean reduction in P concen-
tration was 27.5 ± 30.8%. Calculations for the lifetime were not
useful because of oversized filter (Hill et al., 2000). Hence the siz-
ing and optimization of hydraulic conditions in the filter cell plays
an important role in removal effectiveness. For instance, Drizo et
al. (2006) reported hydraulic retention time as a key factor for the
growing of hydroxyapatite crystals, and thus had a significant effect
on P removal by electric arc furnace steel slag.
The mixing of materials which can improve over all performance
can also be effective, for instance, Gervin and Brix (2001) studied
a vertical flow system to reduce P in combined sewer overflows
using a substrate of gravel mixed with crushed marble. Gravel has
good hydraulic conductivity, and marble has been shown to have
good P removal. During the initial two years of operation, phos-
phorus removal for combined sewer overflows was consistently
high (94–99% of inflow concentrations). In addition to the mix-
ing of materials, the addition of a reactive source has also been
used when processing special man-made products for P retention.
Lime addition during the process of the production of Leca can, for
instance, increase P removal about 10 times, which is the range
between the sorption capacities of Swedish and Norwegian Leca
(Johansson, 1997a,b; Jenssen et al., 1991).
In addition to chemical composition, which determines the
sorption capacity of the filter media, phosphorus availability in sat-
urated media is also important. The material that is enriched with P
can be used as a fertilizer, provided that P is available to the plants,
and the contents of toxic compounds and pathogens do not restrict
such use. For example, slag originating from the steel industry can
effectively sorb phosphorus, and in saturated slag the phospho-
Ca% (CaO%) Material; reference
30.1 (42.1) Heated Opoka; Brogowski and Renman (2004)
21.7 Dolomite; Karaca et al. (2004)
– Blast furnace slag (calculated after Langmuir); Mann and Bavor (1993)
20.9 (29.2) Hydrated sediment of oil shale ash; Kaasik et al. (2008)
– Lab-made LWA; Jenssen and Krogstad (2003)
46.5 USA LWA; Zhu et al. (1997)
86 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
rus is also available for plants. In LECA material without added
Ca, phosphorus is mainly bound with Al- and Fe-compounds. Al-
compounds and phosphorus formulate compounds are known to
be difficult for plants to obtain. Phosphates bound to Ca in hydroxyl-
apatite form (Hap, Ca10 (PO4 )6 (OH)2 ) are also not easily released
from the material in a short time, because of their low solubility
(Johansson, 1997a,b; Kvarnstrom et al., 2004). Ca-bound P has also
been found to take the form of tricalcium phosphate (Ca3 (PO4 )2 )
and dibasic calcium phosphate (CaHPO4 ), which are more solu-
ble forms (Kim et al., 2006). For instance, bound P in Filtralite P,
Filtra P and Polonite is found to be at least partly plant available
(Kvarnstrom et al., 2004; Hylander et al., 2006; Gustafsson et al.,
2008). Producing Filtralite and LWA products, however, is a process
with a huge energy demand, which is why the benefit of using LWA
as substrate is doubtful (Drizo et al., 1999). Phosphorus-sorbing
materials with additional beneficial characteristics may be used.
For example, lime can be used to counteract acidification so as to
improve soil structure (Rex, 2000). Most of the filter materials that
have been used are characterised by high pH values (9–12), which
first create an unfavourable environment for bacteria (Renman et
al., 2004), but secondly, effluent with pH >9 is also not allowed to be
discharged into water bodies. In that case, an extra filter decreasing
pH or extra methods such as dilution or aeration are needed.
3.3. Influence of material media size and composition on
P-removal processes
Large differences between P-sorption capacities were recorded
according to the nature of the treated water (e.g. Table 2). Several
columns investigations were stopped due to clogging. Clogging was
a big issue when using reactive media in filtration systems. This was
mainly associated to the use of fine media size, to biofilm devel-
opment caused by large amount of TSS and COD in the supplied
effluent, and in a minor extent, to CO2 capture and precipita-
tion under CaCO3 inside media, and to the flow rate. Since the
main mechanism of P sorption on reactive material is related to
CaO dissolution followed by P precipitation and crystallisation it
is likely that the smaller the size of the material, the greater the
surface available for CaO dissolution. This could lead to increasing
pH and probably to increase CaCO3 precipitation and crystallisa-
tion and finally cementation of the system. To overcome clogging
several solutions have been proposed including the use of pre-
filter to remove soluble CO2 and organic carbon (Chazarenc et al.,
2007), and the use of larger sized media (more than 5 mm medium
diameter, e.g. Shilton et al., 2006). One other major issue was the
high pH recorded at the outlet especially at the beginning of the
experiments. In many studies pH was greater than 9 and more-
over, in nearly one third of the studies, a pH decrease at outlet
was observed along with a decrease in P-removal efficiency. Thus
reducing outlet pH represents a major challenge but doing so could
affect P-removal efficiency so care must be taken when solving this
problem.
3.4. Influence of hydraulic loading rate and retention time on
P-removal processes
Hydraulic loading rate and hydrological retention time and their
relation to P retention were correctly registered only in a few lit-
erature sources (Tables 1–3). Due to the large variability of data,
we could not find any significant correlation between the HRT and
P retention. However, analysis made on full-scale and pilot-scale
treatment filter systems and column experiments shows that there
is probably an optimal level for HLR at which the P removal is the
highest (Fig. 3). This is similar to the findings from other studies
which suggest that for selected filter media the optimal P reten-
Fig. 3. Relationship of P retention capacity (g P kg−1 ) and hydraulic retention time
(HLR; mm d−1 ) of various filter materials. Quadrates indicate full-scale and pilot-
scale constructed wetlands, triangles: column experiments.
tion occurs at medium HRT level (Song et al., 2002). In particular,
too long HRT induces chemical clogging of hydrated oil shale ash
and reduces its phosphates removal capacity (Liira et al., 2009).
Fig. 3 only illustrates a general relationship between the hydraulic
parameters and P retention. For each individual filter material the
optimal range can be different.
3.5. Lifetime of substrates in treatment wetlands
As the materials by themselves and the methods for testing P-
removal capacity vary greatly, it is quite difficult to make conclusive
lifetime calculations. Many authors have stated that when testing
materials, those that show very high phosphorus removal in the
laboratory do not give similarly good results in field systems (Arias
et al., 2001; Drizo et al., 2002; Àdàm et al., 2006). There are a great
variety of reported results described for the same type of mate-
rial. Most of the studies that demonstrate the phosphorus retention
capacity of various materials have been conducted in the labora-
tory. Only a few materials out of the extensive group that has been
tested so far have also been studied in full-scale systems.
It has been stated only the comparison between various mate-
rials and relative potential as a filter media can be made on the
basis of batch experiments (Drizo et al., 1999; Arias et al., 2001,
2003). Since hydraulic conditions do play an important role in
removal processes and their effectiveness, at least column studies
are needed to predict possible removal capacity in the real system.
Àdàm et al. (2006) showed that even using smaller imitating filters,
it is difficult to extrapolate the results to full-scale systems.
If one uses maximal P retention capacity calculated from the
Langmuir equation or from final concentrations, it is easy to make
overestimations. P retention capacity is influenced by study dura-
tion, water/material ratio and temperature, the range of initial P
concentrations, the chemicals used, rotation speed and many other
differences in methods described in greater detail in Drizo et al.
(2002). For instance, the regeneration effect of removal capacity in
filter media during the resting period (Faulkner and Richardson,
1989; Cooper and Findlater, 1990) can yield higher overall P reten-
tion capacity. If we use the resting periods in one study and not
in another, the longevity prediction based on these results can
differ considerably (Àdàm et al., 2006). Brooks et al. (2000) have
stated that seeding effects could be a possible explanation for the
increment in the P-sorption capacities of the material after the rest-
ing periods. The seeds of calcium phosphates increased adsorption
processes by enlarging the specific surface area of the material
or increased nucleation and precipitation of amorphous calcium
phosphates over the nucleated.
Several by-products are tested as reactive media (materials rich
in Ca, Mg, Al and Fe) for P removal in real CW systems. Pilot and
full-scale systems with the most often studied by-product apart
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
from ashes – blast furnace slag – have shown removal rates of 98%
(Grüneberg and Kern, 2001) and 99% (Cameron et al., 2003). Shilton
et al. (2006) studied the full-scale active slag filters over 5 years, and
reported an average TP removal efficiency of 77%.
At the beginning of the use of constructed wetlands for the
removal of contaminants from wastewater, it was most common
for natural sands or gravels to be used as a filter media in beds.
As is known, in the sand or gravel substrate, phosphorus is mainly
bound to the media mainly as a consequence of adsorption and
precipitation reactions with calcium (Ca), aluminium (Al) and iron
(Fe). The most commonly chosen filter media did not contain large
amounts of these minerals, and thus the filter bed did not removed
P for more than a few years. For instance, gravel-based systems in
Richmond, Australia showed a decline in removal efficiency after
only 1–2 years of operation (Mann and Bavor, 1993). Tanner et al.
(1999) showed the saturation in the gravel-filled wetland system
that purified dairy farm wastewater during a 5-year period. Vohla
et al. (2005, 2007) described the saturation of an HSSF sand fil-
ter after 5 years of operation. Kadlec and Knight (1996) showed
that initial P-removal rates from wetland systems in the U.S.A. are
often in excess of 90%, but decline sharply after only 4–5 years
of cumulative P addition. Peat has also shown good results (up to
58–93%) in P removal in small-scale vertical flow filters, but satu-
ration appeared after 6 months of operation (Kõiv et al., 2009a, b).
Meso-scale CW with shellsand saturated before 2 years had passed
(Søvik and Kløve, 2005). Korkusuz et al. (2005) reported average P
removal of only 4.33% in the gravel bed during a 1-year monitoring
period.
Of man-made products, LECA systems are known to have an
extremely high P-sorption capacity (4 kg m−3 ), and have indicated
promising P removal (90%) after 2–3 years of operation (Zhu et
al., 2003; Heistad et al., 2006; Öövel et al., 2007). The results from
the literature indicate that the life span of CW for P removal dif-
fers. However, even if a medium with high P binding capacity has
been selected, it will become saturated after a few years (Arias
et al., 2001). Some new man-made products for P removal have
not initially shown such promising results. For example, Filtra P
(P removal 98%) clogged after 971 pore volumes probably due to
structural degradation.
In cases in which CW systems are used, where all contaminants
(SS, BOD, TN, TP etc.) are removed in one filter bed, the clogging of
substratum active particle surfaces and pore spaces, with organic
matter (litter, biofilm etc.), can lead to decreasing P removal. In
addition, clogging also decreases the hydraulic retention time in
the filter bed. An obvious and sustainable solution would also be
a separate filter unit containing replaceable material with a high P
binding capacity (Brix et al., 2001). In that case, appropriate pre-
treatment would also allow for a longer lifetime of the filter media,
by decreasing the risk of clogging or even decreasing the pH and
allowing the use of finer reactive filter media with higher sorption
capacity (Hedström, 2006).
4. Conclusions
A great variety (more than 30 main categories and over 80
subtypes) of both natural and man-made materials plus indus-
trial by-products have been applied as filter media for phosphorus
retention in constructed wetlands.
A majority of these materials have a pH value >7.0 and high Ca
and/or CaO content. Thus the main process of P retention used in
constructed wetlands is precipitation.
Although very few investigations have been performed in the
long-term saturation time of materials, most of calculations based
on the batch experiments suggest, and some data from full size sys-
87
tems confirm, that the P retention capacity of most filter materials
significantly decreases after a 5-year period of application.
Some new and possibly promising materials such as Filtralite,
Opoka, and dehydrated oil shale ash with extremely high P-
sorption rates should be evaluated for efficiency of P removal over
longer time. Also, well monitored long-term experiments in full-
size systems are needed.
The recyclability of saturated materials as fertilizer plays an
important role in the further application of the technology of
treatment wetlands. Therefore adequate experimental studies are
needed to ensure the applicability of recycled filter media. Success-
ful use of filter media also depends on their availability at the local
level and the possibility of harmful side-effects such as contami-
nation of the environment due to the high concentration of heavy
metals.
The follow-up research on filter materials for phosphorus reten-
tion should be focussed on their hydraulic parameters combined
with the analysis how to avoid the possible clogging. Likewise,
more attention should be given to investigate obvious constraints
such as poor hydraulic conductivity, low surface area, or high con-
tent of undesirable contaminants such as heavy metals.
Acknowledgements
This study has been supported by the Ministry of Education and
Science of Estonia (grants SF0182534s03 and SF0180127s08) and
Estonian Science Foundation grants 6083 and 7527.
References
Àdàm, K., Søvik, A.K., Krogstad, T., 2006. Sorption of phosphorous to Filtralite-P
(TM)—the effect of different scales. Water Res. 40, 1143–1154.
Àdàm, K., Krogstad, T., Vrale, L., Søvik, A.K., Jenssen, P.D., 2007. Phosphorus reten-
tion in the filter materials shellsand and Filtralite P (R)—batch and column
experiment with synthetic P solution and secondary wastewater. Ecol. Eng. 29,
200–208.
Àdàm, K., Krogstad, T., Suliman, F.R.D., Jenssen, P.D., 2005. Phosphorous sorption
by Filtralite-PTM —small-scale box experiment. J. Environ. Sci. Health A40 (6/7),
1239–1250.
Agyei, N.M., Strydom, C.A., Potgieter, J.H., 2002. The removal of phosphate ions from
aqueous solution by fly ash, slag, ordinary Portland cement and related blends.
Cement Concrete Res. 32, 1889–1897.
Akhurst, D.J., Jones, G.B., Clark, M., McConchie, D., 2006. Phosphate removal from
aqueous solutions using neutralised bauxite refinery residues (BauxsolTM ). Env-
iron. Chem. 3, 65–74.
Akratos, C.S., Tsihrintzis, V.A., 2007. Effect of temperature, HRT, vegetation and
porous media on removal efficiency of pilot-scale horizontal subsurface flow
constructed wetlands. Ecol. Eng. 29, 173–191.
Altundoğan, H.S., Tümen, F., 2002. Removal of phosphorus from aqueous solutions
by using bauxite. 1. Effect of pH on the adsorption of various phosphates. J. Chem.
Technol. Biotechnol. 77, 77–85.
Altundoğan, H.S., Tümen, F., 2003. Removal of phosphates from aqueous solutions by
using bauxite. II. The activation study. J. Chem. Technol. Biotechnol. 78, 824–833.
Arias, C.A., Del Bubba, M., Brix, H., 2001. Phosphorus removal by sands for use as
media in subsurface flow constructed reed beds. Water Res. 35 (5), 1159–1168.
Arias, C.A., Brix, H., Johansen, N.H., 2003. Phosphorus removal from municipal
wastewater in an experimental two-stage vertical flow constructed wetland
system equipped with a calcite filter. Water Sci. Technol. 48 (5), 51–58.
Baker, M.J., Blowes, D.W., Ptacek, C.J., 1998. Laboratory development of perme-
able reactive mixtures for the removal of phosphorus from onsite wastewater
disposal systems. Environ. Sci. Technol. 32 (15), 2308–2316.
Banerjee, K., Cheremisinoff, P.N., Cheng, S.L., 1997. Adsorption kinetics of oxylene
by flyash. Water Res. 31, 249–261.
Bellier, N., Chazarenc, F., Comeau, Y., 2006. Phosphorus removal from wastewater
by mineral apatite. Water Res. 40, 2965–2971.
Bennett, E.M., Carpenter, R., Caraco, N.F., 2001. Human impact on erodable phos-
phorus and eutrophication: a global perspective. BioScience 51, 227–234.
Brix, H., Arias, C.A., Del Bubba, M., 2001. Media selection for sustainable phospho-
rus removal in subsurface flow constructed wetlands. Water Sci. Technol. 44
(11–12), 47–54.
Brogowski, Z., Renman, G., 2004. Characterization of opoka as a basis for its use in
wastewater treatment. Polish J. Environ. Stud. 13, 15–20.
Brooks, A.S., Rozenwald, M.N., Geohring, L.D., Lion, L.W., Steenhuis, T.S., 2000. Phos-
phorus removal by wollastonite: a constructed wetland substrate. Ecol. Eng. 15,
121–132.
88 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Brown, P.A., Gill, S.A., Allen, S.J., 2000. Metal removal from wastewater using peat.
Water Res. 34 (16), 3907–3916.
Bulc, T., Vrhovšek, D., Kukanja, V., 1997. The use of constructed wetlands for landfill
leachate treatment. Water Sci. Technol. 35, 301–306.
Cameron, K., Madramootoo, C., Crolla, A., Kinsley, C., 2003. Pollutant removal from
municipal sewage lagoon effluents with a free-surface wetland. Water Res. 37,
2803–2812.
Cha, W., Kim, J., Choi, H., 2007. Evaluation of steel slag for organic and inorganic
removals in soil aquifer treatment. Water Res. 40, 1034–1042.
Chazarenc, F., Brisson, J., Comeau, Y., 2007. Slag columns for upgrading phosphorus
removal from constructed wetland effluents. Water Sci. Technol. 56, 109–115.
Chen, J., Kong, H., Wu, W., Chen, X., Zhang, D., Sun, Z., 2007. Phosphate immobi-
lization from aqueous solution by fly ashes in relation to their composition. J.
Hazard. Mater. B139, 293–300.
Chen, J., Kong, H., Wu, D., Hu, Z., Wang, Z., Wang, Y., 2006. Removal of phosphate
from aqueous solution by zeolite synthesized from fly ash. J. Colloid Interf. Sci.
300, 491–497.
Cheug, K.C., Venkitachalam, T.H., 2000. Improving phosphate removal of sand infil-
tration system using alkaline fly ash. Chemosphere 41, 243–249.
Ciupa, R., 1996. The experience in the operation of constructed wetlands in North-
Eastern Poland. In: Proceedings of Fifth International Conference Wetland
Systems for Water Pollution Control, IWA and Universität für Bodenkultur,
Vienna (Chapter IX/6).
Cooper, P.F., Findlater, B.C., 1990. Constructed Wetlands in Water Pollution Control.
Pergamon Press, Oxford, UK.
DeBusk, T.A., Grace, K.A., Dierberg, F.E., Jackson, S.D., Chimney, M.J., Gu, B., 2004.
An investigation of the limits of phosphorus removal in wetlands: a meso-
cosm study of a shallow periphyton-dominated treatment system. Ecol. Eng. 23,
1–14.
Diamadopoulos, E., Ioannidis, S., Sakellaropoulos, G.P., 1993. As (V) removal from
aqueous solutions by fly ash. Water Res. 27, 1773–1777.
Drizo, A., 1998. Phosphate and ammonium removal from wastewater, using con-
structed wetland systems. Ph.D. Thesis. University of Edinburgh, Scotland.
Drizo, A., Frost, C.A., Smith, K.A., Grace, J., 1997. Phosphate and ammonium removal
by constructed wetlands with horizontal subsurface flow, using shale as a sub-
strate. Water Sci. Technol. 35, 95–102.
Drizo, A., Frost, C.A., Grace, J., Smith, K.A., 1999. Physico-chemical screening of
phosphate-removing substrates for use in constructed wetland systems. Water
Res. 33 (17), 3595–3602.
Drizo, A., Comeau, Y., Forget, C., Chapuis, R.P., 2002. Phosphorus saturation poten-
tial: a parameter for estimating the longevity of constructed wetland systems.
Environ. Sci. Technol. 36, 4642–4648.
Drizo, A., Forget, C., Chapuis, R.P., Comeau, Y., 2006. Phosphorus removal by electric
arc furnace steel slag and serpentinite. Water Res. 40, 1547–1554.
Erstad (Jørgensen), K.J., 1982. Sammenlikning av norske kalkingsmidler I sammen-
heng med finfordelingsgradens betydning for virkninga på jordreaksjon og
plantevekst. Hovedoppgave ved NHL/Institutt for Jordkultur.
Eye, J.D., Basu, T.K., 1970. The use of fly ash in wastewater treatment and sludge
conditioning. J. Water Pollut. Control Fed. 42, 125–135.
Farahbakhshazad, N., Morrison, G.M., 2003. Phosphorus removal in a vertical upflow
constructed wetland system. Wat. Sci. Technol. 48, 43–50.
Faulkner, S.P., Richardson, C.J., 1989. Physical and chemical characteristics of fresh-
water wetland soils. In: Hammer, D. (Ed.), Constructed Wetlands for Waste
Water Treatment. Municipal, Industrial and Agricultural. Lewis Publishers,
Chelsea, MI, pp. 121–129.
Gerritse, R.G., 1993. Mobility of phosphate from waste water in calcareous sands of
Rottnest Island (W.A.). Aust. J. Soil Res. 31, 235–244.
Gervin, L., Brix, H., 2001. Reduction of nutrients from combined sewer overflows and
lake water in a vertical-flow constructed wetland system. Water Sci. Technol.
44 (11–12), 171–176.
Giesler, R., Andersson, T., Lövgren, L., Persson, P., 2005. Phosphate sorption in
aluminium- and iron-rich humus soils. Soil Sci. Soc. Am. J. 69, 77–86.
Gray, C.A., Schwab, A.P., 1993. Phosphorus-fixing ability of high pH, high calcium,
coal-combustion, waste materials. Water Air Soil Pollut. 69, 309–320.
Gray, M.N., Rock, C.A., Pepin, R.G., 1988. Pretreating landfill leachate with biomass
boiler ash. J. Environ. Eng. 114, 465–470.
Gray, S., Kinross, J., Read, P., Marland, A., 2000. The nutrient assimilative capacity of
maerl as a substrate in constructed wetland systems for waste treatment. Water
Res. 34, 2183–2190.
Grubb, D.G., Guimaraes, M.S., Valencia, R., 2000. Phosphate immobilization using an
acidic type F fly ash. J. Hazard. Mater. 76, 217–236.
Grüneberg, B., Kern, J., 2001. Phosphorus retention capacity of iron-ore and blast
furnace slag in subsurface flow constructed wetlands. Water Sci. Technol. 44,
69–75.
Gupta, G.S., Prasad, G., Singh, V.N., 1990. Removal of chrome dye from aqueous
solutions by mixed adsorbents fly ash and coal. Water Res. 24, 45–50.
Gustafsson, J.P., Renman, A., Renman, G., Poll, K., 2008. Phosphate removal by
mineral-based sorbents used in filters for small-scale wastewater treatment.
Water Res. 42, 189–197.
Hall-Spencer, J., 1998. Conservation issues relating to maerl beds as habitats for
molluscs. J. Conchol. Special Publ. 2, 271–286.
Hare, C.H., 1993. The evolution of calcium metasilicate in paint and coatings. Mod.
Paint Coating. 83 (12), 56–63.
Harris, T.Z., Mæhlum, T., 2003. Nitrogen removal in light-weight aggregate pre-
treatment filter columns and mesocosm wetlands. In: Mander, Ü., Jenssen,
P.D. (Eds.), Constructed Wetlands for Wastewater Treatment in Cold Climates,
Advances in Ecological Sciences, vol. 11. WIT Press, Southampton, Boston, pp.
273–297.
Hartikainen, H., 1982. Relationship between phosphorus intensity and capacity
parameters in Finnish mineral soils. II. Sorption–desorption isotherms and their
relation to soil characteristics. J. Agric. Sci. Finland 54, 251–262.
He, S.-B., Yan, L., Kong, H.-N., Liu, Z.-M., Wu, D.-Y., Hu, Z.-B., 2007. Treatment efficien-
cies of constructed wetlands for eutrophic landscape river water. Pedosphere
17, 522–528.
Heal, K.V., Younger, P.L., Smith, K.A., Glendinning, S., Quinn, P., Dobbie, K.E., 2003.
Novel use of ochre from mine water treatment plants to reduce point and diffuse
phosphorus pollution. Land Contam. Reclam. 11, 145–152.
Heal, K.V., Dobbie, K.E., Bozika, E., McHaffie, H., Simpson, A.E., Smith, K.A., 2005.
Enhancing phosphorus removal in constructed wetlands with ochre from mine
drainage treatment. Water Sci. Technol. 51, 275–282.
Hedström, A., 2006. Wollastonite as a reactive filter medium for sorption of wastew-
ater ammonium and phosphorus. Environ. Technol. 27, 801–809.
Heikkinen, K., Ihme, R., Osma, A.-M., Hartikainen, H., 1995. Phosphate removal by
peat from peat mining drainage water during overland flow wetland treatment.
J. Environ. Qual. 24, 597–602.
Heistad, A., Paruch, A.M., Vråle, L., Ádám, K., Jenssen, P.D., 2006. A high-performance
compact filter system treating domestic wastewater. Ecol. Eng. 28, 374–379.
Hill, C.M., Duxbury, J., Geohring, L., Peck, T., 2000. Designing constructed wetlands
to remove phosphorus from barnyard runoff: a comparison of four alternative
substrates. J. Environ. Sci. Health A35, 1357–1375.
Hylander, L.D., Kietlinska, A., Renman, G., Simán, G., 2006. Phosphorus retention in
filter materials for wastewater treatment and its subsequent suitability for plant
production. Bioresour. Technol. 97, 914–921.
Inglethorpe, S.D.J. 1992. Measurement of selected physical properties of three sam-
ples submitted by SAC consultants. British Geological Survey Technical Report
MPSR/92/17.
Jenssen, P.D., Krogstad, T., 2003. Design of constructed wetlands using phospho-
rus sorbing lightweight aggregate (LWA). In: Mander, Ü., Jenssen, P.D. (Eds.),
Constructed Wetlands for Wastewater Treatment in Cold Climates, Advances in
Ecological Sciences, vol. 11. WIT Press, Southampton, Boston, pp. 259–272.
Jenssen, P.D., Krogstad., T., Briseid, T., Norgaard, E., 1991. Testing of reactive filter
media (LECA) for use in agricultural drainage systems. In: International Seminar
of the Technical Section of CIGR on Environmental Challenges and Solutions in
Agricultural Engineering, Ås-NLH.
Johansson, L., 1997a. Phosphorus sorption to filter substrates-potential benefits for
on-site wastewater treatment. Doctoral Thesis. Royal Institute of Technology
(KTH), Sweden.
Johansson, L., 1997b. The use of LECA (Light Expanded Clay Aggregates) for the
removal of phosphorus from wastewater. Water Sci. Technol. 35, 87–93.
Johansson, L., 1999a. Industrial by-products and natural substrata as phosphorus
sorbents. Environ. Technol. 20, 309–316.
Johansson, L., 1999b. Blast furnace slag as phosphorus sorbents column studies. Sci.
Total Environ. 229, 89–97.
Johansson, L., Gustafsson, J.P., 2000. Phosphorus removal from wastewater by filter
media: retention and estimated plant availability of sorbed phosphorus. Water
Res. 34, 259–265.
Johansson, L., Hylander, L.D., 1998. Phosphorus removal from wastewater by filter
media: retention and estimated plant availability of sorbed phosphorus. J. Polish
Acad. Sci. 458, 397–409.
Johansson Westholm, L., 2006. Substrates for phosphorus removal—potential ben-
efits for on-site wastewater treatment? Water Res. 40, 23–36.
Joko, I., 1984. Phosphorus removal from wastewater by the crystallization method.
Water Sci. Technol. 17, 121–132.
Kaasik, A., Vohla, C., Mõtlep, R., Mander, Ü., Kirsimäe, K., 2008. Hydrated calcareous
oil-shale ash as potential filter media for phosphorus removal in constructed
wetlands. Water Res. 42, 1315–1323.
Kadlec, R.H., Knight, R.L., 1996. Treatment Wetlands. Lewis Publishers, CRC Press,
Boca Raton, 893 pp.
Kadlec, R.H., Wallace, S.D., 2008. Treatment Wetlands, 2nd ed. CRC Press, Boca Raton,
952 pp.
Kao, P.-C., Tzeng, J.-H., Huang, T.-L., 2000. Removal of chlorophenols from aqueous
solution by fly ash. J. Hazard. Mater. 76, 237–249.
Karaca, S., Gürses, A., Ejder, M., Açıkyıldız, M., 2004. Kinetic modeling of liquid-phase
adsorption of phosphate on dolomite. J. Colloid Interface Sci. 277, 257–263.
Kim, E.H., Yim, S.B., Jung, H.C., Lee, E.J., 2006. Hydroxyapatite crystallization from
a highly concentrated phosphate solution using powdered converter slag as a
seed material. J. Hazard. Mater. 136 (3), 690–697.
Kõiv, M., Kriipsalu, M., Vohla, C., Mander, Ü., 2009a. The secondary treatment of
landfill leachate in vertical flow filters using hydrated oil shale ash and peat.
Fresen. Environ. Bull. 18, 189–195.
Kõiv, M., Vohla, C., Mõtlep, R., Liira, M., Kirsimäe, K., Mander, Ü., 2009b. The per-
formance of peat-filled subsurface flow filters treating landfill leachate and
municipal wastewater. Ecol. Eng. 35, 204–212.
Korkusuz, E.A., Beklioglu, M., Demirer, G.N., 2005. Comparison of the treatment per-
formances of blast furnace slag-based and gravel-based vertical flow wetlands
operated identically for domestic wastewater treatment in Turkey. Ecol. Eng.
24, 187–200.
Korkusuz, E.A., Beklioglu, M., Demirer, G.N., 2007. Use of blast furnace granulated
slag as a substrate in vertical flow reed beds: field application. Bioresour. Tech-
nol. 98, 2089–2101.
 C. Vohla et al. / Ecological Engineering 37 (2011) 70–89
Krogstad, T., Sogn, T.A., Asdal, A., Saebo, A., 2005. Influence of chemically and bio-
logically stabilized sewage sludge on plant-available phosphorous in soil. Ecol.
Eng. 25, 51–60.
Kukier, U., Sumner, M.E., Miller, W.P., 1994. Boron release from fly ash and its uptake
by corn. J. Environ. Qual. 23, 596–603.
Kvarnstrom, M.E., Morel, C.A.L., Krogstad, T., 2004. Plant-availability of phospho-
rus in filter substrates derived from small-scale wastewater treatment systems.
Ecol. Eng. 22, 1–15.
Kwon, H.-B., Lee, C.-W., Jun, B.-S., Yun, J-d., Weon, S.-Y., Koopman, B., 2004. Recy-
cling waste oyster shells for eutrophication control. Resour. Conserv. Recycl. 41,
75–82.
Li, Y., Liu, C., Luan, Z., Peng, X., Zhu, C., Chen, Z., Zhang, Z., Fan, J., Jia, Z., 2006. Phosphate
removal from aqueous solutions using raw and activated red mud and fly ash.
J. Hazard. Mater. B137, 374–383.
Liira, M., Kõiv, M., Mander, Ü., Mõtlep, R., Vohla, C., Kirsimäe, K., 2009. Active fil-
tration of phosphorus on Ca-rich hydrated oil-shale ash: does longer retention
time improve the process? Environ. Sci. Technol. 43, 3809–3814.
Mæhlum, T., 1998. Cold-climate constructed wetlands: aerobic pre-treatment and
horizontal subsurface flow systems for domestic sewage and landfill leachate
purification. Ph.D. Thesis. Agricultural University of Norway, Ås.
Mæhlum, T., 1999. Wetlands for treatment of landfill leachate in cold climates. In:
Mulamoottil, G., McBean, E.A., Rovers, F. (Eds.), Constructed Wetlands for the
Treatment of Landfill Leachates. Lewis Publishers, Florida, Boca Raton, US, pp.
33–46.
Mæhlum, T., Jenssen, P.D., Warner, W.S., 1995. Cold-climate constructed wetlands.
Water Sci. Technol. 32, 95–101.
Mander, Ü., Teiter, S., Kuusemets, V., Lõhmus, K., Öövel, M., Nurk, Augustin, J.,
2003. Nitrogen and phosphorus budgets in a subsurface flow wastewater treat-
ment wetland. In: Brebbia, C.A. (Ed.), Water Resources Management. IWIT Press,
Southampton, Boston.
Mann, R., 1990. Phosphorus removal by constructed wetlands: substratum adsorp-
tion. In: Cooper, P.F., Findlater, B.C. (Eds.), Constructed Wetlands in Water
Pollution Control. Pergamon Press, Oxford, UK.
Mann, R.A., Bavor, H.J., 1993. Phosphorus removal in constructed wetlands using
gravel and industrial waste substrata. Water Sci. Technol. 27, 107–113.
Mayes, W.M., Batty, L.C., Younger, P.L., Jarvis, A.P., Kõiv, M., Vohla, C., Mander, U.,
2009. Wetland treatment at extremes of pH: a review. Sci. Total Environ. 407,
3944–3957.
Molle, P., Lienard, A., Grasmick, A., Iwema, A., Kabbabi, A., 2005. Apatite as an inter-
esting seed to remove phosphorus from wastewater in constructed wetlands.
Water Sci. Technol. 51 (9), 193–203.
Netter, R., 1992. Flow characteristics of planted soil filters. Water Sci. Technol. 29,
29–36.
Nieminen, M., Jarva, M., 1996. Phosphorus adsorption by peat from drained mires
in Southern Finland. Scand. J. Forest Res. 11, 321–326.
Oguz, E., 2004. Removal of phosphate from aqueous solution with blast furnace slag.
J. Hazard. Mater. B114, 131–137.
Öövel, M., Tooming, A., Mauring, T., Mander, Ü., 2007. Schoolhouse wastewater
purification in a LWA-filled hybrid constructed wetland in Estonia. Ecol. Eng.
29, 17–26.
Özacar, M., 2006. Contact time optimization of two-stage batch adsorber design
using second-order kinetic model for the adsorption of phosphate onto alunite.
J. Hazard. Mater. B 137, 218–225.
Pant, H.K., Reddy, K.R., Lemon, E., 2001. Phosphorus retention capacity of root bed
media of subsurface flow constructed wetlands. Ecol. Eng. 17, 345–355.
Piekos, R., Paslawska, S., 1999. Fluoride uptake characteristics of fly ash. Fluoride 32,
14–19.
Prochaska, C.A., Zouboulis, A.I., 2006. Removal of phosphates by pilot vertical-flow
constructed wetlands using a mixture of sand and dolomite as substrate. Ecol.
Eng. 26, 293–303.
Proctor, D.M., Fehling, K.A., Shay, E.C., Wittenbornand, J.L., Green, J.J., Avent, C.,
Bigham, R.D., Connolly, M., Lee, B., Shepker, T.O., Zak, M.A., 2000. Physical and
chemical characteristics of blast furnace, basic oxygen furnace, and electric arc
furnace steel industry slags. Environ. Sci. Technol. 34, 1576–1582.
Renman, G., Kietlinska, A., Cabamas, V., 2004. Treatment of phosphorus and bacteria
by filter media in onsite wastewater disposal systems. In: 2nd International
Symposium, Ecosan Closing the Loop, Lübeck, Germany, pp. 573–576.
Rex, M., 2000. Blast furnace and steel slags as liming materials for sustainable
agricultural production. In: Proceedings of the 2nd European Slag Conference,
Düsseldorf, EUROSLAG Publication, No. 1, pp. 137–149.
Richardson, C.J., Qian, S.S., Craft, C.B., 1996. Predictive models for phosphorus reten-
tion in wetlands. In: Vymazal, J. (Ed.), Proceedings of Conference on Nutrient
Cycling and Retention in Wetlands and Their Use for Wastewater Treatment,
Prague, Institute of Botany, Trebon, Czech Republic, pp. 125–150.
Rizzuti, A.M., Cohen, A.D., Hunt, P.G., Ellison, A.Q., 2002. Retention of nitrogen and
phosphorous from liquid swine and poultry manures using highly characterized
peats. J. Environ. Sci. Health B37, 587–611.
Roseth, R., 2000. Shell sand a new filter medium for constructed wetlands and
wastewater treatment. J. Environ. Sci. Health A35, 1335–1355.
Rustige, H., Tomac, I., Höner, G., 2003. Investigations on phosphorus retention in
subsurface flow constructed wetlands. Water Sci. Technol. 48, 67–74.
Sakadevan, K., Bavor, H.J., 1998. Phosphate adsorption characteristics of soils, slags
and zeolite to be used as substrates in constructed wetland systems. Water Res.
32, 393–399.
89
Saltnes, T., Føllesdal, M., 2005. Final Report: Material Development. 02056 Wastew-
ater treatment in filter beds, maxit Group AB.
Schindler, D.W., 1977. Evolution of phosphorus limitation in lakes. Science 195,
260–262.
Seo, D.C., Cho, J.S., Lee, H.J., Heo, J.S., 2005. Phosphorus retention capacity of filter
media for estimating the longevity of constructed wetland. Water Res. 39 (11),
2445–2457.
Shannon, E.E., Verghese, K.I., 1976. Utilisation of aluminised red mud solids for
phosphorus removal. JWPCF 48, 1948–1954.
Sharpley, A.N., Tunney, H., 2000. Phosphorus research strategies to meet agricultural
and environmental challenges of the 21st century. J. Environ. Qual. 29, 176–
181.
Shilton, A.N., Elmetri, I., Drizo, A., Pratt, S., Haverkamp, R.G., Bilby, S.C., 2006. Phos-
phorus removal by an ‘active’ slag filter-a decade of full scale experience. Water
Res. 40, 113–118.
Shilton, A., Pratt, S., Drizo, A., Mahmood, B., Banker, S., Billings, L., Glenny, S., Luo,
D., 2005. ‘Active’ filters for upgrading phosphorus removal from pond systems.
Water Sci. Technol. 51 (12), 111–116.
Song, Y., Hahn, H.H., Hoffmann, E., 2002. Effects of solution conditions on the precip-
itation of phosphate for recovery: a thermodynamic evaluation. Chemosphere
48, 1029–1034.
Soranno, P.A., Hubler, L., Carpenter, S.R., Lathrop, R.C., 1996. Phsophorus loads to
surface waters: a simple model to account for spatial pattern of land use. Ecol.
Appl. 6, 865–878.
Søvik, A.K., Kløve, B., 2005. Phosphorus retention processes in shell sand filter sys-
tems treating municipal wastewater. Ecol. Eng. 25 (2), 168–182.
Strang, T.J., Wareham, D.G., 2006. Phosphorus removal in a waste-stabilization pond
containing limestone rock filters. J. Environ. Eng. Sci. 5, 447–457.
Stumm, W., Morgan, J.J., 1981. Aquatic Chemistry—An Introduction Emphasizing
Chemical Equilibrist in Natural Waters. Wiley, New York.
Szögi, A.A., Humenik, F.J., Rice, J.M., Hunt, P.G., 1997. Swine wastewater treatment
by media filtration. J. Environ. Sci. Health B32, 831–843.
Talbot, P., Bélanger, G., Pelletier, M., Laliberté, G., Arcand, Y., 1996. Development of a
biofilter using an organic medium for on-site wastewater treatment. Water Sci.
Technol. 34, 435–441.
Tanner, C.C., Sukias, J.P.S., Upsdell, M.P., 1999. Substratum phosphorus accumulation
during maturation of gravel-bed constructed wetlands. Water Sci. Technol. 40,
147–154.
Tiessen, H., 1995. Phosphorus in the Global Environment: Transfers, Cycles, and
Management. John Wiley and Sons, New York.
Tisdale, S.L., Nelson, W.L., Beaton, J.D., Havlin, J.L., 1993. Soil Fertility and Fertilizers,
5th ed., Macmillan Coll. Div., p. 634.
Tsitouridou, R., Georgiou, J., 1988. Contribution to the study of phosphate sorption
by three Greek fly ashes. Toxicol. Environ. Chem. 17, 129–138.
Vohla, C., Alas, R., Nurk, K., Baatz, S., Mander, Ü., 2007. Phosphorus retention capacity
in a horizontal subsurface flow constructed wetland. Sci. Total Environ. 380,
66–74.
Vohla, C., Põldvere, E., Noorvee, A., Kuusemets, V., Mander, Ü., 2005. Alternative
filter media for phosphorus removal in a horizontal subsurface flow constructed
wetland. J. Environ. Sci. Health A 40, 1251–1264.
Vollenweider, R.A., 1968. The scientific basis of lake and stream eutrophication
with particular reference to phosphorus and nitrogen as eutrophication factors.
Technical Report OECD, DAS/C81/68, Paris, France.
Vymazal, J., Brix, H., Cooper, P.F., Green, M.B., Haberl, R., 1998. Constructed Wet-
lands for Wastewater Treatment in Europe. Backhuys Publishers, Leiden, The
Netherlands.
Vymazal, J., Brix, H., Cooper, P.F., Haberl, R., Grüneberg, B., Kern, J., 2000.
Phosphorus retention capacity of iron-ore and blast furnace slag in sub-
surface flow constructed wetlands. In: 7th International Conference of
Wetlands Systems for Water Pollution Control, vol. 1, University of
Florida, Grosvenor Resort, Lake Buena Vista, Florida, November 11–16, p.
113–20.
Willadsen, C.T., Riger-Kusk, O., Qvist, B., 1990. Removal of nutrient salts from two
Danish root zone systems. In: Cooper, B.C. (Ed.), Use of Constructed Wetlands in
Water Pollution Control. Pergamon, Oxford, pp. 115–126.
Wood, R.B., McAtamney, C.F., 1996. Constructed wetlands for waste water treat-
ment: the use of laterite in the bed medium in phosphorus and heavy metal
removal. Hydrobiologia 340, 323–331.
Xu, D.F., Xu, J.M., Wu, J.J., Muhammad, A., 2006. Studies on the phosphorus sorption
capacity of substrates used in constructed wetland systems. Chemosphere 63,
344–352.
Yamada, H., Kayama, M., Saitu, K., Hara, M., 1986. A fundamental research on phos-
phate removal by using slag. Water Res. 20, 547–557.
Yan, J., Kirk, D.W., Jia, C.Q., Liu, X., 2007. Sorption of aqueous phosphorus onto
bituminous and lignitous coal ashes. J. Hazard. Mater. 148, 395–401.
Zhu, T., 1998. Fate of phosphorous in a light-weight aggregate (LWA) wastewater
treatment wetland. Ph.D. Thesis. Agricultural University of Norway, Ås.
Zhu, T., Jenssen, P.D., Mæhlum, T., Krogstad, T., 1997. Phosphorus sorption and chem-
ical characteristics of lightweight aggregates (LWA)—potential filter media in
treatment wetlands. Water Sci. Technol. 35, 103–108.
Zhu, T., Mæhlum, T., Jenssen, P.D., Krogstad, T., 2003. Phosphorus sorption charac-
teristics of light-weight aggregate. Water Sci. Technol. 48, 93–100.