Journal of Cleaner Production 218 (2019) 459e464

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Ferrous sludge from water clarification: Changes in waste

management practices advisable
Josef Marou
sek*, Vojte
ch Stehel, Marek Vochozka, Ladislav Kola

r, Anna Marou
skova
,
Otakar Strunecký, Ji
rí Peterka, Marek Kopecký, Sowmya Shreedhar


The Institute of Technology and Business in Cesk e Bud


ejovice, Okru
zní 517/10, 370 01, Cesk e Bud

ejovice, Czech Republic

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

Article history: Clarification via floccules of ferric hydroxide is a globally leading technology in processing and treating
Received 17 December 2017 surface water, and converting it into drinking water. The ferricebased coagulation sludge obtained is
Received in revised form routinely dewatered and mixed with biowaste, assuming that the finest colloidal fractions of clay present
24 December 2018
will improve the cationeexchange capacity of the composts produced. However, in relation to the
Accepted 3 February 2019
Available online 4 February 2019
application of these types of compost, farmers repeatedly and independently of one another reported
lower yields and crops suffering from phosphorus deficiency, even under proper phosphorus fertiliza-
tion. A 5-year study revealed that the cationeexchange capacity tends to increase, which is beneficial
Keywords:
Water clarification
over the long term. Nevertheless, the analyses performed revealed, for the first time, that this wide-
Coagulation sludge spread practice lowers the level of mobile phosphorus, on average, by 62% and the level of extractable
Flocculation phosphorus by 55%. To make things worse, the quality of the extractable phosphorus declines, since the
Phosphorus bioavailability biologically available calcium, magnesium and aluminum based phosphates are gradually being replaced
Process management by ferric phosphates (originating from the ferric sludge). Given that phosphorus is the most expensive
Bioeconomy nutrient, this finding is of great environmental and economic importance, since the formation of ferric
phosphates locks this most expensive nutrient into a form available neither to soil microbiota nor plants.
It is recommended that new ways of using ferricebased coagulation sludge be developed.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Freshwater is estimated to make up only 2.5% of all the water on
Earth (Choy et al., 2014). Both its quality and availability are dete-
riorating due to population growth and changes in standards of
living. As reviewed by Kravchenko and Panchenko (2017), a
plethora of research has been carried out on water purification.
Most impurities can be removed by coagulation, although the hy-
drophobic fraction and high molar mass compounds can be
removed more efficiently than the hydrophilic fraction and the low
molar mass compounds (Matilainen et al., 2010). Coagulation is a
process wherein the repulsive potential of the electrical double
layers of colloids is reduced in such a way that micro-particles can
be produced. These micro-particles collide with each other and
form larger structures (flocs) during the flocculation process. The
effectiveness of coagulation depends on several factors, including
* Corresponding author.
E-mail addresses: josef.marousek@gmail.com, marousek@mail.vstecb.cz
(J. Marou
sek).
the coagulant type and dosage, mixing conditions, pH, tempera-
ture, properties of impurities (such as size, functionality, charge and
hydrophobicity), as well as the presence of divalent cations and
concentrations of destabilizing anions (bicarbonate, chloride and
sulfate). The presence of plant-based coagulants has been known
since ancient times. However, recently it has been discovered that
in some cases they also have antimicrobial and heavy metal
removing properties (Rezania et al., 2016). Nevertheless, except for
the rare use of tannin extracts, today’s commercial practice prefers
“chemical” coagulants. Ferric salts (in particular ferric chloride and
ferric sulfate), alum and aluminum chloride were probably among
the first to be widely applied. Their use is still traceable today,
especially in developing countries (Jahn, 2011). When added to
water, ferric salts decompose into respective trivalent ions, hy-
drolyze and form several soluble complexes with high positive
charges, thus adsorbing onto the surface of the negative colloids
(Borchate et al., 2014). This practice has now been abandoned due
to the high operating costs involved (Matilainen et al., 2010).
Aluminum chloride can leave, especially during periods of cold
temperatures or at low pH levels, relatively high (0.01e0.15 mg L
1)

https://doi.org/10.1016/j.jclepro.2019.02.037
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
460 J. Marou
sek et al. / Journal of Cleaner Production 218 (2019) 459e464
residual aluminum levels. These are associated with serious health
problems, such as the development of Alzheimer’s disease and
senile dementia (Exley, 2017). Numerous organic synthetic polymer
flocculants are now available on the market to cater to the diverse
requirements of individual water treatment plants. It should be
noted that the development of low-pressure membranes (Huang
et al., 2009) and filtration techniques (Marou
sek et al., 2017) have
undergone accelerated development in the past few decades.
However, so far they have not been put into widespread commer-
cial practice for economic reasons. Economic reasons and low ef-
ficacy have also prevented the commercial deployment of cleaning
by magnetism (Ambashta and Sillanpa €€
a, 2010) or nanoparticles
(Simeonidis et al., 2016). Coagulation and flocculation thus remain
the most widely used techniques due to their simplicity and
technoeeconomic effectiveness. Aluminum and ferric hydroxides
are most commonly used for flocculation (Matilainen et al., 2010).
Aluminumebased flocculation is easier, as it only requires
aluminum sulfate to be dosed into the water, thereby spontane-
ously turning into aluminum hydroxide and subsequent reactions
including hydrolysis, complexation, precipitation and adsorption
follow (Edzwald, 1993). However, the simplicity is corrupted by
higher price and neurotoxic risks that are analogous to aluminum
chloride. Flocculation using ferric hydroxide is carried out on the
basis of the continuous calculated application of ferric chloride and
calcium hydroxide. Although technically more demanding, it is
commercially more widespread because of its low costs. The
coagulation sludge obtained from flocculation is routinely dried in
the open air in order to reduce its volume. The recuperation of
reactants is technically easy but unprofitable, as chemicals are
relatively inexpensive (Ha
skova , 2017). The content of the nutrients
captured in the sludge is too low to be used as a fertilizer. The
amount of organic matter is insufficient for combustion or pyrolysis
(Marou
sek et al., 2018). Since no profitable use has yet been found
and the finest colloid fractions of clay are present, the sludge is
currently being mixed with biowaste and composted, assuming the
increase of its cationeexchange capacity.
Phosphorus is an essential nutrient and also the most expensive
one (Dockhorn, 2009), with complex environmental impacts (Horta
et al., 2018). Much of the phosphorus in soils occurs in compounds
that differ in their availability to organisms (Turner et al., 2007).
Plants take in phosphorus in the form of phosphoric acid anions
under conditions in which its concentration in the plant signifi-
cantly exceeds the phosphorus content in the soil (Vance et al.,
2003). For this reason, it is (actively) accepted, compared to the
concentration gradient, where the intensity of intake depends on
the oxygen content, light intensity, temperature and the presence
of calcium ions, nitrates and borates that reduce it (Vance, 2001).
Mkhabela and Warman (2005) report that organic materials
applied to soils can influence soil phosphorus dynamics. However,
the mechanism is far from being fully understood. Mobility of
phosphorus in soils is generally low and is strongly influenced by
the sorption index, kinetics factor, intensity factor, pH and also
indirectly by soil redox conditions (Kovar and Pierzynski, 2009).
Langmuir’s isotherms (adsorption maximum and binding energy
constant) were used in the past to describe sorption phenomena
between phosphates and soil (Olsen and Watanabe, 1957). How-
ever, gradual saturation of phosphorus is time-consuming; that is
why the sorption index is nowadays calculated from a single point
of the adsorption isotherm (Bache and Williams, 1971). The rate at
which phosphorus transition from the solid to the liquid phase is
expressed using the kinetics factor, as proposed by Cook (1966).
Difficulties with interpreting all the soil phosphorus fractionation
methods (Sharpley et al., 1995) turned research towards identifi-
cation of factors describing interactions of mobile (plant-acces-
sible) phosphates (Pote et al., 1996). The transition from the solid
phase into the liquid soil solution phase occurs when lowering the
phosphorus concentration in the soil solution impairs the dynamic
equilibrium. The amount of phosphorus released (intensity factor)
is a measure of phosphorus solubility in a saturated soil environ-
ment (Schonfield, 1955). Phosphorus anions are bound to particles
with a positive electric charge, mainly to calcium, aluminum and
iron hydroxides, and clay minerals, where they replace OH ion
bonds to these particles. The extractable phosphorus can be further
divided into three calcium classes (CaPI, CaPII and CaPIII),
aluminum class (AlP) and iron class (FeP). Sorting from the most
readily biologically available class to the least available, is as fol-
lows: CaPI, CaPII, CaPIII, AlP, FeP (John, 1972). The CaP I class rep-
resents the most readily available group of phosphates to plants
and soil microorganisms (bound to soluble calcium, magnesium
and partly divalent iron). The CaP II class is readily available (bound
by calcium, magnesium and a part of divalent iron). Phosphates
classified as CaP III are strongly bound by calcium and still quite
available. AlP represents a class bound to aluminum; therefore, the
availability of such phosphorus is low. FeP corresponds to the least
available phosphates (bound to trivalent iron). The fraction of ferric
phosphates is dependent on the soil acidification, and thus on the
concentration of ionic iron (Vadas et al., 2005). Iron phosphates in
soil interact with organic soil matter, or with humic acids and
organic chelates (Karczmarczyk, 2004).
Old-time farmers used to ferment compost for 10e12 years and
reached an ion-exchange capacity of 300e400 mmol chem. eq.
1000 g
1 (Kol a
r et al., 2011). However, such timely practices are not
of interest commercially. Therefore, compost quality standards had
to be downgraded (minimum nutrient content, amount of dry
matter, absence of hazardous elements and the fact that the par-
ticles of original organic material are so decomposed that the origin
of such material cannot be identified) in order to support com-
posting practices over landfilling (Marou
sek et al., 2016). Such pa-
rameters can be achieved within a few weeks. However,
experienced farmers are not interested in accepting these “pseudo“
composts, even free of charge, since the fertilization effect hardly
covers transportation and handling costs (Kol a
r et al., 2011). In
commercial practice, composting for about 2 years is being
employed, since it has been repeatedly and independently proven
that such fermentation time is the minimum necessary to reduce
soil-borne pathogens and diseases (Bastioli, 1998). The current
practice is based on the assumption that application of the com-
posts made of coagulation sludge from water clarification should
improve crop yields based on the following assumptions: 1) in-
crease in organic matter and nutrients; 2) increase in
cationeexchange capacity obtained from the finest colloid fractions
of clay that was captured from clarified water. However, there are
indications that some of these assumptions are questionable. Quite
the reverse, farmers have repeatedly and independently of each
other reported that the plants farmed in locations treated by such
composts show signs of phosphorous deficiency (small and elon-
gated leaves with red to purple color, along with delayed devel-
opment of reproductive organs), despite sufficient phosphorus
fertilization (Vance et al., 2003). To the best of our knowledge, there
is a research gap that limits understanding the interactions of plant
phosphorus intake in relation to composts made of ferrous sludge
from water clarification.
Based on the above, the following hypothesis was formulated:
the application of composted coagulation sludge obtained from
water clarification via ferric hydroxide flocculation influences the
phosphorus behavior in the topsoil.
2. Material and methods
Firstly, ferricebased coagulation sludge was obtained from local
 J. Marou
sek et al. / Journal of Cleaner Production 218 (2019) 459e464
waterworks and analyzed (Table 1). Volatile solids (hereinafter as
VS) were determined by an OV400 oven (Memmert GmbH, Ger-
many) and an LH 06/13 muffle furnace (Fisher Scientific Ltd., Czech
Republic) according to Mardoyan and Braun (2015). The oxidizable
carbon was analyzed by the Tjurin method (oxidation of soil
organic matter by mixture of potassium dichromate and sulfuric
acid followed by iron-ammonium sulfate titration) in modification
by Tirol-Padre and Ladha (2004). The cellulose and lignin contents
were determined using a Fibertec 1020 (M6) fiber analyzer (FOSS A/
S, Denmark). The higher heating value was analyzed using the auto-
calculating bomb calorimeter (CA-4AJ, Shimadzu, Japan). Levels of
nutrients were analyzed, as described in Dan et al. (2008).
Secondly, ferricebased coagulation sludge (15%) was mixed
with cattle slurry (30%), peat (25%), pond mud (22%), limestone
(6%) and inoculate (topsoil from farmed fields, neutral cambisol,
2%) as is common commercial practice. The control mixture (blank
sample) did not contain the ferricebased coagulation sludge, while
the ratios of other feedstock were identical. In order to manage an
optimal balance of bioavailable nutrients for microorganisms acting
in composting, the carbon-nitrogen ratio was adjusted through the
addition of urea to achieve the ratio of 20:1 and the phosphorus
content was improved through the addition of ground phosphate to
achieve a concentration of 0.15% (in accordance with commercial
practice, Marou
sek et al., 2016). Both mixtures were composted
(row width 2.5 m, height 1.6 m, weekly turning) for 2 years in
accordance with commercial practice.
Thirdly, noneagricultural soil locations (A and B) that were not
affected by previous fertilization were selected for field trials. A is
located at an average altitude of 510 m and B, at 910 m above sea
level, both sandyeloam cambisols. Both locations were character-
ized by pHKClusing the method developed by Pionke and Corey
(1967) and the MW101-SOIL pH analyzer. The level of soil parti-
cles that are most chemically and physically active (% of grains
smaller than 0.01 mm) was determined by the Kopecký apparatus.
This analytical tool consists of a series of successively connected
larger tubes, with the soil sample being placed in the smallest tube
and water passing upward through the tubes at a set volume per
unit time (Kemper and Rosenau, 1986). The upward velocity of the
water is smaller in the larger tubes; hence, successively smaller
equivalent sizes of particles remain in the successively larger tubes,
where they are subsequently weighed. After the initial analysis (see
Table 1), both composts obtained (50 tons in fresh weight applied
per hectare) were introduced into the upper 20 cm of the arable
land at chosen locations.
The field trial ran for 5 years. The total extractable, organic and
mobile phosphorus were analyzed according to Kovar and
Piezinsky (2009). The extractable classes were analyzed based on
Table 1
The composition of coagulation sludge obtained from water clarification
via ferric hydroxide flocculation. All data are expressed in % (by weight in
VS).
analysis (% VS)
Volatile solids 20.0 ± 4.1
Oxidizable carbon 2.28 ± 0.5
Cellulose and lignin 3.50 ± 1.6
Higher heating value (kJ kg
1) 0.73 ± 0.4
Silicon oxide 3.48 ± 0.7
Aluminum oxide 0.94 ± 0.2
Manganese oxide 0.10 ± 0.04
Phosphorus pentoxide 0.03 ± 0.01
Calcium oxide 0.48 ± 0.05
Magnesium oxide 0.15 ± 0.02
Sulfur 0.06 ± 0.04
Iron oxide 9.08 ± 1.9
461
the methods developed by Bray and Kurtz (1945) and modified by
John (1972). The analysis is a lengthy procedure, where the CaPI;
CaPII; AlP; FeP and finally CaP III are sequentially determined. In
brief, CaPI is determined (according to Aspila et al., 1976) after
extraction in a mixture of ammonium sulfate and ammonium
molybdate that is followed by intensive shaking and centrifugation.
The remaining solid fraction is subsequently washed with a satu-
rated solution of sodium chloride and centrifuged. The washed
sample is then extracted with a mixture of acetic acid and ammo-
nium molybdate (during intensive shaking and centrifugation) and
the level of released phosphates (CaPII) is analyzed according to
Aspila et al. (1976). The remaining solid sediment is washed once
more with a saturated solution of sodium chloride and centrifuged.
The supernatant is extracted with an ammonium fluoride solution
for 1 h. The AlP extracted is determined photometrically by a
method developed by Hanson et al. (1950) in modification by
Johnson and Pilson (1972). The solid residue is washed once more
with a saturated solution of sodium chloride and centrifuged to be
subsequently extracted with sodium hydroxide for 24 h, which is
followed by another intensive centrifugation. The released class of
phosphates FeP is then determined from the liquid fraction ac-
cording to Aspila et al. (1976). The sediment in the centrifuge vessel
is washed again with a saturated sodium chloride solution and
intensively centrifuged. The sediment is extracted with sulfuric acid
for one hour. After centrifugation, the supernatant is neutralized
and then phosphates are determined photometrically according to
Hanson et al. (1950) in modification by Johnson and Pilson (1972).
In this way, the level of CaP III is determined. The sorption index
was analyzed from a single point of the adsorption isotherm at a
starting concentration of 2.5 mmol P L
1 according to Bache and
Williams (1971). The rate of release of phosphorus from the solid
phase to the liquid kinetics factor was analyzed by the amount of
phosphorus absorbed by annex in the soil OH
cycle, as proposed
by Cook (1966). The intensity factor is determined from the topsoil
leaching in calcium chloride according to Schonfield (1955). Crop
yields were calculated manually from an area of 25 m2. All the
samples n ¼ 5, a ¼ 0.05.
3. Results and discussion
3.1. Verification of reproducibility
Analysis of the ironebased coagulation sludge obtained as a
result of the application of ferric chloride with calcium hydroxide
confirmed that the organic matter content was low (see Table 1).
This therefore excludes its use for energy recovery, which is in
agreement with Huang et al. (2009) and other researchers. The
levels of nutrients were also determined to be negligible (see
Table 1), which is in agreement with Matilainen et al. (2010) and
other researchers. As a result, the sludge cannot therefore be used
for fertilizing purposes due to economic reasons (the price of
available nutrients is far from being able to cover the cost of its
application). All the analyses of the ferricebased coagulation sludge
from water clarification showed only slight deviations compared to
the data already published in reviewed literature (Choy et al., 2015),
which creates a good premise for the generalization of the
knowledge subsequently acquired. The analyses revealed that at
higher altitudes, a greater proportion of phosphorus is present in an
organic form and the pH is lower (see column I in Tables 2 and 3).
These findings are in good agreement with the observations of local
farmers, who report lower yields in elevated areas. With regards to
the soil analyses performed before the start of the experiment, both
sandyeloam cambisols proved to be moderately acidic with low
mobile phosphorus content (see Tables 2 and 3). The total and
extractable phosphorus levels were also low; however, the organic
462 J. Marou
sek et al. / Journal of Cleaner Production 218 (2019) 459e464

Table 2
Time dynamics of agrochemical characteristics of topsoil A, where: I ¼ before the start of the experiment; II ¼ one week after the introduction of the compost into the soil
profile; III ¼ 1 year later; IV ¼ 2 years later; V ¼ 3 years later; VI ¼ 4 years later; VII ¼ 5 years after introduction.

I II III IV V VI VII

Total phosphorus (mg kg
1) 691 ± 63 705 ± 52 702 ± 47 709 ± 60 697 ± 55 695 ± 51 707 ± 44
Organic phosphorus (mg kg
1) 276 ± 35 270 ± 38 277 ± 42 285 ± 33 289 ± 39 295 ± 31 297 ± 42
Mobile phosphorus (mg kg
1) 28 ± 6 29 ± 5 26 ± 5 21 ± 4 16 ± 5 12 ± 4 9±2
Extractable phosphorus (mg kg
1) 235 ± 36 220 ± 20 205 ± 25 185 ± 19 166 ± 11 135 ± 31 112 ± 15
CaPI (%) 26.3 20.2 16.8 12.6 11.2 10.4 10.1
CaPII (%) 20.7 19.5 18.2 15.5 13.4 12.7 11.3
CaPIII (%) 24.3 28.4 25.6 20.1 16.3 14.3 13.0
AlP (%) 13.2 13.6 13.5 14.2 14.3 15.7 15.8
FeP (%) 15.5 18.3 25.9 37.6 44.8 46.9 49.8
Intensity factor 0.21 0.20 0.18 0.16 0.15 0.13 0.11
±0.05 ±0.05 ±0.04 ±0.03 ±0.05 ±0.03 ±0.02
Kinetics factor 0.61 0.51 0.50 0.46 0.40 0.35 0,33
±0.11 ±0.25 ±0.22 ±0.15 ±0.08 ±0.11 ±0.07
Sorption index 2.81 3.00 3.12 3.26 3.65 4.01 4.12
±0.70 ±0.63 ±0.55 ±0.49 ±0.50 ±0.42 ±0.63
CEC (mmol kg
1) 142 ± 18 140 ± 21 140 ± 13 143 ± 9 145 ± 25 147 ± 16 146 ± 14
pHKCl 5.83 5.79 ± 0.14 5.85 ± 0.18 5.77 ± 0.24 5.81 ± 0.17 5.85 ± 0.19 5.82 ± 0.15
±0.18
Grains smaller than 0.01 mm (%) 27.1 27.6 27.0 27.4 27.3 27.6 26.9
±2.8 ±3.4 ±1.9 ±2.9 ±2.5 ±3.0 ±3.6

Table 3
Time dynamics of agrochemical characteristics of topsoil B, where I - VII as in Table 2.

I II III IV V VI VII

1
Total phosphorus (mg kg ) 840 ± 69 792 ± 54 833 ± 62 801 ± 73 805 ± 54 796 ± 63 812 ± 50
Organic phosphorus (mg kg
1) 428 ± 54 432 ± 46 438 ± 32 440 ± 41 443 ± 55 444 ± 52 445 ± 49
Mobile phosphorus (mg kg
1) 25 ± 7 20 ± 5 17 ± 3 15 ± 6 14 ± 5 12 ± 5 11 ± 3
Extractable phosphorus (mg kg
1) 218 ± 31 194 ± 25 170 ± 21 143 ± 11 121 ± 19 103 ± 30 94 ± 12
CaPI (%) 14.5 10.0 7.7 6.9 6.1 5.5 5.3
CaPII (%) 15.4 13.6 10.6 10.0 9.2 8.4 8.0
CaPIII (%) 13.8 14.6 14.3 13.3 13.1 12.9 10.6
AlP (%) 18.6 15.5 17.5 17.3 18.1 18.8 19.4
FeP (%) 37.7 46.3 49.9 52.5 53.5 54.4 56.7
Intensity factor 0.12 0.10 0.10 ± 0.02 0.10 ± 0.03 0.07 ± 0.02 0.06 ± 0.04 0.06
±0.05 ±0.03 ±0.01
Kinetics factor 0.25 0.21 0.19 ± 0.02 0.18 ± 0.05 0.17 ± 0.03 0.16 ± 0.05 0.16
±0.07 ±0.05 ±0.03
Sorption index 4.12 4.45 4.51 ± 0.88 4.60 ± 0.34 4.76 ± 0.59 4.87 ± 0.62 4.98
±0.90 ±0.75 ±0.73
CEC (mmol kg
1) 92 ± 8 93 ± 10 93 ± 11 94 ± 5 95 ± 10 96 ± 8 95 ± 7
pHKCl 5.26 5.22 5.29 5.27 5.21 5.25 5.26
±0.08 ±0.05 ±0.11 ±0.09 ±0.12 ±0.09 ±0.10
Grains smaller than 0.01 mm (%) 23.8 22.9 23.5 24.1 23.4 23.2 23.7
±3.5 ±4.5 ±3.3 ±3.7 ±4.0 ±3.6 ±4.1

AC A BC B

Clover 19.8 ± 0.0 19.8 ± 0.0 17.4 ± 0.0 17.3 ± 0.0

Wheat 5.4 ± 0.0 5.3 ± 0.0 5.3 ± 0.0 5.3 ± 0.0
Potatoes 26.1 ± 0.0 26.0 ± 0.0 25.3 ± 0.0 25.3 ± 0.0
Wheat 5.5 ± 0.1 5.3 ± 0.0 5.4 ± 0.0 5.3 ± 0.1
Oats 3.5 ± 0.0 3.4 ± 0.0 3.6 ± 0.0 3.5 ± 0.0

phosphorus was nearly double at the higher altitude. These ob-
servations are indirectly consistent with other findings described in
published literature (Dockhorn, 2009) and confirm that the loca-
tions were chosen appropriately, because they had not been sub-
jected to farming activities in the past. An analysis of the pHKCl
revealed that the topsoil at the higher altitude is less favorable for
farming, which corresponds with the findings of Haynes and
Mokolobate (2001) and also indirectly supports the subsequent
generalizations based on the findings.
3.2. Changes in phosphorus bioavailability
Regarding the control sample (application of compost without
coagulation sludge), 5 years of analyses on phosphorus did not
show any changes (in limits of usual inaccuracy of analytical
measurements, data not stated). However, as for the composted
ferricebased coagulation sludge from water clarification, the re-
sults presented in Tables 2 and 3 reveal that one week after the
introduction of the sludge, all the agronomical soil phosphorous
indicators deteriorated. In the 5-year term, not only the mobile
phosphorus (trial A: 56%, trial B: 68%), but also the extractable
phosphorus (trial A: 52%, trial B: 57%) were reduced at both trial
sites. With regards to the extractable phosphorus, the content of
ferric phosphates increased. However, these are inavailable to
plants for their nutrition (Vadas et al., 2005). In contrast, the levels
of calcium phosphates (CaP I, CaP II and CaP III) were lower (see
Fig. 1). An increase in organic phosphorus was detected, which
demonstrates that the introduction of the compost did not
 J. Marou
sek et al. / Journal of Cleaner Production 218 (2019) 459e464
Fig. 1. Visualization of time changes in classes of extractable phosphorus.
contribute positively to the soil biota, since good living soils have
low organic phosphorus content (Turner et al., 2007). All the other
indicators for phosphorus dynamics (sorption index; kinetics factor
and intensity factor) also proved to be lower, which, as a conse-
quence, reduces the economics of crop production even further
(see Horta et al., 2018). All results give an overall picture showing
that there is a slow-down in the further deterioration of the
phosphorus availability in the soil. Nevertheless, such high losses in
biologically available phosphorus burden the yields of crop
production.
3.3. Economic considerations
Taking into account location A, the upper 25 cm (area where the
majority of the root system of conventional plants is located) in 1 ha
represents 6 M kg of arable land that (multiplied by 28 mg kg
1, see
Table 2) represents some 168 kg of mobile phosphorus. Over 5
years, the application of compost made of ferrous sludge resulted in
its reduction to 9 mg kg
1, respectively, to a loss of 114 kg of mobile
phosphorus ha
1, that can be expressed as 261 kg P2O5 or 390 EUR
ha
1 (converted to triple superphosphate at 284 EUR t
1 as priced
on the global market in August of 2018). Considering loses in yields
(Table 3) and corresponding commodity market prices, the total
loss ha
1 may be expressed illustratively as 310 EUR/ha
1 over a 5-
year horizon. Regarding location B, the loss of mobile phosphorus in
topsoil is 84 kg/ha
1, which can be interpreted as 192.5 kg P2O5
(289 EUR). Taking into account the losses in crop production
(Table 3), simplified estimation of financial loss over a 5-year ho-
rizon is similar to the loss in location A. At the same time, it was also
confirmed that the cationeexchange capacity increased (on
average by 1%). However, taking into consideration that phos-
phorus is the most expensive nutrient and the current practice
causes its loss by more than half, such a small improvement cannot
be considered reasonable (even in terms of money).
4. Conclusions
There are indications that the proposed hypothesis is valid. The
463
incorporation of composted coagulation sludge from water clarifi-
cation via ferric hydroxide flocculation into the topsoil influences
the phosphorus behavior in the topsoil. It turns out that iron pre-
sent in the sludge turns the phosphorus in its vicinity into iron
phosphates. As a result, the phosphorus present gradually becomes
unavailable to plants and soil microorganisms as well. Conse-
quently, the ferricebased coagulation sludge degrades the arable
land on a large scale and causes economic losses.
It seems advisable to focus future research on finding other in-
dustrial applications for ferricebased coagulation sludge. Prefer-
able are those that are not related to its application into arable land,
for instance, civil engineering.
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