23. - 25. 10.

2012, Brno, Czech Republic, EU

PHOSPHORUS REMOVAL FROM WASTEWATER VIA ENVIRONMENTALLY FRIENDLY

TECHNOLOGIES
Marek HOLBAa,b, Ondej KORVANa,c, Elika MARLKOVb, Blahoslav MARLEKb
a

ASIO, spol. s r.o., Brno, Czech Republic, EU, holba@asio.cz

Institute of Botany of the Academy of Science of the Czech Republic, v.v.i., Brno, Czech Republic, EU,
sinice@sinice.cz
c

Institute of Chemical Technology, Prague, Czech Republic, EU, skorvan@asio.cz

Abstract
Stringent parameters for outlet wastewater quality lead to the development of advanced technologies for
pollutant removal. It can be expected that not only nutrients, but also other pollutant as bacteria, viruses,
hormons, PPCPs are expected to be subject of WWTP outlet quality standards. Phosphorus is essential
nutrient for living beings, however its excessive concentration in water environment could lead to the
proliferation of cyanobacteria and water bloom creation. Not sufficiently treated wastewater treatment plant
outlets are important sources of the phosphorus in water environment. Many developed countries already
adopted legislation dealing with phosphorus removal, however outlet standards are still high (more than 1
mg/L) and not sufficient for the elimination of excessive phosphorus elimination from the environment. Our
team tested unique techniques for phosphorus removal via tertiary treatment using iron nanoparticles. We
present data of phosphorus elimination from several municipal wastewater treatment plant outlets.
Keywords: phosphorus removal, wastewater treatment, nanoiron, tertiary treatment
1.

INTRODUCTION

Non-effectively treated domestic, municipal and industrial wastewater can cause environmental problem that
has harmful consequences on public health. Nutrients dissolved in the surface and groundwater are directly
responsible for the creation of water bloom and eutrophication that negatively affects many natural water
bodies [1].
Phosphorus can be present in the environment in different forms: orthophosphate, polyphosphate and
organic phosphorus. The principal phosphorus compounds in wastewaters are generally orthophosphates
often linked to smaller amounts of organic phosphorus. Phosphorus fractions can be differentiated in terms
of soluble (pass 0.45 m filter) and particulate forms, as well as their reactivity under acid and heat, which
was the basis for analytical methods applied to analyze different forms of phosphorus. For both particulate
and soluble form of phosphorus, they can be fractionized into reactive phosphorus (normally assumed as
orthophosphates, which can be a free ion or chemically bound), acid hydrolysable phosphorus (e.g.
polyphosphate and condensed P), and organic phosphorus (e.g. intracellular molecules that contain
phosphorus, element and refractory (non-biodegradable) phosphorus associated with cell decay debris) [2].
As more advanced treatment processes are pushed to eliminate nearly all the orthophosphates in order to
meet future expected extremely low TP limits, other factions of P in the final effluent become relevant and
important. Currently, little is known about the nature of various forms of P and their susceptibility to different
P removal processes. A few recent studies showed that the fractional composition of phosphorus and their
removal efficiency vary among wastewater effluents from different treatment processes [3,4].
The concentrations of phosphorus most often encountered in domestic and industrial wastewaters range
between 3 and 15 mg/L [5]. EU Directive 91/271/EEC species a limit value of phosphate for efuent

23. - 25. 10. 2012, Brno, Czech Republic, EU

discharge in the receiving waters in function of the size of the sewage treatment plants. A limit value of 2.0
mg TP/L is recommended by European Union for a population equivalent ranging between 10 000 and 100
000, whereas an acceptable phosphate level of 1.0 mg TP/L is recommended for a population equivalent
higher than 100 000 [6]. By comparison, Czech governmental direction 23/2011 requests similar values and
enacts 3.0 mg TP/L as limit value for municipal wastewater treatment plant outlets from 2 000 to 10 000 PE
[7]. On the other hand American state environmental agencies and the U.S. Environmental Protection
Agency (EPA) are requiring dischargers to reduce and achieve total phosphorus effluent concentrations as
low as 0.009 to 0.05 mg/L in the U.S. to address water quality problems [8].
Current phosphorus removal practice employs biological, chemical, or combined biological and chemical
processes. Biological phosphorus removal relies on the function of a specific group of polyphosphateaccumulating microorganisms that are capable of taking up excessive phosphorus as intracellular storage,
and the phosphorus is removed from the liquid by sludge wasting. Chemical phosphorus removal is achieved
by the addition of salts of multivalent metal ions (e.g. FeCl3, Fe2(SO4)3, Al2(SO4)3, or Ca(OH)2) to form
precipitates of sparingly soluble metal phosphate complexes. Both of these processes target at eliminating
only soluble orthophosphates or those forms in the influent that can convert into ortho-P during the treatment
process, by transforming it into solids phase followed by subsequent solid and liquid separations. Since most
permit limits are based on total phosphorus (TP), the effluent P level is affected by both the effectiveness of
chemical and/or biological P treatment processes as well as the final solid and liquid separation efficiencies
[9].
Novel technologies for phosphorus removal via tertiary treatment include advanced oxidation processes
such as electrochemical processes. Expected direction of legislation dealing with wastewater treatment plant
outlets will cover also removal of xenobiotics, hormons, endocrine disruptors and PPCPs. Therefore it seems
to be clear that it is necessary to focus on technologies that enable to solve the problem in holistic approach.
Nanotechnology has the potential to create novel and effective in situ treatment since nanoparticles have
unique and tunable physical and chemical properties. Their properties can be adjusted to make them highly
reactive with other pollutants and to minimize the formation of the toxic by-products. Highly reactive
nanoparticles such as nanoscale zerovalent iron (nanoiron or NZVI), nanocatalysts and nanosorbents have
been developed to show their potential, Nanoparticles can sequester wastewater contaminants (via
adsorption or complexation) making them immobile, or can degrade or transform them into innocuous
compounds. Contaminant transformations by zerovalent nanoiron, which is a strong reductant, are typically
redox reactions [10].
2.

MATERIAL AND METHODS

2.1.

Plant description

Plant A is designed for 8000 PE with biological nitrogen removal (nitrification with front-end denitrification)
and chemical phosphous removal (40 % w/ solution of Fe2(SO4)3). Plant B is designed for 150 PE and no
phosphorus removal is applied here.
2.2.

Material

Zerovalent and hexavalent nanoiron were used commercial types from Nanoiron company (Nanofer 25S).
2.3.

Analytical methods

Samples were taken from wastewater treatment plants outlets as grabbed. Orthophosphate concentration
was determined by EN ISO 6878 [11].

23. - 25. 10. 2012, Brno, Czech Republic, EU

3.

RESULTS AND DISCUSSIONS

We chose two municipal wastewater treatment plants (WWTPs) with and without phosphorus removal and
tested zerovalent nanoiron and ferrates for phosphorus removal. WWTPs were chosen carefully with regard
to further research with phosphorus fractionation and determination of hormons, endocrine disruptors and
PPCPs. The main task was to verify hypothesis of possible NZVI and ferrate full-scale application for
phosphorus removal as a tertiary treatment step. Coagulants are recently used for the phosphorus removal
at the municipal wastewater treatment plants and they are effective and efficient, however it is not expected
that coagulants are able to handle with pharmaceuticals, EDs and hormons in the future.
We took grabbed samples of the wastewater treatment plant outlets several times per year to carry out
kinetic tests. Both WWTPs were working in satisfactorily way and they were capable to fulfill governmental
directions 23/2011 about discharge to the recipient. There were no special operational occasions that could
negatively affect measured data.

Fig.1: Kinetic tests with NZVI from WWTP B with different Fe:P ratio

Fig.2: Kinetic tests at WWTP A with ferrates with different Fe:P ratios

23. - 25. 10. 2012, Brno, Czech Republic, EU

Fig.3: Kinetic tests at WWTP B with ferrates with different Fe:P ratios
Kinetic tests were performed in order to find proper ratio between dosage of nanoiron to phosphorus present
in the wastewater. WWTP A had already installed phosphorus removal and therefore concentration of P was
usually very low (< 1 mg/L) and therefore we needed to spike it up to 3-4 mg/L as can be seen at the Fig.2.
WWTP have no installed P removal and therefore phosphorus is removed only via incorporation into
activated sludge biomass. If we compare efficiency of NZVI and ferrates then it is easily visible that P
removal by NZVI is very low (ca. 20%) compared with application of ferrates. Ferrates showed very good P
III
removal even in very small dosages. It can be counted to the coagulation effect of Fe salts in the solution.
4.

CONCLUSIONS

Our research is recently focused on the phosphorus removal from wastewater treatment plant outlets. We
chose two municipal wastewater treatment plants (with and without phosphorus removal) and tested
zerovalent and hexavalent nanoiron for phosphorus removal. Ferrates showed promising results even for
smaller dosages, whilst NZVI showed not satisfactorily results for full-scale application. Next work will include
phosphorus fractionation and fate of different phosphorus fractions at the tertiary treatment. Increasing
interest on xenobiotics, hormons, endocrine disruptors, heavy metals and PPCPs and their removal from the
plant outlets will extend our testing in the future.
ACKNOWLEDGEMENT
This research is supported by Ministry of Industry and Trade through project FR-TI3/196: Advanced
technologies for hygienic and toxicology provisions of the wastewater treatment plant outlet.
LITERATURE
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L.E. De-Bashan, Y. Bashan, Recent advances in removing phosphorus from wastewater and its future use as
fertilizer, Water Res. 38 (19) (2004) 42224246.

[2]

Standard Methods, American Public Health Association (APHA), the American Water Works, Association
(AWWA) and the Water Environment Federation (WEF). Washington DC, USA (2005).

[3]

M. Benisch, D. Clark, J.B. Neethling, A.Z. Gu, Can Tertiary Phosphorus Removal Reliably Produce 10 g/L Pilot
Results from Coeur D'Alene, IWA/WEF Nutrient Conference, Baltimore, Maryland, USA, (2007).

23. - 25. 10. 2012, Brno, Czech Republic, EU

[4]

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electrochemical coagulation or chemical coagulation as tertiary treatment. Sep. Purif. Technol. 95 (2012) 1625

[6]

European Commission, Council directive 91/271/EEC of 21 May 1991 concerning urban waste-water treatment,
Off. J. Eur. Union L135 (1991) 4052.

[7]

Czech Governmental Direction 23/2011 that changes 61/2003 as amended by 229/2007.

[8]

D. Ragsdale, Advanced Wastewater Treatment to Achieve Low Concentration of Phosphorus. EPA, (2007).

[9]

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Removal, Nutrient Recovery and Management, (2011) 11921204.

[10]

M.R. Wiesner, J.Y. Bottero, Environmental Nanotechnology, Applications and Impact of Nanomaterials, McGrawHill Companies, (2007).

[11]

SN EN ISO 6878:2004, Water quality determination of phosphorus Ammonium molybdate spectrometric

method.