Water Research 143 (2018) 19e27

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CO2-assisted phosphorus extraction from poultry litter and selective

recovery of struvite and potassium struvite
Utsav Shashvatt, Josh Benoit, Hannah Aris, Lee Blaney*
University of Maryland Baltimore County, Department of Chemical, Biochemical, and Environmental Engineering, 1000 Hilltop Circle, Engineering 314,
Baltimore, MD, 21250, USA

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

Article history: Phosphorus recovery from industrialized poultry operations is necessary to ensure sustainable waste
Received 2 April 2018 management and resource consumption. To realize these goals, an innovative, two-stage process
Received in revised form chemistry has been developed to extract nutrients from poultry litter and recover value-added products.
14 June 2018
Over 75% phosphorus extraction was achieved by bubbling carbon dioxide into poultry litter slurries and
Accepted 15 June 2018
Available online 18 June 2018
adding strong acid to reach pH 4.5e5.5. After separating the nutrient-deficient poultry litter solids and
the nutrient-rich liquid, the extract pH was increased through aeration and strong base addition. Over
95% of the extracted phosphorus was recovered as solid precipitate at pH 8.5e9.0. High-purity struvite
Keywords:
Phosphorus
and potassium struvite products were selectively recovered through pH control, introduction of a
Nutrient recovery calcium-complexing agent, and addition of magnesium chloride. The nitrogen-to-phosphorus-to-
Struvite potassium (NPK) ratio of the recovered solids was controlled through aeration and pH adjustment.
Poultry litter Precipitation at pH 8.5e9.0 and 10.5e11.0 resulted in NPK ratios of 2.0:1.0:0.1 and 0.9:1.0:0.2, respec-
Animal manure tively. The process effluent was effectively recycled as makeup water for the subsequent batch of poultry
Fertilizer litter, thereby decreasing water consumption and increasing overall nutrient recovery. Sequencing batch
operation yielded greater than 70% phosphorus recovery within a 45-min process, demonstrating the
potential for this technology to alleviate nutrient pollution in agricultural settings and generate an
alternative supply of phosphorus fertilizers.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction concern due to increased eutrophication of inland water bodies (Le

While wastewater treatment plants and agricultural operations
both introduce nutrients into water bodies (Alexander et al., 2008;
EPA, 2017; Maryna et al., 2016), the nutrient loads from regions
with intensive agricultural practices often drive negative environ-
mental outcomes (Alexander et al., 2008). This problem manifests
as nutrient transport through runoff from over-fertilized cropland
(Hart et al., 2004) and discharge from manure management sys-
tems (Mallin and Cahoon, 2003). Passive waste management stra-
tegies, such as piling, composting, and lagooning, have been
adopted by animal feeding operations (AFOs) to effectively treat
organic carbon and nitrogen. However, the unfavorable redox
chemistry of phosphorus does not allow any significant phosphorus
abatement in manure management systems (Vendramelli et al.,
2016). The fate of phosphorus in agricultural systems is a growing
* Corresponding author.
E-mail address: blaney@umbc.edu (L. Blaney).
et al., 2010). Compounding this issue, geospatially-limited phos-
phorus reserves are being rapidly depleted due to the increasing
food demand associated with the growing global population
(Cooper et al., 2011). Together, the environmental effects of phos-
phorus pollution and the economic vulnerability of phosphorus
markets mandate a need for phosphorus recovery from agricultural
waste.
In this context, poultry operations are especially important due
to the higher phosphorus content in poultry litter compared to
other animal manures. A typical nitrogen-to-phosphorus-to-
potassium (NPK) ratio for broiler (i.e., meat-producing bird) litter
is 0.2:1.0:0.5 mol/mol/mol (Shashvatt et al., 2016). Since fertilizers
are usually applied to meet nitrogen targets (Beegle and Durst,
2002; Mishima et al., 2010), the excess phosphorus in poultry-
based manure represents poor resource management and raises
environmental concerns about nutrient levels in agricultural
runoff. The State of Maryland (USA), which contains dense poultry
AFOs on the Eastern Shore of the Chesapeake Bay (National Chicken
Council, 2010), recently limited the use of poultry litter as a soil

https://doi.org/10.1016/j.watres.2018.06.035
0043-1354/© 2018 Elsevier Ltd. All rights reserved.
20 U. Shashvatt et al. / Water Research 143 (2018) 19e27
amendment on fields with high fertility index values (State of
Maryland, 2015). The fertility index value is computed using the
orthophosphate (P(V)), calcium (Ca2þ), magnesium (Mg2þ), and
potassium (Kþ) concentrations in soil and essentially describes the
potential for phosphorus runoff following land-application of fer-
tilizers, soil amendments, or animal manure (University of
Maryland Extension, 2006). As of March 2016, over 160,000 acres
of farm fields were required to monitor soil phosphorus levels;
furthermore, over 10,400 acres were banned from applying
phosphorus-containing fertilizers. The initial economic impact
model suggested that up to 228,000 tons of poultry litter would
require active management (Salisbury University, 2014).
Previous efforts to recover nutrients from poultry litter have
mostly focused on mechanical, thermochemical, and biological
treatment schemes. Mechanical processes have examined volume
reduction through compaction and pelletization systems that in-
crease the nutrient content per unit mass (Fasina et al., 2006).
However, these systems have the inherent drawback of not modi-
fying the NPK ratio and, therefore, the pelletized product may still
result in over-application of phosphorus to agricultural fields.
Thermochemical processing of poultry litter produces biochar that
can be used for a variety of applications: feed additive (Prasai et al.,
2016); soil amendment (Chan et al., 2008); and, remediation (Tang
et al., 2013). However, widespread adoption of thermochemical
operations does not represent a sustainable waste management
solution. Biological processes are being increasingly employed for
heat and energy recovery (Tiquia and Tam, 2002), but these sys-
tems do not have any independent benefits for treatment or re-
covery of phosphorus.
A number of processes have been developed for and applied to
recover phosphorus from wastewater treatment plants (Blaney
et al., 2007; Nieminen, 2010). While these technologies offer
viable phosphorus recovery for municipal wastewater, high-
strength animal manure poses challenges due to the differences
in inorganic chemistry, organic matter load, and solids content.
These parameters affect the extraction of phosphorus from waste
solids and the form of recovered products. The inorganic compo-
sition of the waste stream, especially the Ca2þ and Mg2þ content,
influence the chemical form of recovered phosphorus. High Ca2þ
content favors precipitation of hydroxyapatite, Ca10(PO4)6(OH)2,
while higher Mg2þ levels promote recovery of struvite,
MgNH4PO4$6H2O (Shashvatt et al., 2016). The elevated levels of
dissolved organic matter (DOM) in animal waste increase the
chemical demands associated with nutrient extraction and product
precipitation (Sommer and Husted, 2009); furthermore, DOM
competes with phosphorus in sorption-based technologies (Hunt
et al., 2007) and complexes divalent cations needed for precipita-
tion of nutrient-laden solids (Yan et al., 2015). As poultry litter has a
lower water content than cow and swine manure (Wolf et al.,
2005), nutrient extraction from the relatively dry solids requires
water consumption. However, large volumes of wastewater inhibit
sustainable process implementation. For these reasons, new para-
digms need to be explored with respect to nutrient recovery from
high-strength agricultural waste streams.
To date, phosphorus recovery from AFOs has mostly focused on
swine (Suzuki et al. 2005, 2007) and cattle (Mulbry et al., 2008;
Wilkie and Mulbry, 2002) manure, with only a few studies on
€ gi et al., 2008; Yilmazel and Demirer, 2011). Szo
poultry litter (Szo € gi
et al. (2008) reported 60% phosphorus recovery from poultry litter,
but the recovered hydroxyapatite is not an ideal agrochemical due
to its low solubility (Wier et al., 1971). Yilmazel and Demirer (2011)
primarily focused on nitrogen recovery through addition of phos-
phorus and magnesium to anaerobically digested poultry litter to
recover struvite and calcium phosphates; however, the need for an
exogenous P(V) source may prevent widespread application in
agricultural systems. Unlike hydroxyapatite, struvite represents a
slow-release fertilizer with a balanced ratio of nitrogen to phos-
phorus. Under certain conditions, potassium struvite
(MgKPO4$6H2O) can also be recovered (Graeser et al., 2008). Stru-
vite and potassium struvite can be mixed to produce nutrient-laden
solids with controllable NPK ratios.
To address the shortcomings identified above, the process
chemistry shown in Fig. 1 was devised to facilitate the selective
recovery of struvite and potassium struvite from poultry litter.
Briefly, poultry litter was added to water to generate a high-
strength slurry. Then, phosphorus was extracted through addition
of CO2(g) and strong acid. The nutrient-deficient solids were
separated from the nutrient-rich extract, which was aerated and
dosed with NaOH to precipitate struvite-based solids. The objec-
tives of this study were to (1) optimize the extraction of phos-
phorus from poultry litter as a function of pH and slurry strength,
(2) lower the acid/base demands of the process chemistry through
CO2 gas bubbling/aeration, and (3) selectively recover struvite and
potassium struvite from poultry litter. To prevent production of
large volumes of wastewater, the process effluent was reused to
generate subsequent poultry litter slurries, and this recycle scheme
was evaluated for impacts on nutrient extraction and precipitation
efficiency. The findings from this work enable sustainable recovery
of nutrient-balanced fertilizer products from agricultural waste
streams, while also preventing negative environmental outcomes
associated with nutrient pollution.
2. Materials and methods
2.1. Chemicals
Unless otherwise stated, all chemicals were procured from
Fisher Scientific (Hampton, NH). Phosphate standards were pre-
pared by adding disodium hydrogen phosphate (Na2HPO4) to
deionized (DI) water (Neu-Ion Systems; Windsor Mill, MD).
Concentrated hydrochloric acid (HCl; 35%) was used to prepare 1 M
HCl for pH adjustment. Sodium hydroxide (NaOH; 97%) was dis-
solved in DI water to generate 1e2 M NaOH solutions for pH
correction. Ethylenediaminetetraacetic acid (EDTA; 99.5%) was
obtained from Sigma-Aldrich (St. Louis, MO) and used to generate a
0.1 M EDTA solution at pH 8.0. A 0.1 M magnesium chloride
(MgCl2$6H2O; 99%) solution was prepared in DI water for use in
select precipitation experiments.
2.2. Poultry litter source and composition
Poultry litter was sourced from three different farms in the
Chesapeake Bay watershed. The litters have been anonymously
labeled as PL-1, PL-2, and PL-3. Before experimentation, 1 kg
batches of poultry litter were dried at 50  C for 3 days. The dried
litter was passed through stainless steel sieves with US mesh #16
(1.18 mm) to remove feathers, woodchips, bones, and other debris.
Slurries were generated by adding the dry, sieved poultry litter to
DI water. To investigate the impact of slurry strength on nutrient
recovery, poultry litter slurries were prepared at 4, 20, and 80 g/L.
For recycle experiments, a 100 g/L poultry litter slurry was
employed. All slurries were used within 2 h of generation.
Total phosphorus was measured using the EPA 3050B digestion
method (EPA, 1996). In accordance with previous reports (Szo €gi
et al., 2008; Yilmazel and Demirer, 2011), acid hydrolysis was
employed to measure the concentration of extractable phosphorus
and other inorganic ions. In particular, the pH of a 40 g/L slurry was
adjusted to approximately 1.0 with 1 M HCl, and the acid extract-
able phosphorus was measured using the stannous chloride
method (APHA et al., 2006) with a UVevisible spectrophotometer
 U. Shashvatt et al. / Water Research 143 (2018) 19e27 21

Fig. 1. Schematic of the process chemistry used for nutrient extraction from poultry litter and recovery of struvite-based solids.

(Thermo Scientific Evolution 600; Waltham, MA) or microplate with pH values in the 1.0e7.0 range. Solution pH was measured
reader (BioTek Eon; Winooski, VT). The difference in total phos- using an Orion Ross Ultra probe (Thermo Scientific; Waltham, MA).
phorus and acid extractable phosphorus was considered organic Poultry litter slurries were equilibrated under constant mixing for
phosphorus. Inorganic phosphorus was approximately 85% of the 30 min and then centrifuged at 5000 g for 10 min. Due to the high
total phosphorus, in agreement with previous reports for poultry strength of these slurries, the supernatant was diluted
litter (Sharpley and Moyer, 2000). 100e1000  before P(V) analysis. The extraction efficiency was
Other inorganic ions, such as Ca2þ, Mg2þ, Kþ, sodium (Naþ), calculated using Eq. (1).
ammonium (NHþ 2 
4 ), sulfate (SO4 ), and nitrate (NO3 ), were deter-
mined by flame atomic absorption spectroscopy (Perkin Elmer ½PðVÞpH i
hext;pH i ¼ (1)
3100 AAS; Waltham, MA) or ion chromatography (Dionex ICS-2100; ½PðVÞpH 1
Sunnyvale, CA). The ion chromatograph was run under isocratic
conditions with 12 mM potassium carbonate (anions) or 32 mM In Eq. (1), hext;pH i is the fraction of P(V) extracted into the
methanesulfonic acid (cations). Dissolved organic carbon (DOC) water-phase at pH i, ½PðVÞpH i is the P(V) concentration at pH i, and
concentrations in the poultry litter extracts were measured using a ½PðVÞpH 1 is the total acid-extractable P(V).
total organic carbon (TOC) analyzer (Shimadzu TOC-L; Columbia,
MD). Titration curves for poultry litter slurries were recorded with
an autotitrator (Radiometer Analytical TIM 865; Lyon, France). The 2.4. Struvite recovery from poultry litter extracts
inorganic content, DOC, and alkalinity for 40 g/L slurries of PL-1, PL-
2, and PL-3 are reported in Table 1. All compositional analyses were To generate nutrient-rich extracts, 80 g/L poultry litter slurries
conducted in triplicate, and data are reported as mean ± standard were bubbled with CO2(g) for 5 min and 1 M HCl was added to
deviation. reach pH 4.5. After 30 min of continuous mixing, the slurry was
centrifuged at 5000 g for 10 min. To remove any remaining parti-
2.3. Phosphorus extraction from poultry litter cles, the supernatant was passed through 20 mm paper filters
(Whatman; Maidstone, United Kingdom). For precipitation exper-
To investigate the impact of pH on phosphorus extraction, 1 M iments, the acidified poultry litter extracts were bubbled with
HCl was added to 40 g/L poultry litter slurries to generate solutions compressed air for 10 min, and then 2 M NaOH was added to attain
solution pH in the 7.0e11.0 range. Samples were vortexed for 10 s,
and the precipitate was allowed to settle for 30 min. The pre-
Table 1 cipitates were washed three times with DI water to remove soluble
Aqueous-phase composition (mean ± standard deviation; n ¼ 3) of acidified, filtered salts, such as sodium chloride (NaCl) and potassium chloride (KCl),
40 g/L poultry litter slurries.
and then freeze-dried (Labconco Freezone 4.5; Kansas City, MO) at
Inorganic Species PL-1 PL-2 PL-3 103 mbar and 50  C. Phosphorus concentrations were analyzed
Ca2þ (mg/L) 631.6 ± 11.5 952.4 ± 18.9 754.1 ± 5.1 in the supernatant to calculate precipitation efficiency (Eq. (2)).
Kþ (mg/L) 1042.6 ± 19.0 1331.6 ± 23.4 1516.7 ± 17.8
Mg2þ (mg/L) 187.8 ± 3.0 224.2 ± 5.1 265.0 ± 2.9 ½PðVÞpH j
Naþ (mg/L) 177.9 ± 4.7 433.6 ± 8.3 334.8 ± 3.3 hprec;pH j ¼1 (2)
NHþ 546.7 ± 4.6 423.8 ± 6.7 275.2 ± 1.9
½PðVÞpH 4:5
4 (mg/L)
NO3 (mg/L) 46.1 ± 1.6 n.d. a 0.2 ± 0.4
PO3 943.4 ± 24.9 1462.4 ± 55.3 1540.5 ± 62.3 In Eq. (2), hprec;pH j is the fraction of P(V) in the poultry litter
4 (mg/L)
SO2
4 (mg/L) 342.0 ± 8.2 969.9 ± 49.6 1000.3 ± 117.6 extract that precipitated at pH j, ½PðVÞpH j is the aqueous P(V)
Alkalinity (meq/L) 44.2 ± 0.0 44.6 ± 0.0 32.3 ± 0.0 concentration at pH j, ½PðVÞpH 4:5 is the aqueous-phase P(V) con-
Extractable DOC (mgC/L) 2532.0 ± 10.1 3110.6 ± 14.0 3309.3 ± 12.9 centration at pH 4.5, which represents the nutrient-rich extract.
a
n.d. ¼ not detected. The overall recovery efficiency, htot , was calculated using Eq. (3).
22 U. Shashvatt et al. / Water Research 143 (2018) 19e27
htot ¼ hext;pH i hprec;pH j (3)
For selective precipitation of struvite and potassium struvite, the
acidified extract from an 80 g/L PL-3 slurry was dosed with
stoichiometry-based amounts of EDTA and/or MgCl2. The calcium
concentration in the acidified extract was 13.6 mM. Thus, 13.6 mM
EDTA was added to complex Ca2þ ions and prevent precipitation of
calcium phosphates. In separate experiments, 13.6 mM EDTA and
13.6 mM Mg2þ were added to complex Ca2þ ions and compensate
for the complexed Ca2þ, respectively. Samples were vortexed for
10 s to ensure complete mixing. Then, 2 M NaOH was added to raise
the solution pH to 7.0e11.0. The samples were vortexed for 10 s, and
the phosphorus-laden precipitate settled for 30 min. Precipitates
were rinsed three times with DI water, freeze-dried, and stored at
4  C until analysis.
2.5. Recycling the liquid process effluent
To reduce water consumption, the process effluent from the
precipitation reaction was used to generate the subsequent poultry
litter slurry, as shown in Fig. 1. Here, a 100 g/L slurry was processed
using the extraction, solid-liquid separation, and precipitation
protocols described above. Filtered process effluent and fresh
poultry litter were used to prepare the slurry for the next cycle.
After nutrient extraction, separation, and precipitation in the sec-
ond cycle, the process effluent was again recycled to generate the
poultry litter slurry for the third cycle. In this manner, the input of
freshwater was reduced and nutrients were retained within the
system, ultimately increasing the overall nutrient recovery.
2.6. Compositional analysis of recovered solids
Scanning electron microscopy (SEM; FEI Nova NanoSEM 450;
Hillsboro, Oregon) was employed to examine the morphology of
recovered solids. Freeze-dried samples were loaded onto con-
ducting graphite tape fixed on aluminum supports. No sample
pretreatment was required because the precipitates were partially
conducting. Microphotographs were taken at different magnifica-
tion levels and the aspect ratio of recovered solids was calculated
using 10 random crystals. Energy dispersive X-ray spectroscopy
(EDS; Oxford Instruments Nanoanalysis; Abingdon, United
Kingdom) was employed on at least three areas to investigate the
atomic composition of distinct features in the samples. In addition,
approximately 300e600 mg of recovered solids were added to 1 L
of 10 mM HCl to confirm the inorganic composition and DOC con-
tent. These solutions were sonicated for 15 min to ensure complete
dissolution of the recovered solids. Inorganic ions and DOC were
analyzed using the techniques identified above.
3. Results and discussion
3.1. pH-dependent phosphorus extraction from poultry litter
Phosphorus extraction efficiencies were recorded for 40 g/L
slurries of PL-1, PL-2, and PL-3 as a function of pH (Fig. 2);
furthermore, the acid demand per gram of poultry litter is reported
in Fig. S1 of the Supporting Information (SI). All three poultry litter
slurries had an initial pH of approximately 6.7e6.9 and released
33e46% of the total extractable phosphorus upon addition of DI
water. The aqueous P(V) concentration increased to 62e65% of the
total extractable phosphorus after acidification to pH 5.0. Further
acid addition marginally increased the aqueous P(V) concentration
for the pH 5.5 to 3.5 range to around 67e72%. Below pH 3.0, the
aqueous P(V) concentration was greater than 80% of the total
Fig. 2. Phosphorus extraction from 40 g/L PL-1, PL-2, and PL-3 slurries overlaid
with the speciation-based models from Eq. (4) (solid curves). The slurry pH was
adjusted using 1 M HCl. Data symbols represent the mean of three replicate experi-
ments. The colored curves represent models for the individual poultry litter sources,
and the black solid and dotted curves represent the model and 95% confidence bands,
respectively, applied to all experimental data.
extractable phosphorus. Szo €gi et al. (2008) reported similar P(V)
extraction efficiencies for poultry litter with citric acid; however,
weak organic acids increase the buffer capacity of the slurry and,
ultimately, the amount of base needed for subsequent precipitation
of the recovered nutrients. For these reasons, slurry pH was
adjusted to 4.5e5.5 with HCl to optimize P(V) extraction efficiency
and avoid the costs associated with excessive acid/base addition.
Previous work in soil and sediment systems has elucidated pH
dependent P(V) adsorption-desorption behavior; furthermore,
calcium, aluminum, iron, and organic matter play important roles
in these reactions (Huang et al., 2005). Given the similarity of the
P(V) extraction curves for PL-1, PL-2, and PL-3 in Fig. 2 to phos-
phoric acid dissociation chemistry, chemical interactions were hy-
pothesized for individual P(V) species with poultry litter solids. This
conceptual framework enabled modeling of the nonlinear rela-
tionship between P(V) extraction efficiency and pH. Assuming that
the four aqueous P(V) species, namely H3PO4, H2PO 2
4 , HPO4 , and
3
PO4 , independently interact with poultry litter solids, the overall
extraction efficiency was modeled using Eq. (4).
hext;obs ¼ a0 hext; þ a1 hext; þ a2 hext; þ a3 hext; (4)
0 1 2 3
In Eq. (4), a is the ionization fraction (Stumm and Morgan, 2012)
of individual P(V) species, obs is the observed P(V) extraction effi-
ciency, and the 0, 1, 2, and 3 subscripts correspond to the H3PO4,
H2PO 4 , HPO4 , and PO4 species, respectively. The a values were
2 3
calculated using the slurry pH and acid dissociation constants for
phosphoric acid (i.e., pKa1 ¼ 2.15, pKa2 ¼ 7.20, and pKa3 ¼ 12.38;
Benjamin, 2010).
Experimental data were fit to Eq. (4) using a least squares
approach to calculate the hext;i terms. Because all experimental data
was at pH < 7, the hext;3 term was not included since a3 was
negligible (i.e., a3 < 105.7). The hext;0 , hext;1 , and hext;2 terms are
reported as average ± 95% confidence interval in Table S1 (see SI)
for the three poultry litter sources. Importantly, hext;1 controls the
 U. Shashvatt et al. / Water Research 143 (2018) 19e27 23

phosphorus extraction efficiency at the operational pH of the

extraction reactor (i.e., pH 4.5e5.5). The phosphorus extraction
efficiencies for the three poultry litters demonstrated similar trends
with solution pH, specifically in the operational pH range of
4.5e5.5. This finding may derive from the reasonably consistent
inorganic (Table 1) and organic (Mangalgiri et al., 2017) composi-
tion of these poultry litter sources. As shown in Fig. 2, the P(V)
speciation-based model fits the experimental data well. Note, this
model does not replace comprehensive compositional analysis and
equilibrium modeling, but rather serves as a quick validation of
operating conditions to optimize P(V) extraction from poultry litter
from diverse farms.

3.2. Recovery of nutrient-laden fertilizers

As indicated in Table 1, poultry litter has an inherently favor-

able chemical composition that includes high P(V), NHþ 2þ
4 , Mg ,
Ca2þ, and Kþ contents. With optimized stoichiometric and pH
conditions, these species can react to form a number of
phosphorus-laden minerals, including struvite, potassium struvite,
and calcium phosphates. Recovery of struvite minerals is preferred
due to the slower nutrient release kinetics compared to traditional
fertilizers (Talboys et al., 2016) and the balanced nitrogen-to-
phosphorus (MgNH4PO4$6H2O) and potassium-to-phosphorus
(MgKPO4$6H2O) ratios. The slower release kinetics reduce both
nutrient runoff and fertilizer demand. The use of nutrient-
balanced struvite minerals in custom fertilizer formulas will also
decrease consumption of energy-intensive traditional fertilizers,
such as urea, ammonium sulfate, mono-ammonium phosphate,
and potash. Nevertheless, struvite products may still need to be
mixed with traditional fertilizers to meet particular NPK
requirements.
Recall from Eq. (2) that the precipitation efficiency was
measured with respect to the P(V) concentration in the acidified
poultry litter extract; therefore, the precipitation efficiency was 0%
at pH 4.5 with no aeration or NaOH addition. The NaOH dataset in
Fig. 3 shows that the P(V) precipitation efficiency increased with
increasing pH. At pH 6.7 and 8.2, the P(V) precipitation efficiencies
were 48 (±3.5)% and 91 (±1.9)%, respectively. Above pH 9.0, more
than 95% of the extracted P(V) was precipitated in the form of
nutrient-laden minerals. Szo € gi et al. (2008) also reported high
precipitation efficiencies for P(V) extracted from poultry litter,
although Ca(OH)2 was used as base, an organic P-containing floc-
culant was required, and the final product was not in a preferred
fertilizer form. In separate experiments (Fig. S2 in the SI), increased
dosing of exogenous magnesium did not improve phosphorus
precipitation efficiency, although the composition of recovered
products may vary under these conditions.
The solids recovered from precipitation experiments were
analyzed by SEM-EDS. Fig. 4 presents microphotographs of solids
generated using the process chemistry described in Fig. 1, namely
extraction with CO2(g) and HCl followed by precipitation with air
and NaOH. The solids shown in Fig. 4a and b are representative of
products precipitated at pH 8.5e9.0 and 10.5e11.0, respectively, for
all three poultry litter sources. Under both pH conditions, small,
needle-like crystals and larger, granular particles were observed.
EDS analysis (Fig. S3 in the SI) indicated that the larger, irregular
solids were calcium phosphates, whereas the needle-like particles
were struvite and potassium struvite. Previous work has reported
co-recovery of calcium- and magnesium-based phosphates in
wastewater, although the presence of calcium and other cations
affects struvite purity, morphology, crystallinity, and particle size
(Hao et al., 2008; Le Corre et al., 2005). Matynia et al. (2013) re-
ported that other cations form hydroxide agglomerates on the
surface of struvite crystals, but these products were not observed in
Fig. 3. Phosphorus precipitation efficiency from poultry litter extracts for three
operating conditions: NaOH addition (NaOH dataset); NaOH and 13.6 mM EDTA
addition (NaOHþEDTA dataset); and, NaOH, 13.6 mM EDTA, and 13.6 mM MgCl2
addition (NaOHþEDTAþMg dataset). The poultry litter extract was generated from a
filtered 80 g/L PL-3 slurry at pH 4.3. To reach the pH setpoint, the appropriate volume
of 1 M NaOH was added to the poultry litter extract. The symbols and error bars
represent the means and standard deviations, respectively, of three replicate
experiments.
the SEM microphotographs of recovered products from this study.
Similarly, co-precipitation of amorphous calcium and magnesium
oxyhydroxides has been reported for waste streams with compa-
rable Ca2þ and Mg2þ concentrations (Crutchik and Garrido, 2011;
Pastor et al., 2008), but those solids were not identified in the
products recovered from poultry litter in this work.
Compositional analyses of the mixed products were confirmed
with ion chromatography, and the results are presented in Fig. 5.
The amount of NHþ 4 present in the recovered solids decreased at pH
10.5e11.0. Recall that the precipitation protocol involved aeration,
thereby increasing the favorability of NH3 off-gassing at higher pH.
The NH3(g) can be subsequently recovered using a sulfuric acid trap
(Ndegwa et al., 2009), but this operation was not included in the
present study. These conditions allowed a greater incorporation of
Kþ in the recovered products through precipitation of potassium
struvite. The NPK molar ratios for the recovered precipitates were
2.0:1.0:0.1 and 0.9:1.0:0.2 in the 8.5e9.0 and 10.5e11.0 pH ranges,
respectively. The precipitation pH and aeration time, therefore,
control the relative nitrogen-to-phosphorus ratio of the recovered
product, offering clear advantages in customized generation of
nutrient-balanced fertilizers without expensive systems for phos-
phorus separation, elution, and precipitation (Blaney et al., 2007).
3.3. Selective recovery of struvite and potassium struvite
Due to the lower agrochemical preference for calcium-based
phosphates, suppression of the calcium content in the recovered
product was investigated by adding EDTA to the poultry litter
extract. Because EDTA preferentially complexes with calcium (log
KCa-EDTA ¼ 10.65) over magnesium (log KMg-EDTA ¼ 8.62) (Benjamin,
2010), the addition of EDTA to the poultry litter slurry lowers the
free Ca2þ concentration and decreases precipitation of calcium-
based solids. In fact, Zhang et al. (2010) used EDTA to inhibit
24 U. Shashvatt et al. / Water Research 143 (2018) 19e27

Fig. 4. Morphology of precipitates obtained during nutrient recovery at the following conditions: NaOH addition to (a) pH 8.5e9.0 and (b) pH 10.5e11.0; 13.6 mM EDTA and
NaOH addition to (c) pH 8.5e9.0 and (d) pH 10.5e11.0; 13.6 mM EDTA, 13.6 mM MgCl2, and NaOH addition to (e) pH 8.5e9.0 and (f) pH 10.5e11.0. The extracts were generated
from 100 g/L PL-3 slurries by CO2 bubbling and HCl addition to pH 4.3. Precipitation pH was adjusted using a 1 M NaOH solution. The precipitates were washed with DI water three
times to remove soluble salts and freeze-dried before SEM analysis.

precipitation of calcium phosphates in dairy effluent, and Sabbag

Fig. 5. Inorganic composition (based on select ions) of the solids recovered at
different precipitation conditions. As the Ca2þ, Kþ, Mg2þ, NHþ
4 , and P(V) ions are
most important to the chemical structure of recovered solids, these species were
included here; note the corresponding phosphorus recoveries for these operating
conditions are reported in Fig. 3.
et al. (2014) used EDTA to preferentially precipitate struvite in
wastewater with high calcium levels. Here, a stoichiometric
amount of EDTA (1 mol EDTA per mol Ca) was added to the poultry
litter extracts to complex approximately 90% of the dissolved cal-
cium with minimal changes to the dissolved magnesium chemistry
(e.g., <10% of dissolved magnesium as EDTA-Mg). As shown in
Fig. 3, the inclusion of EDTA in the poultry litter extracts resulted in
P(V) recoveries that were 36% lower (averaged across the pH
8.0e11.0 conditions) due to inhibition of the calcium-phosphate
precipitation mechanism. These data suggest that Mg2þ is slightly
limiting in the EDTA-modified poultry litter slurries.
The composition of recovered products was fairly homogeneous
in the EDTA treatment scenario as evidenced in Fig. 4ced, which
highlights the absence of the large, irregular solids associated with
calcium phosphates. Increasing the precipitation pH from 8.5-9.0 to
10.5e11.0 produced crystals with a higher aspect ratio. The aspect
ratios of struvite crystals generated at pH 8.5e9.0 and 10.5e11.0
were calculated to be 2.9 (±0.62) and 5.5 (±1.7), respectively.
Mathew and Schroeder (1979) reported that substitution of NHþ 4
with Kþ produces minor structural changes, and so the observed
differences in aspect ratio may stem from the longer aeration or
mixing conditions used at higher pH. Ion chromatography analyses
 U. Shashvatt et al. / Water Research 143 (2018) 19e27
(Fig. 5) confirmed that more potassium was incorporated into the
needle-like structures that exhibited higher aspect ratios.
As the untreated poultry litter sources exhibited molar ratios of
0.9e1.1 mol Mg/mol P, complexation of calcium may result in
magnesium-limited conditions; therefore, concurrent addition of
EDTA and MgCl2 resulted in high recovery efficiencies that were
similar to the baseline NaOH scenario (Fig. 3). For example, the
NaOHþEDTAþMgCl2 treatment scheme resulted in 91.6 (±7.1)%
P(V) recovery at pH 8.9, which was comparable to the 96.3 (±1.7)%
recovery observed for NaOH only. Importantly, this operational
scheme generated a much more homogeneous product, as seen in
Fig. 4eef, and resulted in lower TOC content in the recovered
product (see Table S2 in the SI). These findings align with previous
results stemming from EDTA use in dairy effluent (Zhang et al.,
2010) and municipal wastewater (Sabbag et al., 2014). Although
the overall recovery changed, no major differences in solids
composition were observed for the NaOHþEDTA and
NaOHþEDTAþMgCl2 operating conditions (see compositional data
in Fig. 5). Thus, the combination of pH control and chemical addi-
tion was used to optimize not only recovery efficiency, but also the
NPK ratio of the recovered products.
3.4. Effect of slurry strength on P(V) extraction and precipitation
The effects of slurry strength on the phosphorus extraction and
precipitation efficiencies were tested at 4, 20, and 80 g/L using PL-3.
As expected, buffer intensity increased with increasing slurry
strength (Fig. S4 in the SI), thereby affecting the acid demand
during extraction. The phosphorus extraction efficiency during the
CO2 bubbling operation was highest for the 4 g/L loading and
consistently decreased at higher solids content (Fig. 6). Importantly,
these data showcase the ability of CO2(g) to significantly offset the
strong acid demand. CO2 bubbling achieved 88.2 (±5.2)%, 80.3
(±2.8)%, and 63.7 (±7.5)% phosphorus extraction for the 4, 20, and
80 g/L slurries, respectively. Additional CO2 dissolution, and lower
slurry pH, may be achieved in pressurized reactors, but the eco-
nomics and operational complexity of such reactors are expected to
limit translation to on-farm solutions. For high poultry litter solids
loading (i.e., greater than 100 g/L), mineral acid was required to
achieve extraction efficiencies greater than 70%. In those cases, HCl
was dosed until the pH was 4.5e5.5. The equivalents of acid
Fig. 6. Extraction and recovery efficiencies for low- (4 g/L), medium- (20 g/L), and
high- (80 g/L) strength PL-3 slurry conditions. Extraction of phosphorus from PL-3
involved CO2 bubbling and 1 M HCl addition to achieve pH 4.5. The nutrient-rich
extract was aerated and 1 M NaOH was added to reach pH 8.8. The columns and er-
ror bars represent the means and standard deviations, respectively, of three replicate
experiments.
25
required per gram of poultry litter remained consistent at 0.77
(±0.10) meq/g for all slurry strengths. Overall, the extraction effi-
ciencies were in the 76e90% range, indicating enhanced P(V)
extraction with the combined CO2 bubbling and strong acid addi-
tion scheme compared to strong acid alone (Fig. 2).
Unsurprisingly, the initial slurry strength impacted the con-
centrations of extracted species (e.g., P(V), Mg2þ, NHþ þ
4 , K , etc.) in
the precipitation reactor. For all three slurry strengths, the calcu-
lated saturation indices of hydroxyapatite, struvite, and potassium
struvite suggested the potential for spontaneous precipitation at
pH 8.5e9.0. The degree of super-saturation was directly correlated
to slurry strength; therefore, the 80 g/L poultry litter slurry
exhibited the most favorable potential for precipitation. For the 4 g/
L and 20 g/L poultry litter loadings, 3% and 45% P(V) precipitation
efficiencies were achieved at pH 8.8. In the 80 g/L slurry, over 94% of
the P(V) was precipitated at pH 8.8. Ronteltap et al. (2010) reported
that greater degrees of super-saturation negatively affect crystal
size. For that reason, a suite of precipitation studies were conducted
using extracts from 50, 100, and 200 g/L poultry litter slurries of PL-
3. No influence of poultry litter loading was observed with respect
to the size of recovered struvite particles (Fig. S5 in the SI). The
lengths of the recovered crystals from the 50, 100, and 200 g/L
poultry litter slurries were 107.9 (±21.7), 106.5 (±19.5), and 98.7
(±30.7) mm, respectively. The aspect ratios were also consistent,
ranging from 4.4 (±1.0) to 5.1 (±1.7). Based on these findings, the
optimal slurry strength was set to 100e200 g/L. Although higher
solids contents (e.g., greater than 200 g/L) are expected to be
chemically favorable, these conditions may negatively affect
pumping and mixing operations.
3.5. Sequencing batch phosphorus extraction and recovery
Slurry pH was the key operational parameter in the phosphorus
extraction and recovery stages. By maintaining optimal pH condi-
tions, providing adequate reaction times, and incorporating a solid-
liquid separation step, a combined system can be developed for
extension to continuous-flow or sequencing batch operation. An
offline kinetic study with three poultry litter loadings indicated
that a 20 min extraction at pH 4.5e5.5 with continuous mixing was
sufficient for phosphorus release (Fig. S6 in the SI).
A sequencing batch operation was conducted with 80 g/L of PL-
3, as documented in Fig. 7. The poultry litter slurry was mixed for
3 min and the pH equilibrated to 6.6 (±0.03). After 4 min of CO2
bubbling, the pH decreased to 6.0 (±0.1) and P(V) extraction was
68.5 (±5.2)%. The solution was then adjusted to pH 4.6 (±0.1)
through addition of 0.65 meq of acid (as HCl)/g poultry litter. The
acidified poultry litter slurry was mixed for 20 min to ensure
optimal P(V) extraction. The P(V) extraction efficiency was 78.0
(±6.7)%. After separating the solids, 0.20 meq of base (as NaOH)/g
poultry litter was dosed into the nutrient-rich extract raising the
pH to 6.6 (±0.03). Then, the solution was mixed for 2 min. A 10 min
aeration step did not significantly affect the pH, but did provide
nucleation sites for particle precipitation and growth (Mondal et al.,
2017). While a diffuser stone was employed here, the aeration
system can be optimized for on-farm systems to enable production
of finer bubbles that increase mass transfer involved with CO2
stripping reactions and, thereby, increase the overall effectiveness
of the aeration step. Following aeration, 0.24 meq of base (as
NaOH)/g poultry litter was added to raise the pH to 9.0 (±0.02), and
the solution was gently mixed for 8 min. The final precipitation
efficiency was 91.0 (±3.7)%. Overall, 71.0 (±8.0)% P(V) recovery was
achieved, and the dominant form of the recovered solids was
struvite. The complete run time for sequencing batch operation was
45 min, demonstrating the quick and efficient process chemistry.
26 U. Shashvatt et al. / Water Research 143 (2018) 19e27

Fig. 7. (a) Schematic of the process chemistry with numbered process steps; (b) P(V) and pH profiles during nutrient extraction and recovery for an 80 g/L PL-3 slurry; and,
(c) extraction and recovery efficiencies for each process step. The numbers in the x-axis of (c) refer to the time points labeled in (b). For pH adjustment, 1 M HCl and NaOH
solutions were employed. Solids were separated through centrifugation and filtration. Error bars represent the standard deviation of three replicate experiments.

3.6. Recycling process effluent 4. Conclusions

To reduce both water consumption and wastewater generation
during phosphorus recovery from poultry litter, a recycle scheme
was incorporated into the process chemistry. The liquid process
effluent from one cycle was used to generate the poultry litter
slurry in the next cycle. Table 2 reports the extraction and pre-
cipitation efficiencies, overall P(V) recovery, and effective water
usage for a three-cycle experiment at a solids loading of 100 g/L of
PL-3. The P(V) extraction and precipitation efficiencies were
67e73% and 97e99%, respectively, for all three cycles. Because
nutrients that are not precipitated remain in the system, the
overall recovery increased from cycle 1 to cycle 3. The cumulative
P(V) recovery was greater than 70%. The effective water usage was
calculated as the total water consumed over three cycles divided
by the total mass of poultry litter processed. At the end of three
cycles, the effective water consumption was approximately 4.4 L/
kg of poultry litter, compared to 10 L/kg for the no-recycle sce-
nario. From cycle 1 to cycle 3, the strong acid (HCl) and base
(NaOH) demands increased from 0.8 to 1.4 meq/g and 0.6e1.0
meq/g, respectively, presumably due to incremental increases in
DOC concentration. A ten-stage recycle experiment demonstrated
90% overall P(V) recovery with an effective water consumption of
only 2.3 L/kg (Table S3 in the SI).
Table 2
Extraction, precipitation, and recovery efficiencies, effective water use, and acid/
base demands (mean ± standard deviation; n ¼ 3) for a 3-stage recycle experiment
with 100 g/L PL-3.
Parameters Cycle 1 Cycle 2
This work demonstrated a sustainable technology for rapid
treatment and recovery of nutrients in poultry litter. Carbon diox-
ide bubbling enabled P(V) recoveries of 63e88% for poultry litter
slurries with less than 100 g/L. Strong acid was added to achieve
P(V) extraction efficiencies greater than 70% for waste slurries with
more than 100 g/L. The liquid process effluent was reused over a
number of treatment cycles to ensure that the nutrient recovery
process does not create a separate liability for farmers in the form of
excessive wastewater volumes. For a three-stage recycle scenario,
fresh water usage was reduced by 56%. The final, nutrient-enriched
liquid effluent may also serve as a useful fertilizer product.
Importantly, the process was highly effective, demonstrating over
70% phosphorus recovery and allowing selective production of
struvite and potassium struvite through the introduction of
calcium-complexing agents and exogenous magnesium. Overall,
the successful extraction and recovery of phosphorus from poultry
litter in the form of two valuable, slow-release fertilizer products
represents a sustainable alternative to natural phosphate rock
supplies that are being increasingly depleted.
Acknowledgements
This work was supported by the United States National Science
Foundation [CBET 1511667] and the Maryland Industrial Partner-
ships program [project #5428]. We also thank anonymous poultry
farmers for donating litter to this project.
Appendix A. Supplementary data
Cycle 3

Extraction a (%) 67.1 ± 6.1 72.7 ± 7.1 71.9 ± 11.3 Supplementary data related to this article can be found at
Precipitation b (%) 97.0 ± 1.4 98.1 ± 3.1 99.3 ± 0.62 https://doi.org/10.1016/j.watres.2018.06.035.
Recovery (%) 64.9 ± 5.1 71.4 ± 9.0 71.4 ± 10.8
Effective water usage (L/kg) 10.0 ± 0.0 5.8 ± 0.0 4.4 ± 0.10
Acid demand (meq/g) 0.8 ± 0.0 1.2 ± 0.0 1.4 ± 0.10 References
Base demand (meq/g) 0.6 ± 0.0 1.0 ± 0.0 1.0 ± 0.20
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