Plant Soil (2016) 401:93107

DOI 10.1007/s11104-015-2519-0

REGULAR ARTICLE

Pig slurry acidification, separation technology and thermal

conversion affect phosphorus availability in soil amended
with the derived solid fractions, chars or ashes
Wibke Christel & Sander Bruun & Jakob Magid &
Witold Kwapinski & Lars Stoumann Jensen

Received: 17 December 2014 / Accepted: 13 May 2015 / Published online: 24 May 2015
# Springer International Publishing Switzerland 2015

Abstract declining with time, indicating soil P fixing reactions.

Aims The aim was to study effects of slurry acidifica-
tion, separation technology and thermal processing on
the availability of P in soil amended with the solid
fraction of pig slurry.
Methods Acidified and non-acidified slurry were sepa-
rated using different technologies: screw press (SCR),
decanting centrifuge (DEC) and drainage after chemical
pretreatment (CHE). Solids and pyrolysed (400 C or
600 C, char) or combusted (625 C, ash) solids were
applied to two soils, with triple superphosphate (TSP) as
a reference. Soil P availability was determined over
12 weeks using diffusive gradients in thin films (DGT).
Results The initial availability of P from DEC and CHE
solids was similar to TSP in both soils. After 6 weeks no
significant difference was observed between DEC solids
and DEC chars. Acidification did not significantly affect
P availability in the solids-amended soils over time, but
it did affect P availability with the thermally processed
materials.
Conclusions Application of separated pig slurry solids
generally increased soil P availability initially, but
Responsible Editor: Tim S. George.
W. Christel : S. Bruun : J. Magid : L. S. Jensen (*)
Department for Plant and Environmental Sciences, University
of Copenhagen, Thorvaldsensvej 40, DK-1871 Frederiksberg
C, Denmark
e-mail: lsj@plen.ku.dk
W. Kwapinski
Carbolea Research Group, Department of Chemical and
Environmental Science, University of Limerick, Limerick,
Ireland
Chars and ashes on the other hand showed lower initial
P availability, but remained constant or increased slight-
ly with chars yielding P availability similar to solids
after 12 weeks.
Keywords Decanter centrifuge . Screw press . Slurry
flocculation . Pyrolysis . Combustion . Diffusive
gradients in thin films (DGT)
Introduction
Slurry separation is one management option for distribut-
ing and utilising the liquid and solid fraction of pig manure
in a more environmentally friendly way that is better suited
to plant demand for individual nutrients than the applica-
tion of unprocessed slurry. The separated solid fraction is
rich in particulate organic matter and nutrients, which may
precipitate during storage and be captured during floccu-
lation or be bound in particulate organic matter and mi-
crobial residues (Hjorth et al. 2010; Peters et al. 2011).
Slurry separation is used on many large-scale animal farms
in livestock-intensive regions across Europe, i.e., in
Catalonia, Brittany, Flanders and the Netherlands; in
Denmark around 3 % of all slurry is separated
(Birkmose, pers. comm.). The essential nutrient phospho-
rus (P) is of great interest, since recycling of the solid
fraction would reduce environmental issues associated
with surplus P on livestock-intensive farms and make
recipient farmers less dependent on mineral P fertiliser,
94
thereby contributing to a more sustainable use of this non-
renewable resource.
Slurry acidification is a treatment option that can be
used to minimise ammonia volatilisation in the animal
house and during storage, separation and field applica-
tion (Kai et al. 2008; Petersen et al. 2012). Acidification
affects the chemical and physical properties of the pig
slurry and the resulting fractions obtained by subsequent
slurry separation (Sommer et al. 2015; Hjorth et al.
2015). Slurry acidification technologies are currently
mainly used on livestock farms in Denmark due to very
strict ammonia emission regulations, whereas in other
European countries its application is highly scattered. In
2014, approximately 12 % of all animal slurry in
Denmark was acidified (Birkmose, pers. comm.), but
this proportion is expected to increase.
The physicochemical properties of the solid and liquid
fractions are also highly dependent on the separation tech-
nology used (Jrgensen and Jensen 2009). The perfor-
mance with respect to separation of the smallest particles
(<250 m or even <10 m) in particular is crucial for P
content in the dry-matter rich fraction (Masse et al. 2005;
Peters et al. 2011). Simple mechanical techniques are
usually rather inefficient at retaining the smallest particles
in the solid fraction, whereas more advanced slurry sepa-
ration techniques ensure a high P separation coefficient
(Kumaragamage et al. 2013; Popovic et al. 2012).
Besides energy production, thermal processing of the
solid fraction, such as pyrolysis, gasification and com-
bustion of the dried solids, has also been suggested as a
suitable way of enriching P in the product (Mller et al.
2007; Cantrell et al. 2008; Ro et al. 2009, 2010; Wnetrzak
et al. 2013), while also stabilising it for long-term storage
and transportation. However, the high temperatures dur-
ing processing have been shown to decrease the easily
available fraction of the contained P through changes in
the chars biochemical structure (Cantrell et al. 2012; Tsai
et al. 2012) or in the types of minerals present in the ashes
(Huang et al. 2011; Thygesen et al. 2011). Thermal
processing has so far mainly been employed with high
dry-matter manures such as poultry litter, with several
large-scale facilities in operation in the UK and the
Netherlands. However, with the current proliferation
across Europe of anaerobic digestion for biogas and
subsequent liquidsolid separation of the digestate, ther-
mal processing of solids is expected to increase.
It is not yet clear, however, whether further combined
treatments of manure products could potentially improve
their applicability. Most studies of different manure-
Plant Soil (2016) 401:93107
derived products and their potential use as a P-fertilising
soil amendment have investigated the effect of just one
slurry treatment option at a time: either acidification
(Roboredo et al. 2012), the separation technology used
(Kumaragamage et al. 2013), pyrolysis conditions (Tsai
et al. 2012) or combustion temperature (Thygesen et al.
2011). Based on extractions, these studies either charac-
terise P fractions in the resulting manure-derived products
alone or, if the change in P availability in soil over time has
been investigated at all, the discussion concerning interac-
tions with the soil after amendment has been limited to one
soil type only. Few studies on pig manure-derived mate-
rials have addressed the influence of soil properties
(Christel et al. 2014). However soil properties, i.e., the
mineral phase and presence of sorption sites, have also
been identified as key factors controlling P dynamics in
soils in a related study, using poultry manure as the
amendment (Waldrip-Dail et al. 2009). With such a
fragmented collection of results from greatly varying ma-
terials, methods and scales, it is difficult to draw a general
conclusion on the combined effect of the above-mentioned
slurry treatment processes.
The objective of the current study was to investigate
the combined effect of slurry acidification, separation
technology and thermal treatment (pyrolysis or combus-
tion) on P availability in soils after amendment with
various solid materials derived from pig slurry. Firstly,
the aim was to examine whether acidification prior to
slurry separation by different technologies had an im-
pact on the potential use of the respective solid fractions
as organic P fertiliser in two different soils and then test
whether the effect of acidification was preserved after
thermal processing of one of the solid fractions.
Materials and methods
Manure solids
Two pig slurries from fattening pigs were collected from a
research farm at the Grnhj Pig Trial Station in Karup,
Denmark in the spring of 2012: (I) untreated pig slurry and
(II) pig slurry that had been continuously acidified to
pH 5.5 in the animal house through the addition of
sulphuric acid (H2SO4). Both pig slurries were separated
at farm scale using three different separation technologies:
i) a screw press (SCR; Brger BS50, Germany), ii) a
decanter centrifuge (DEC; Pieralisi, Italy) and iii) chemical
pretreatment (CHE; flocculation using polymers),
Plant Soil (2016) 401:93107
followed by drainage on a filter band separator (AL-2
model 812P, Denmark; polymers: Praestol K133L and
K144L (Demols Inc., United States of America) for un-
treated and acidified slurry respectively). The solid frac-
tions were collected in plastic buckets, covered with a
tight-fitting lid and frozen to 18 C for storage within
3 days of sampling.
Shortly before experimental use, a large aliquot of
each solid fraction was defrosted and subsequently dried
at 80 C for water removal. The drying was necessary in
order to be able to weigh off a representative, but small
mass needed as amendment for soil incubation.
The origin and a detailed description of the slurries
and solid fractions (for abbreviations see Table 1), as
well as their (bio)chemical characterisation can be found
in Sommer et al. (2015). The water-extractable share of
total P was below 5 % of total P for the non-acidified
fresh solid fraction, whereas it ranged between 12 % and
29 % for the acidified solids (Sommer et al. 2015).
Pyrolysis and combustion of the manure solids
In the Bygholm Research Centre of Aarhus University
(Horsens, Denmark), the solid fractions from DEC-
separation (DEC- & DECacid-Solids) were dried by blow-
ing slightly preheated ambient air (<30 C) through a
0.25 m thick layer of fibre material until an approximate
gravimetrical water content of 13 % was attained.
Subsequently, the dried fractions were pelletised (JS
Trading ApS, Fredericia, Denmark). The pellets were
slowly pyrolised (heating rate 20 C min1) in a self-
constructed bench-periodic reactor of 1.5 L capacity in
the laboratories of the University of Limerick, Ireland. The
reactor was evacuated for oxygen at low temperatures in
the early heating phase. During pyrolysis, no air was able
to enter the reactor, but pyrolysis gases could escape. The
manure solid feedstock remained for one hour at a peak
temperature of 400 or 600 C, resulting in four different
char samples in total. Ash was produced from the same
materials combusting the pellets in a laboratory-scale fur-
nace (Lenton, United Kingdom) at 625 C until constant
mass, providing two different ash materials. Dry matter
loss during pyrolysis and combustion was determined and
the respective char yields and ash content are given in
Table 1. Finely ground aliquots (5070 mg) of the chars,
ashes and dried solids were digested in nitric acid (2.5 mL
69 % HNO3), hydrogen peroxide (1 mL 15 % H2O2) and
hydrofluoric acid (200 L 49 % HF) in a ModBlock
system (CPI International, The Netherlands).
95
Subsequently total P (Table 1) was analysed by inductively
coupled plasma optical emission spectrometry (ICP-OES,
Optima 5300 DV, Perkin Elmer, Ontario, Canada) using
the procedure described in detail by Hansen et al. (2009).
The water-extractable share of P in the DEC-Char600
was approximately 2 % of total P, whereas no P in DEC-
Ash was found to be extractable in water (1:60 solid:water
mass ratio, 16 h shaking). Based on the findings of Christel
et al. (2014), over 50 % of total P in the thermally
processed DEC-materials is extractable in citric acid.
Phosphorus fertiliser as the reference treatment
A commercially available granulated triple superphos-
phate (TSP, mainly Ca(H2PO4)2 H2O) fertiliser, with a
P content of 173 mg g1 (Table 1), was used as a
reference treatment and applied at the same target P
level (see below). Before soil amendment, the TSP
granules were also crushed and coarsely ground.
Soil properties
Based on the experience acquired from an earlier incuba-
tion study (Christel et al. 2014), two Danish agricultural
soils were selected for this incubation study that varied in
both texture and pH: (A) a sandy soil with a strongly acidic
pH and (B) a sandy loam with a neutral soil pH. The sandy
soil (A) was sampled from an arable field near the city of
Aarhus, Denmark (56 08 N, 9 59 E), while the loamy
soil (B) was collected from the long-term Nutrient
Depletion Trial (NDT) on the research farm of the
University of Copenhagen in Taastrup, Denmark (55
40 N, 12 17 E), from a plot that had not received any
P fertiliser since 1964, but had been continuously cropped
and had therefore reached a very low P status. Details on
the texture, pH and P availability of the sampled soils are
given in Table 2. After sampling from the 025 cm horizon
of the agricultural fields, the bulk soil samples were air-
dried and sieved (2 mm). Before soil application, the char
pellets were disintegrated by coarse grinding.
Incubation set-up
The aim was to use the same target P application rate
(Table 3) in all treatments (corresponding to ca. 38 kg P
ha1 if the materials were incorporated into the top 5 cm of
field soil with a bulk density of 1.3 g cm3). The respective
mass of treatment dry matter was mixed into 10.0 g of air-
dried soil, thoroughly mixed and subsequently moistened
96 Plant Soil (2016) 401:93107

Table 1 Phosphorus (P) content in the dry matter (DM) and yield DEC(acid)-Solids-derived char materials at the two pyrolysis tem-
(w/w% of feedstock DM, in italics) of the six solid slurry fractions peratures (400 and 600 C) and ash products after combustion
(3 control+3 acidified), separated by the given technology, and the (625 C), as well as P content in the reference mineral fertiliser

Samples Separation method Slurry treatment -Solids -Char400 -Char600 -Ash

drying pyrolysis pyrolysis combustion
80 C 400 C 600 C 625 C
mg P g1 DM1 mg P g1 DM1
yield (w/w% of DM)

SCR Screw press Control 7.6

DEC Decanter centrifuge Control 20.4 40.0 53.8 155
(56.2) (38.4) (13.0)
CHE Flocculation + drainage Control 20.1
SCRacid Screw press Acidified 5.1
DECacid Decanter centrifuge Acidified 8.1 17.6 21.4 89.6
(55.7) (35.7) (10.8)
CHEacid Flocculation + drainage Acidified 11.8
TSP Triple superphosphate (reference) 173

with purified water (MilliQ; filtered by Millipore, 18.2
M) to the desired water content for incubation. As al-
ready described in Christel et al. (2014), the gravimetrical
water content needed to obtain a moist, but still well-
aggregated and aerated soil was different for the two soils
due to the different textures of the soils: 16.5 w/w % for the
sandy soil and 19.0 w/w % for the sandy loam. Three
replicates were prepared for each type of sample. The
samples were incubated in darkness, partly covered by a
lid at room temperature (22 C3 C). Once a week,
gravimetrically-determined individual water loss was
compensated for by the addition of purified water.
All 12 different manure solids, char and ash materials
listed in Table 1 were incubated in the pH-neutral sandy
loam (B). For the sandy soil with low pH (A), the
number of amendments was reduced to six different
materials: all the treatments separated by the decanting
centrifuge (DEC & DECacid) plus the derived chars
(600 C pyrolysis temperature: DEC(acid)-Char600)
and ashes (DEC(acid)-Ash). Soil without any application
(CON) and soil with triple superphosphate (TSP) were
prepared for both soil types as reference treatments.
Soil phosphorus availability testing with the diffusive
gradient in thin films (DGT) technique
To determine changes in available P over time, the DGT
technique (e.g., Davison and Zhang 2012; Six et al.
2014) was applied. This method was chosen as it has
been proposed as a better predictor of plant response to
applied P in comparison to traditional soil P tests
(Mason et al. 2013; Six et al. 2013). Commercially
available-DGT devices (DGT Research Ltd.,
Lancaster, United Kingdom) were applied several times
during incubation. For each sampling time, three blank
DGT devices, which were placed in incubation con-
tainers without any soil or amendment, were included

Table 2 Characterisation of the soils (A & B) used for incubation

Soil Soil texture clay silt sand pH Olsen-Pa CDGTb

[w/w%] [w/w%] [w/w%] (in 0.01 M CaCl2) [mg P kg1 soil] [g PO4-P L1]

A sand 6.2 6.0 87.8 5.1 48.3 (4.0) 262.6 (26.3)

B sandy loam 16.0 17.0 67.0 7.2 9.8 (2.4) 39.2 (7.8)
a
average Olsen-P (Olsen et al., 1954) of the non-amended soil (n=3 for soil A, n=4 for soil B), standard deviation is given in parentheses
b
average CDGT of control treatment (non-amended soil) from all sampling times during the incubation period (n=15), standard deviation is
given in parentheses
Plant Soil (2016) 401:93107
in the analysis. Incubation sampling was performed
destructively over time. For all the treatments with solid
fractions separated by decanting centrifuge (DEC &
DECacid) and their derived char and ash, three DGTs
were applied five times during incubation: after 24 h
(Bweek 0^) and 1 week, 3, 6 and 12 weeks after set-up.
However, the number of DGT application times was
reduced for the other treatments: the soils amended with
manure fibre fractions (SCR(acid) & CHE(acid)) were
measured in weeks 0, 3 and 6 only. The control treat-
ments, soil without any amendment (CON) and soil with
TSP addition were sampled on all five occasions during
the incubation period.
One day before DGT application, the water con-
tent in the respective incubation cups had to be
increased to obtain a thin water film on the surface,
which is necessary to ensure good contact and hence
diffusive transport of P between the soil solution
phase and the DGT device. As described in a pre-
vious study (Christel et al. 2014), the gravimetrical
water content was therefore increased to 23.0 % for
the sandy soil and 27.0 % for the sandy loam during
DGT application. These moisture levels were chosen
to secure sufficiently high water contents near satu-
ration (>80 % of water-holding capacity) in all treat-
ments, even after amendment of char or ash mate-
rials, in order to facilitate proper application of the
DGT method (Hooda et al. 1999). Subsequently, the
soil was mixed and some soil paste was directly
smeared onto the filter layer of the DGT device,
before carefully pressing the DGT device onto the
rest of the soil in the incubation container. After
24 h application time at room temperature, the
C DGT soil amended with P sourceC DGT control soil
C DGT
C DGT index
Ptotal
total P added
pH measurements in soil-amendment mix
After removing the DGT, 0.01 M CaCl2 solution was
added to the wet soil mix to reach a solidliquid ratio of
1:2.5. After equilibration for a minimum of 30 min, the
pH was measured in the supernatant using a pH meter
(PHM 210 lab pH meter, Radiometer, Denmark).
97
DGT devices were removed, rinsed on the filter
surface with MilliQ-water and opened. The iron-
containing binding gel was put into 1.5 mL of 1
molar nitric acid (HNO3) for elution. After another
minimum period of 24 h, the gel was removed from
the acid and 0.5 mL of the acid was diluted with
4.5 mL purified water (MilliQ) at a ratio of 1:10.
Samples were stored refrigerated (5 C) before PO4-
P analysis on a Flow Injection Analyser (FIAstar
5000, FOSS, Denmark), connected to an auto-
sampler (5027, FOSS, Denmark). All P captured in
the binding gel was assumed to be eluted in nitric
acid and therefore an elution factor of 1.0 (Christel
et al., unpublished results) was used for the calcula-
tion of P mass recovered in the eluted binding gel.
The concentration of P in the soil solution at the
interface between the DGT filter and soil matrix
(CDGT) was calculated from the P mass captured in
the DGT binding gel and Ficks law of diffusion
(Zhang et al. 1998). The diffusion coefficient for
phosphate in the DGT gel at 22 C (D = 5.57
106 cm2 s1) was provided by the DGT supplier
(DGT Research Ltd., Lancaster, United Kingdom).
As the CDGT of the two unamended soils (controls)
were very different (Table 2), they were subtracted from
the CDGT from the respective P-treated soil in order to
present the resulting increase in P availability only. By
dividing by the amount of total P applied, the slight
deviations from the target P amendment for the various
treatments (Table 3) were also taken into consideration.
The P-fertilising effect of the soil amendment is there-
fore expressed as absolute increase in CDGT per P added
as CDGT-index (Eq. 1):
 
g PO4 P
L
  1
mg P
kg soil
Statistics
Linear models were used to carry out the analysis of
variances (ANOVA) to evaluate the treatment effects on
the CDGT-index and pH, where soil, acidification,
separation technology, and type as well as temperature
of thermal treatment were considered as discrete
98
Table 3 P application rate in comparison to the anticipated 59 mg
P kg1 soil1 (see Table 1 for abbreviations)
Treatment -Solids -Char400 -Char600
mg P kg1 soil1
SCR 52
DEC 55 61 56
CHE 60
SCRacid 51
DECacid 63 77 60
CHEacid 61
TSP 59
variables (factors), while incubation time was a quanti-
tative variable. Additionally, the effect of the treatment,
i.e., type of amendment, on the CDGT-index and pH
was tested in a one-way ANOVA for each sampling time
and soil separately. For multiple comparisons, the Tukey
test was used. For any statistical differences to be re-
ferred to as significant in the text, the p-value had to be
below 0.05. All data were analysed using the statistical
software R (Version 3.0.1, R Development Core Team
2011).
Results
CDGT-index
The increase in P availability (expressed as CDGT-in-
dex, Eq. 1) in the amended sandy soil A was generally
around up to four times greater (Fig. 1-A1 and A2)
compared to the amended sandy loam B (Fig. 1-B1 and
B2) during the experimental period. The effect of the soil
as a discrete variable was also found to be highly signif-
icant in the ANOVA of the linear model (P<0.001). All
amendments resulted in a positive CDGT-index, al-
though for some weeks it was not statistically significant-
ly different from 0 for all treatments (especially DECacid-
Char600 and Ash in both soils).
Over time, very different trends in the CDGT-index
for all DEC-derived materials were observed. The ma-
nure solids and the TSP had a higher initial CDGT-
index, but decreased continuously during the initial
incubation phase, stabilising after 3 to 6 weeks irrespec-
tive of soil type. The thermally processed materials
resulted in a fairly stable CDGT-index over the whole
incubation period. Accordingly, both time and the
Plant Soil (2016) 401:93107
interaction of time with thermal treatment were found
to be significant factors in the statistical models for the
-Ash two soils. However, as thermal treatment in itself also
had a significant effect on the CDGT-index, the in-
crease in P availability after char or ash applications
was lower than after treatment with solids or TSP, espe-
54
cially at the beginning of the incubation.
When comparing the individual DEC treatments, all
materials derived from the non-acidified fraction (DEC-
76 Solids/-Char600/-Ash), the acidified solids (DECacid-
Solids) and TSP increased the CDGT-index significant-
ly throughout the whole incubation period compared to
the unamended sandy soil A. For the loamy soil B, only
the DEC-Solids, the DEC(acid)-Char400, DEC-Char600
and TSP resulted in a significant increase in the CDGT-
index in the period from week 1 to week 12. At the
majority of sampling times (weeks 1, 3 and 12), DEC-
Ash significantly increased CDGT-index, but compa-
rably large standard deviations in week 6 caused the
increasing effect to be statistically insignificant.
With slurry acidification, a lower CDGT-index of
the DECacid-Solids and all the materials derived from it
was generally observed, compared to the non-acidified
counterparts (DEC(acid)-Solids in week 3 and -Char400
treatments week 6 in soil B being the only exceptions).
The tendency of lower CDGT-index for materials de-
rived from acidified slurry was only statistically signif-
icant in some cases (DEC(acid)-Solids in week 1 in both
soils, DEC(acid)-Char400 in week 3 in soil B, DEC(acid)-
Char600 in weeks 1, 6 and 12 in soil A, DEC(acid)-Ash
in weeks 1, 3 and 12 in both soils). For the solids,
separated by SCR or CHE however, the CDGT-index
was usually higher for the acidified solids compared to
the non-acidified counterparts. This tendency, however,
was only statistically significant for CHE(acid)-Solids in
weeks 3 and 6. Acidification and its interaction with
time were also found to have a significant effect on the
CDGT-index in both soils in the statistical model. In
soil B, additional interactions were identified with the
factor separation technology.
With respect to thermal conversion of the manure
solids, no significant differences were observed in
CDGT-index between the -Char600 and -Ash-treat-
ments, independent of soil type or slurry acidification.
In the second half of the incubation period (weeks 6
12), the CDGT-index after addition of DEC(acid)-Solids
and DEC-Char400 (only amended to soil B) and
-Char600 was even higher than or not significantly
different from TSP amendment in both soils.
Plant Soil (2016) 401:93107
Fig. 1 Increase in P CDGT (relative to the unamended control soil)
over the incubation period relative to the amendment of total P
(CDGT-index) in the form of the manure fraction products (solids,
chars, ashes) to the (A) sandy soil (pH~5) and the (B) sandy loam
(pH~7): the manure solids and TSP treatments are shown on the left
The manure solids, separated by the SCR or CHE
technique, also showed a generally decreasing trend
of the CDGT-index within the first 6 weeks of the
incubation (see Fig. 1-B1). The factor separation
technology, also in interaction with time or thermal
processing, was found to have a significant effect on
the CDGT-index in the linear model for soil B. The
CDGT-index after amendment of SCR(acid)- and
CHE(acid)-Solids was generally in the same range as
the DEC(acid)-Solids. However, the CDGT-index af-
ter amendment of the acidified fraction after CHE
separation (CHEacid-Solids) was not significantly
lower, but rather at the same level or even higher
compared to the DEC(acid)-Solids. On the other hand,
the amendment of the CHE- and SCR(acid)-Solids
resulted in a lower CDGT-index in comparison to
the DEC(acid)-Solids-treatments (insignificant).
99
(A1, B1), all the chars and ashes are shown on the right (A2, B2).
Only DEC(acid)-Solids, Char600 and -Ash were amended to the
sandy soil (A). Note the different y-axis scaling for the two soils.
Error bars represent the standard deviation of the mean (n=3). For
calculation refer to Eq. 1; for treatment abbreviations see Table 1
pH of the amended soils during incubation
Irrespective of soil type or treatment, a decrease in soil
pH was observed within the first few weeks of incuba-
tion (Fig. 2) and time was also identified as the factor in
the linear models having the most significant effect on
soil pH. With respect to the effect of soil amendment on
pH, no change was observed after amendment with TSP
compared to the non-amended control. In contrast, all
manure-derived treatments caused the pH to rise in both
soils A and B, but there were no consistent, statistically
significant differences between the manure-derived
amendments. In soil A, only the following treatments
had a significantly higher pH at the given times: DEC-
Solids and DEC-Char600 in week 0, DEC-Solids in
week 1 as well as DEC-Solids, DECacid-Char600 and
DECacid-Ash in week 3.
100
Fig. 2 Soil pH (in 0.01CaCl2) after amendment of the manure
materials to the (A) sandy soil and the (B) sandy loam: the manure
solids and TSP treatments are shown on the left (A1, B1), all DEC-
derived chars and ashes are shown on the right (A2, B2). The pH
of the unamended control soil is displayed in all figures as the
For the sandy soil A (Fig. 2-A1 and A2), soil pH
stabilised after 6 weeks incubation at approximately 4.7
for the unamended control treatment, compared to a pH of
5.1 initially (week 0). This drop in pH could possibly be an
effect of nitrification, as the soil had not been pre-incubat-
ed. Initially the pH in soil amended with materials from
acidified slurry was (insignificantly) lower, but this acidi-
fication effect disappeared over time (a significant effect of
acidification in interaction with time in the statistical mod-
el). In weeks 6 and 12, no significant pH differences could
be determined in soil A.
The pH of the control treatment of the loamy soil B
(Fig. 2-B1 and B2) decreased by approximately 0.7 pH
units within the first 3 weeks, stabilising at around
pH 6.5. The only exceptions to the general liming effect
of the manure-derived materials were the treatments
CHEacid-Solids in weeks 3 and 6, as well as SCR-
Plant Soil (2016) 401:93107
reference. Only DEC(acid)-Solids, Char600 and Ash were
amended to the sandy soil (A). Note the different y-axis scaling
for the two soils. Error bars represent the standard deviation of the
mean (n=3). For treatment abbreviations see Table 1
Solids in week 3 (significant effect of the factor separa-
tion technology and acidification in the statistical mod-
el). After 12 weeks incubation, only the DEC(acid)-
Char600 treatments were able to increase soil pH sig-
nificantly, compared to the control and TSP treatment in
soil B.
Discussion
Soil phosphorus availability testing by the DGT
technique
In this study changes in soil available P over time was
quantified by the DGT technique (Davison and Zhang
2012) as a proxy for plant P availability, based on a
number of recent studies. The review by Degryse et al.
Plant Soil (2016) 401:93107
(2009) showed conclusively that DGT performs as well
as, or better than, batch extractions as a soil P availabil-
ity test, if diffusion, and not mass flow or active P
solubilisation such as the exudation of protons or car-
boxylate anions, is controlling nutrient supply.
Furthermore, the ability of the DGT method to predict
soil P availability and plant uptake has been evaluated in
a number of recent studies. DGT was a better predictor
than extraction (Olsen P, water soluble) and resin tech-
niques of relative yield P response of tomato (Menzies
et al. 2005), wheat (Mason et al. 2010) and maize (Six
et al. 2013, 2014; Santner et al. 2015), but not of wetland
rice (Six et al. 2013) and of P uptake by barley (Tandy
et al. 2011). It has also been shown by isotope dilution
studies that the DGT technique samples the soil P frac-
tion which is accessible to plants, since the specific
activity of plant and DGT P were found to be not
significantly different in most soils, while the specific
activity of soil extracts differed significantly from that of
plant P, indicating that extracts only partly measure the
soil P that is plant accessible (Mason et al. 2013; Six
et al. 2012).
However, in order to validate whether our time
courses of CDGT are valid as index for plant P availabil-
ity, plant growth trials would have to be performed, but
such data are not present in the current study. However,
we have good indications that C DGT is valid for
predicting plant P availability from a yet unpublished
study from our group (Lemming, pers. comm.) where
we tested how thermal drying of sewage sludge affected
phosphorus availability, applying the same DGT ap-
proach as in the current study, but also including a pot
trial with barley. In this study the plant P uptake clearly
confirmed both the DGT ranking but also the propor-
tional P availability level of amendments.
Effect of time during incubation
As already reported in a previous study (Christel et al.
2014), the temporal pattern of P availability after applica-
tion of the dried solids differed from thermally processed
fractions. The pronounced increase in P availability after
amendment with the solid fractions was in accordance
with a number of other studies, in which soil was amended
with various manure types (poultry, cattle, goat and pig)
(Reddy et al. 1999; He et al. 2006; Gichangi et al. 2009;
Waldrip-Dail et al. 2009; Roboredo et al. 2012). The
authors investigated the resulting change in P availability
by studying P in different fractionation classes in the
101
amended soils. In these studies (a modified) Hedley frac-
tionation (Hedley et al. 1982) was used to detect changes
in inorganic and organic P pools of decreasing lability. The
water-extractable inorganic P, which was expected to be
correlated with CDGT to some extent (Christel et al. 2014),
decreased in all the above-mentioned studies in the first
few weeks after soil incorporation. These results are in
agreement with the decrease in P availability after amend-
ment of the manure solids and the TSP observed within the
first 3 weeks in the current study. Several studies have
observed a reduced P adsorption after the addition of an
organic P source (Ohno and Crannell 1996; Reddy et al.
1999), whereas no such effect on P sorption in soil could
be observed after TSP addition (Nziguheba et al. 1998),
which highlights the relevance of the co-applied organic
matter. Therefore the initial CDGT-index values for the
TSP treatment may well be lower than for manure solids.
Other than abiotic mechanisms, which will be discussed in
more detail in the following section about the effect of soil
type, immobilisation of labile P in soil microbial biomass
may contribute to reducing the easily extractable P in the
initial incubation phase. Gichangi et al. (2009) found an
increase in microbial biomass P within the first 4 weeks of
application of goat manure with or without TSP amend-
ment, followed by a decline. After the addition of other
organic P sources (compost or plant residues), mainly
labile and non-labile organic P was formed during 8 weeks
of soil incubation, whereas added labile inorganic P
(KH2PO4) was primarily converted into non-labile inor-
ganic P (Malik et al. 2012). Consequently Malik et al.
(2012) conclude that highly concentrated, organic P
sources may release P slowly over time due to the stimu-
lated formation of organic P forms in soils. Roboredo et al.
(2012) also indicate a (re-)mineralisation of intermediately
immobilised P after a total of 26 weeks incubation, as P
speciation according to their modified Hedley fraction-
ation did not differ significantly between the first and final
sampling. However, the results of the present study did not
suggest a return to the high initial level of P availability
caused by the addition of the manure solid fractions, but
then the incubation duration was also less than half as long
(12 weeks). Nevertheless, the high initial availability might
have been due to a high proportion of easily available P
(Christel et al. 2014), which caused a pattern of P avail-
ability similar to the pattern observed after amendment of
TSP.
In contrast to the amendment of soil with manure
solids or TSP, no generally valid effect of time was
observed in the case of the thermally-processed
102
treatments. Their constant, but in all cases positive effect
on P availability in the amended soils indicates that they
may have potential as slow-release P fertilisers.
Effect of soil
Most studies in which organic P fertilisers have been
incubated over a comparably long period have only used
one soil type (e.g. Nziguheba et al. 1998; Reddy et al.
1999; Gichangi et al. 2009; Malik et al. 2012; Roboredo
et al. 2012), most of them being rather depleted in P.
Waldrip-Dail et al. (2009) incorporated poultry manure
into two soils, but they did not considerably differ in
either texture or pH. He et al. (2006) added dairy manure
and inorganic fertiliser to two soils where the main
difference was the silt content, making their set-up not
directly comparable with the present studys. It is gen-
erally accepted that P availability after amendment to
soil is governed by abiotic and biotic mechanisms, the
most predominant being adsorption to, desorption from
and occlusion in soil particles, precipitation as well as
dissolution, and mobilisation by or immobilisation in
soil microorganisms (Barrow 1983; Hansen et al. 1999;
Frossard et al. 2000). The considerably higher clay
content in the loamy soil B, as well as its history of P
depletion, were expected to result in a higher adsorption
to the greater number of (non-occupied) P-binding sites
in the loamy soil B compared to the sandy soil A. Reddy
et al. (1999) assigned low P adsorption to repeated
application of manure P, which in the current study
might only be relevant for the conventionally managed
soil A. A similar pattern of higher P availability from the
low pH, sandy soil A after amendment of a comparable
set of decanter centrifuge-separated dried solid samples
and derived char and ash has already been reported by
Christel et al. (2014), in which the comparable manure-
derived amendments with different extraction methods
were also characterised. A high extractability of P in a
weak organic acid (2 % citric acid), even for the
thermally-processed treatments, might be another rea-
son for the proportionally more pronounced increase in
the CDGT-index in soil A, which had an acidic pH,
even after the addition of treatments, increasing the pH
by approximately 0.5 pH-units. Undoubtedly, further
studies are needed with a larger number of soil types,
varying in texture, organic matter content, management
practices and under more natural conditions, in order to
investigate the effect of soil type on P availability from
(organic) amendments.
Plant Soil (2016) 401:93107
Effect of thermal processing
The temperature-dependent total P contents of all ther-
mally processed materials derived from non-acidified
manure were consistent with values available in litera-
ture (Mller et al. 2007; Huang et al. 2011; Cantrell et al.
2012; Azuara et al. 2013). The char yields were in very
good agreement with the respective char yield at 400
and 600 C reported in these studies, whereas the ash
yield was slightly lower (Christel et al. 2014), which can
be assigned to the much longer combustion time in this
present study.
In agreement with earlier findings (Christel et al.
2014), a general decrease in P availability was observed,
especially shortly after soil incorporation, with increas-
ing Bintensity^ of thermal processing of the solids after
separation, even though this trend was neither consistent
nor statistically significant in all cases. Thermal process-
ing to produce chars and ashes has been reported to
decrease the easily available P fraction in both
products. During combustion of pig manure solids,
Mller et al. (2007) and Thygesen et al. (2011) have
shown that the formation of highly insoluble apatite
minerals and similar compounds decreases availability.
The reason for decreased P availability after pig manure
pyrolysis has been assigned to changes in biochemical
composition, dominated by more aromatic structures
with increasing pyrolysis temperature (Cao et al. 2011;
Tsai et al. 2012; Cantrell et al. 2012). During
carbonisation, either occlusion of inorganic phosphates
in or condensation of organic P compounds (Uchimiya
and Hiradate 2014) into the increasingly complex char
molecule structure reduces the availability of P. The
importance of the processing temperature, both during
combustion and pyrolysis, has previously been
discussed in more detail (Christel et al. 2014).
There was no significant difference in the CDGT-
index between the soils amended with char and ash and
processed at 600 C. It may therefore be concluded that
availability of oxygen during thermal treatment did not
affect the P availability from the final char and ash
products, although the alterations in chemical structure
and P speciation, occurring during pyrolysis or combus-
tion, may be very different. This observation is only
valid, however, for a thermal processing temperature
of 600 C and would require further testing before
generalisation. The observation that the CDGT-index
was generally higher after amendment of DEC-char
pyrolised at 400 C than after treatment at 600 C
Plant Soil (2016) 401:93107
supported the relevance of the choice of temperature
during thermal processing. Nevertheless, as both the
effect of pyrolysis and pyrolysis temperature disap-
peared in weeks 6 and 12, when the CDGT-index was
not significantly lower after amendment of any DEC-
Char compared to DEC-Solids or TSP, it can be con-
cluded that (low-temperature) pyrolysis will not reduce
the suitability of manure-derived char as a slow-release
P fertiliser compared with the raw manure solids. Apart
from the numerous, mainly soil physical and chemical
benefits of char application (e.g., Lehmann et al. 2006;
Atkinson et al. 2010; Spokas et al. 2012), it still remains
to be investigated whether manure-derived char addition
stimulates the microbial turnover of P as much as (fresh)
manure application, as discussed earlier. Whereas char
may provide a habitat for soil microbes (Atkinson et al.
2010) and hence favour their activity close to the
amendment, the mineral composition of ash and hence
its salinity may inhibit microbial activity close to it
(Nayak et al. 2014). Low-temperature chars in particu-
lar, which have not been completely pyrolised, may also
be partly mineralised (Bruun et al. 2011). Regarding the
decrease in P adsorption after organic P source addition
already described, a comparable interaction has already
been observed in a controlled watery solution system
containing rice-straw biochar and ferrihydrite (Cui et al.
2011). Moreover, Uchimiya et al. (2013) report the
release of considerable amounts of dissolved organic
carbon (DOC) from low-temperature chars, which ac-
cording to Ohno and Crannell (1996) are expected to
decrease P sorption in soil and hence provide more
available P. Nevertheless, these assumptions should be
subjected to further studies.
Effect of slurry acidification
There are a number of explanations for the lower
CDGT-index of all materials derived from acidified
manure compared to their respective non-acidified
counterparts. Where the soil was amended with the
manure solid fractions, the decrease in P availability
can be assigned to a higher proportion of organic P after
acidification. As reported by Sommer et al. (2015),
acidification causes a significant increase in dissolved
ortho-phosphate (ortho-P) in pig slurry. Dissolution of
occluded P and Calcium-associated P will transfer more
P into the liquid slurry phase, when pH is decreased to
5.5 (Hjorth et al. 2010; Waldrip et al. 2011).
Consequently a higher total P content is found in the
103
liquid fraction after separation of acidified slurry, where-
as the solid fraction contains less total P, and the P that is
retained is likely to be the organic and insoluble inor-
ganic forms (Sommer et al. 2015). However, due to a
considerable moisture content in the separated solid
fraction (67 % in DEC-Solids vs. 88 % in CHEacid-
Solids, wet-weight-based), the dissolved ortho-P-share
of total P is also higher in the solid fraction of acidified
manure (Sommer et al. 2015). Hence, if a constant rate
of total P is applied, a higher P availability from the
acidified solid fraction would be expected, which is in
line with the present studys findings for the solid frac-
tions after SCR or CHE-separation, but not for DEC-
separated solid fractions. One possible reason for the
opposite trend of the CDGT-index of DEC-Solids be-
ing greater than that of DECacid-Solids might be a sig-
nificant increase in particle size in the acidified slurry
(Hjorth et al. 2015), which facilitated the separation
process, but also resulted in a coarser solid fraction with
lower P content. With a lower mineralisation rate of
larger particles (Ambus and Jensen 1997), less P would
become available after soil incorporation of the organic
matter in the short term. Moreover the application of
acidified (cattle) slurry has been shown to decrease
microbial activity with respect to soil respiration, nitri-
fication and microbial biomass-C (Fangueiro et al.
2013). Based on the change in P speciation of solid
pig slurry fractions, either acidified prior to separation
or non-acidified, Roboredo et al. (2012) conclude that
acidification might have inhibited P immobilisation, but
not mineralisation, which is observed to occur at a faster
rate in soils amended with acidified slurry fractions.
This is in line with the present studys findings that after
6 weeks of incubation no significant effect of acidifica-
tion could still be observed in the loamy soil B, suggest-
ing that in the long run, after adaptation of the microbial
community to the lower pH and coarser substrate, slurry
acidification did not impede the P availability in soils
amended with manure solid fractions.
The effect of slurry acidification on P availability
from the derived thermally-processed materials, chars
and ashes has, to the authors knowledge, not been
investigated before. In the great majority of materials
investigated here, the CDGT-index after amendment
with ash or char derived from acidified slurry was lower
than that derived from non-acidified slurry. A plausible
reason could be that the physical properties of the feed-
stock material were conserved during pyrolysis (e.g.,
Downie et al. 2009) and consequently the chars derived
104
from acidified slurry had a larger particle size, which
could impede P mineralisation, as already discussed
before. However, this argument would not hold true in
the case of full combustion of the manure solids to
ashes. Nevertheless, the DECacid-Ashes showed a sig-
nificantly lower CDGT-index than the DEC-Ash in
both soils at most sampling times. In order to investigate
the effect of acidification on the physicochemical struc-
tures of the derived chars and the mineral speciation of P
in the ashes, further studies on the chemical speciation
and physical structure of the chars and ashes would be
needed.
Effect of slurry separation technology
Although not always statistically significant, higher
CDGT-indices were generally observed for the treat-
ments derived from the more efficient separation tech-
niques DEC and CHE, compared to the simple mechan-
ical SCR technology. Since P is mostly bound in the
smaller slurry particulate matter and DEC and CHE are
more efficient in separating the small particles into the
solid fraction (Peters et al. 2011; Popovic et al. 2012),
the P availability could potentially be higher as more P
could desorb from the larger specific surface area of the
small particles. Moreover, Kumaragamage et al. (2013)
have documented that not only total P removal, but also
the transfer of the most labile P fractions into the solid
fraction is improved when the slurry is chemically treat-
ed with flocculating polymers. Consequently the pro-
portion of easily soluble P is higher in the solid fractions
with smaller particle sizes. In a comparison of five
different separation techniques, including simple
passive and more advanced active separation
techniques, Fangueiro et al. (2014) did not observe a
significant effect on carbon or nitrogen dynamics during
soil incubation. Consequently the slurry separation tech-
nology would not be expected to have a major effect on
microbial P turnover either, but this hypothesis should
be subjected to further studies. Generally, the extent of
abiotic and biotic processes governing P dynamics in
soil after amendment of manure solids, char and ash
should be addressed in future studies.
pH effects on P availability in the amended soils
As the amendment of all manure-derived materials
caused a change in soil pH, the observed increase in P
availability could not be attributed solely to a release of
Plant Soil (2016) 401:93107
P from the added P-rich materials. Especially in the
acidic sandy soil A, the observed pH increase would
be expected to have an impact on the lability of native
soil P-pools. Consequently, P bound to sesquioxides
present in the soil would be likely to be mobilised due
to the liming effect of the amendment addition.
Generally, a decreasing trend in soil pH was observed
over the incubation period, not only for the amended
soils, but also the unamended control treatments. This
phenomenon could most likely be attributed to the fact
that the soils had not been pre-incubated before the start
of the experiment, and hence the physical disturbance
during mixing as well as the re-wetting resulted in a
mineralisation of both soil organic matter (in case of the
control soils) and the organic compounds in the respec-
tive amendments, with oxidation of C, S and N (i.e.,
nitrification of ammonium in amendments) releasing
protons. Furthermore, some of the acidified solids
(SCRacid and CHEacid) also produced a lower pH than
their non-acidified counterparts. Therefore the decrease
in soil P availability over time could also be attributed to
(re-)fixation of soil-borne P or P introduced with the
amendment. However, as soil pH after amendment of
various thermally-treated materials did not differ signif-
icantly, but great differences in resulting P availability
were still observed, the pH effect could not be the only
governing factor for P availability in the amended soils.
Moreover, (local) pH effects favouring P release from
fertiliser (pellets) are in any case one of the modes of
operation of mineral fertiliser (such as TSP).
Consequently, it is from a plant nutritional perspective
only of minor importance whether the increase in soil
P availability is caused by the release of P from a
fertilising product or by other co-occurring effects, such
as induced pH changes in the soil.
Conclusions
Overall, the application of the separated solid fractions
of pig slurry or TSP increased soil P availability in the
amended soils to a similar extent. However, within the
first three to 6 weeks after soil amendment, P availabil-
ity decreased substantially for both solids and TSP. The
highest P availability was found after soil amendment
with non-acidified DEC-solids, while P availability in
soils amended with the corresponding acidified DEC
solids (DEC acid -Solids) was lower in both soils.
However, from this study it cannot be concluded
Plant Soil (2016) 401:93107
whether this difference was caused by the difference in P
release from the solids or by the difference in soil pH
created by the acidified and non-acidified solids.
With pyrolysis or combustion of the solids, increased
availability of P was still found in both soils when
amended with the char or ash produced from slurry
solids, although thermal treatment generally decreased
initial P availability, and it was lowest for the ashes and
chars produced from acidified solids. No explicit change
over time in P availability from these chars or ashes was
observed and, after 6 weeks of soil incubation, the lower
availability of P compared with the dried solids and
TSP-amended soils were no longer significant. Further
studies on the chemical speciation and physical structure
of the chars and ashes are needed in order to understand
the effect of slurry acidification prior to thermal
treatment.
Acknowledgments The authors would like to thank their col-
leagues from the CLEANWASTE project, especially Sven G.
Sommer, Maibritt Hjorth and Rikke Jensen, for their helpful
assistance during sampling, as well as Anja H. Iv, Ea J. Larsen,
Lena A. Byrgesen, Lene Vigh and Thomas H. Hansen for their
support with sample analysis. Special thanks as well to Renata
Wnetrzak at the University of Limerick for thermal processing of
the solid fractions and Kun Zhu for help with the statistical
analysis. The authors would also like to thank Simon Mundus
and Frederik van der Bom for the provision of one of the soils and
its texture and Olsen-P analysis. This study was conducted as part
of the BCLEANWASTE^ research project (grant number: 2104-
09-0056), funded by the Danish Council for Strategic Research.
References
Ambus P, Jensen ES (1997) Nitrogen mineralization and denitri-
fication as influenced by crop residue particle size. Plant Soil
197:261270
Atkinson C, Fitzgerald J, Hipps N (2010) Potential mechanisms
for achieving agricultural benefits from biochar application to
temperate soils: a review. Plant Soil:118
Azuara M, Kersten SR, Kootstra AMJ (2013) Recycling phospho-
rus by fast pyrolysis of pig manure: concentration and ex-
traction of phosphorus combined with formation of value-
added pyrolysis products. Biomass Bioenergy 49:171180
Barrow N (1983) A mechanistic model for describing the sorption
and desorption of phosphate by soil. J Soil Sci 34:733750
Bruun EW, Hauggaard-Nielsen H, Ibrahim N, Egsgaard H, Ambus
P, Jensen PA, Dam-Johansen K (2011) Influence of fast
pyrolysis temperature on biochar labile fraction and short-
term carbon loss in a loamy soil. Biomass Bioenergy 35:
11821189
Cantrell KB, Hunt PG, Uchimiya M, Novak JM, Ro KS (2012)
Impact of pyrolysis temperature and manure source on
105
physicochemical characteristics of biochar. Bioresour
Technol 107:419428
Cantrell KB, Ducey T, Ro KS, Hunt PG (2008) Livestock waste-
to-bioenergy generation opportunities. Bioresour Technol 99:
79417953
Cao X, Ro KS, Chappell M, Li Y, Mao J (2011) Chemical
structures of swine-manure chars produced under different
carbonization conditions investigated by advanced solid-state
13C nuclear magnetic resonance (NMR) spectroscopy.
Energy Fuel 25:388397
Christel W, Bruun S, Magid J, Jensen LS (2014) Phosphorus
availability from the solid fraction of pig slurry is altered by
composting or thermal treatment. Bioresour Technol 169:
543551
Cui H, Wang MK, Fu M, Ci E (2011) Enhancing phosphorus
availability in phosphorus-fertilized zones by reducing phos-
phate adsorbed on ferrihydrite using rice straw-derived bio-
char. J Soils Sediments 11:11351141
Davison W, Zhang H (2012) Progress in understanding the use of
diffusive gradients in thin films (DGT)back to basics.
Environ Chem 9:113
Degryse F, Smolders E, Zhang H, Davison W (2009) Predicting
availability of mineral elements to plants with the DGT
technique: a review of experimental data and interpretation
by modelling. Environ Chem 6:198218
Downie A, Crosky A, Munroe P (2009) Physical properties of
biochar. Biochar Environ Manag: Sci Technol: 1332
Fangueiro D, Coutinho J, Borges L, Cabral F, Vasconcelos E
(2014) Nitrogen and carbon availability of liquid and solid
fractions of pig slurry obtained using different separation
technologies. Biol Fertil Soils 50:333341
Fangueiro D, Surgy S, Coutinho J, Vasconcelos E (2013) Impact
of cattle slurry acidification on carbon and nitrogen dynamics
during storage and after soil incorporation. J Soil Sci Plant
Nutr 176:540550
Frossard E, Condron LM, Oberson A, Sinaj S, Fardeau J (2000)
Processes governing phosphorus availability in temperate
soils. J Environ Qual 29:1523
Gichangi EM, Mnkeni PN, Brookes PC (2009) Effects of goat
manure and inorganic phosphate addition on soil inorganic
and microbial biomass phosphorus fractions under laboratory
incubation conditions. Soil Sci Plant Nutr 55:764771
Hansen H, Hansen P, Magid J (1999) Empirical modelling of the
kinetics of phosphate sorption to macropore materials in
aggregated subsoils. Eur J Soil Sci 50:317327
Hansen TH, Laursen KH, Persson DP, Pedas P, Husted S,
Schjoerring JK (2009) Micro-scaled high-throughput diges-
tion of plant tissue samples for multi-elemental analysis.
Plant Methods 5:12
He Z, Griffin TS, Honeycutt CW (2006) Soil phosphorus dynam-
ics in response to dairy manure and inorganic fertilizer appli-
cations. Soil Sci 171:598609
Hedley M, Stewart J, Chauhan B (1982) Changes in inorganic and
organic soil phosphorus fractions induced by cultivation
practices and by laboratory incubations. Soil Sci Soc Am J
46:970976
Hjorth M, Christensen KV, Christensen ML, Sommer SG (2010)
Solidliquid separation of animal slurry in theory and prac-
tice. A review. Agron Sustain Dev 30:153180
Hjorth M, Cocolo G, Jonassen K, Abildgaard L, Sommer SG
(2015) Continuous in-house acidification affecting animal
106
slurry composition. Biosyst Eng. doi:10.1016/j.
biosystemseng.2015.02.009
Hooda PS, Zhang H, Davison W, Edwards AC (1999) Measuring
bioavailable trace metals by diffusive gradients in thin films
(DGT): soil moisture effects on its performance in soils. Eur J
Soil Sci 50:285294
Huang Y, Dong H, Shang B, Xin H, Zhu Z (2011) Characterization
of animal manure and cornstalk ashes as affected by inciner-
ation temperature. Appl Energy 88:947952
Jrgensen K, Jensen LS (2009) Chemical and biochemical varia-
tion in animal manure solids separated using different com-
mercial separation technologies. Bioresour Technol 100:
30883096
Kai P, Pedersen P, Jensen J, Hansen MN, Sommer SG (2008) A
whole-farm assessment of the efficacy of slurry acidification
in reducing ammonia emissions. Eur J Agron 28:148154
Kumaragamage D, Akinremi O, Grieger L (2013) Phosphorus
fractions in solid and liquid separates of swine slurry separated
using different technologies. J Environ Qual 42:18631871
Lehmann J, Gaunt J, Rondon M (2006) Bio-char sequestration in
terrestrial ecosystemsa review. Mitig Adapt Strat Glob
Chang 11:395419
Malik MA, Marschner P, Khan KS (2012) Addition of organic and
inorganic P sources to soileffects on P pools and microor-
ganisms. Soil Biol Biochem 49:106113
Mason S, McNeill A, McLaughlin MJ, Zhang H (2010) Prediction
of wheat response to an application of phosphorus under field
conditions using diffusive gradients in thin-films (DGT) and
extraction methods. Plant Soil 337:243258
Mason SD, McLaughlin MJ, Johnston C, McNeill A (2013) Soil
test measures of available P (Colwell, resin and DGT) com-
pared with plant uptake using isotope dilution. Plant Soil 373:
711722
Masse L, Masse D, Beaudette V, Muir M (2005) Size distribution
and composition of particles in raw and anaerobically
digested swine manure. Trans ASABE 48:19431949
Menzies NW, Kusumo B, Moody PW (2005) Assessment of P
availability in heavily fertilized soils using the diffusive
gradient in thin films (DGT) technique. Plant Soil 269:19
Mller HB, Jensen HS, Tobiasen L, Hansen MN (2007) Heavy
metal and phosphorus content of fractions from manure
treatment and incineration. Environ Technol 28:14031418
Nayak AK, Kumar A, Raja R, Rao KS, Mohanty S, Shahid M,
Tripathy R, Panda BB, Bhattacharyya P (2014) Fly ash addi-
tion affects microbial biomass and Carbon mineralization in
agricultural soils. Bull Environ Contam Toxicol 92:160164
Nziguheba G, Palm CA, Buresh RJ, Smithson PC (1998) Soil
phosphorus fractions and adsorption as affected by organic
and inorganic sources. Plant Soil 198:159168
Ohno T, Crannell BS (1996) Green and animal manure-derived
dissolved organic matter effects on phosphorus sorption. J
Environ Qual 25:11371143
Olsen S, Cole C, Watanabe F, Dean L (1954) Estimation of
available phosphorus in soil by extraction with sodium bicar-
bonate. US Dep of Agric Circ: 939
Peters K, Hjorth M, Jensen LS, Magid J (2011) Carbon, nitrogen,
and phosphorus distribution in particle sizefractionated sep-
arated Pig and cattle slurry. J Environ Qual 40:224232
Petersen SO, Andersen AJ, Eriksen J (2012) Effects of cattle slurry
acidification on ammonia and methane evolution during
storage. J Environ Qual 41:8894
Plant Soil (2016) 401:93107
Popovic MO, Hjorth M, Jensen LS (2012) Phosphorus, copper and
zinc in solid and liquid fractions from full scale and labora-
tory separated pig slurry. Environ Technol 33:21192131
R Development Core Team (2011) A language and environment
for statistical computing
Reddy DD, Rao AS, Takkar P (1999) Effects of repeated manure
and fertilizer phosphorus additions on soil phosphorus dy-
namics under a soybean-wheat rotation. Biol Fertil Soils 28:
150155
Ro K, Cantrell K, Hunt P, Ducey T, Vanotti M, Szogi A (2009)
Thermochemical conversion of livestock wastes: carboniza-
tion of swine solids. Bioresour Technol 100:54665471
Ro KS, Cantrell KB, Hunt PG (2010) High-temperature pyrolysis
of blended animal manures for producing renewable energy
and value-added biochar. Ind Eng Chem Res 49:10125
10131
Roboredo M, Fangueiro D, Lage S, Coutinho J (2012) Phosphorus
dynamics in soils amended with acidified pig slurry and
derived solid fraction. Geoderma 189:328333
Santner J, Mannel M, Burrell LD, Hoefer C, Kreuzeder A, Wenzel
WW (2015) (2015) Phosphorus uptake by Zea mays L. is
quantitatively predicted by infinite sink extraction of soil P.
Plant Soil 386:371383
Six L, Pypers P, Degryse F, Smolders E, Merckx R (2012) The
performance of DGT versus conventional soil phosphorus
tests in tropical soils - an isotope dilution study. Plant Soil
359:267279
Six L, Smolders E, Merckx R (2013) The performance of DGT
versus conventional soil phosphorus tests in tropical soils
maize and rice responses to P application. Plant Soil 366:4966
Six L, Smolders E, Merckx R (2014) Testing phosphorus avail-
ability for maize with DGT in weathered soils amended with
organic materials. Plant Soil:177192
Sommer SG, Hjorth M, Leahy J, Zhu K, Christel W, Srensen CG,
Sutaryo (2015) Pig slurry characteristics, nutrient balance
and biogas production as affected by separation and acidifi-
cation. J Agric Sci 153:177191
Spokas KA, Cantrell KB, Novak JM, Archer DW, Ippolito JA,
Collins HP, Boateng AA, Lima IM, Lamb MC, McAloon AJ
(2012) Biochar: a synthesis of its agronomic impact beyond
carbon sequestration. J Environ Qual 41:973989
Tandy S, Mundus S, Yngvesson J, de Bang TC, Lombi E,
Schjoerring JK, Husted S (2011) The use of DGT for predic-
tion of plant available copper, zinc and phosphorus in agri-
cultural soils. Plant Soil 346:167180
Thygesen A, Wernberg O, Skou E, Sommer SG (2011) Effect of
incineration temperature on phosphorus availability in bio
ash from manure. Environ Technol 32:633638
Tsai W, Liu S, Chen H, Chang Y, Tsai Y (2012) Textural and
chemical properties of swine-manure-derived biochar perti-
nent to its potential use as a soil amendment. Chemosphere
89:198203
Uchimiya M, Hiradate S (2014) Pyrolysis temperature-dependent
changes in dissolved phosphorus speciation of plant and
manure biochars. J Agric Food Chem 62:18021809
Uchimiya M, Ohno T, He Z (2013) Pyrolysis temperature-dependent
release of dissolved organic carbon from plant, manure, and
biorefinery wastes. J Anal Appl Pyrolysis 104:8494
Waldrip HM, He Z, Erich MS (2011) Effects of poultry manure
amendment on phosphorus uptake by ryegrass, soil phospho-
rus fractions and phosphatase activity. Biol Fertil Soils:112
Plant Soil (2016) 401:93107
Waldrip-Dail H, He Z, Erich SM, Honeycutt WC (2009) Soil
phosphorus dynamics in response to poultry manure amend-
ment. Soil Sci 174:195201
Wnetrzak R, Kwapinski W, Peters K, Sommer SG, Jensen LS,
Leahy JJ (2013) The influence of the pig manure separation
107
system on the energy production potentials. Bioresour
Technol 136:502508
Zhang H, Davison W, Gadi R, Kobayashi T (1998) In situ mea-
surement of dissolved phosphorus in natural waters using
DGT. Anal Chim Acta 370:2938