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DOI: 10.1002/jpln.201100126
Abstract
Appropriate management of P from slurry can increase crop production and decrease nutrient
loss to water bodies. The present study examined how the application of different size fractions
of dairy slurry influenced the quantity and composition of P leached from grassland in a temperate climate. Soil blocks were amended (day 0 = start of the experiment) with either whole slurry
(WS), the > 425 lm fraction (coarse slurry fraction, CSF), the < 45 lm slurry fraction (fine liquid
slurry fraction, FLF), or not amended, i.e., the control soil (CON). Deionized water was added to
the soil blocks to simulate six sequential rainfall events, equivalent to 250 mm (day 0.2, 1.2, 4.2,
11.2) or 500 mm of rainfall (day 18.2 and 25.2), with leachates collected the following day. The
results showed that total dissolved P (TDP), dissolved reactive P (DRP), dissolved unreactive P
(DUP), orthophosphate, phosphomonoester, and pyrophosphate concentrations generally
decreased with the increasing number of simulated rain events. Total dissolved P was leached
in the following order WS > FLF CSF > CON. Dissolved organic C was correlated with TDP,
DRP, and DUP in leachates of all treatments. The highest concentrations of dissolved phosphomonoesters and pyrophosphate (147 lg P L1 and 57 lg P L1, respectively) were detected
using solution 31P-NMR spectroscopy in the WS leachates. Overall, there were significant differences observed between slurry treatments (e.g., relative contributions of inorganic P vs. organic
P of dissolved P in leachates). Differences were independent from the rate at which slurry P was
applied, because the highest dissolved P losses per unit of slurry P applied were measured in
the FLF, i.e., the treatment that received the smallest amount of P. We conclude that the specific
particle-size composition of applied slurry influences dissolved P losses from grassland systems. This information should be taken in account in farm-management approaches which aim
to minimizing dissolved slurry P losses from grassland systems.
Key words: dairy slurry / leachate / dissolved P / total P / reactive P / unreactive P / dissolved organic
carbon / grassland / 31P-nuclear magneticresonance spectroscopy
1 Introduction
Dairy slurry is typically surface-applied to UK pastures as an
organic fertilizer (Anon, 2000). The phosphorus (P) within it
can be taken up by plants and microorganisms, sorbed or
otherwise held in the soil, or lost by leaching or runoff. The
latter signals some inefficiency in recycling or retention of P
in soilplant systems, which may contribute to the eutrophication of water bodies (Withers and Haygarth, 2007; Blackwell
et al., 2010; Granger et al., 2010). Cattle manure contains
total P concentrations of between 4 and 18 g P kg1 (He et al.,
2004; Sharpley et al., 2004; Toor et al., 2006; Fuentes, 2009).
Of this, inorganic P constitutes 60%70% (He et al., 2004;
Fuentes, 2009), with organic and condensed inorganic phosphates constituting the remainder. Studies have documented
the presence of pyrophosphate, phosphomonoesters, phosphodiesters, and phosphonates in animal manures (Hansen
et al., 2004; Turner, 2004; McDowell and Stewart, 2005).
Phosphorus in leachate from grassland soils amended with
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Table 1: Characterization and application rate of slurry and slurry fractions. Data presented are means and standard deviation of four replicate
blocks. Values in parentheses are percentage of inorganic (Pi) and organic P (Po) as a portion of the total P (Pt) for whole slurry and slurry fractions
Dry matter / %
Whole slurry
> 425 lm
< 45 lm
12.6 0.13
11.9 0.06
0.60 0.03
Concentration
Pt / lg g1
4624 62
2506 24
12158 212
Pi / lg g1
2760 51(60%)
1089 52 (43%)
7685 49 (63%)
Po / lg g1
1863 51 (40%)
1417 44 (57%)
Application rate / g
313
125
313
Pt / mg
182 3
37 1
23 1
Pi / mg
109 2 (60%)
16 1 (43%)
14 1 (63%)
Po / mg
73 2 (40%)
21 2 (57%)
8 1 (37%)
Amounts of P applied
through the soil, were collected the day following each wetting event (i.e., 1, 2, 5, 12, 19, and 26 d after slurry application). The soil blocks were incubated at room temperature for
the whole experimental period. Between each rainfall event,
water was added to maintain soil moisture content at 60% of
field capacity.
an acquisition time of 0.4 s, and broadband proton decoupling. The delay time used here allows for sufficient spin-lattice relaxation between scans for P compounds in NaOHEDTA (Cade-Menun et al., 2002). Approximately 30,000
scans were acquired for each sample. Chemical shifts of signals were determined in parts per million (ppm) relative to an
external standard of 85% H3PO4. Spectra were plotted with a
line broadening of 5 Hz, and signals were assigned to P compounds or functional groups based on literature reports (Turner
et al., 2003a). Signal areas were calculated by integration and P
concentrations calculated by multiplying the proportion of the
spectral area assigned to a specific signal by the total P concentration (mg P L1) in the original sample. This assumes
that all P in the original sample was redissolved in the NaOHEDTA and measured in the NMR analysis.
The total quantity of P lost from the soil after six rain events
from WS reached (597 38) lg P (equivalent to 9.6 mg P
m2 or 0.16 g P m3), while in the FSF, CSF, and CON it
reached (180 15) lg, (143 20) lg, and (107 22) lg, respectively. In FSF and CSF the total amount of DRP lost ranged between (88 12) lg and (88 20) lg, while the sum of
the soil DRP losses in CON reached (68 15) lg. However,
most DRP was lost predominantly from the WS ([339 16]
lg). The DUP collected in WS, FSF, and CSF leachates
reached (258 24) lg, (92 12) lg, and (62 8) lg, respectively, whereas the DUP loss in CON was only (39 8) lg.
Overall, the percentage of the applied P that was lost in the
leachates after the six rainfall events was similar at 0.3% in
all four treatments (WS, CSF, FSF, and CON).
The P concentrations leached from slurry and slurry fractions
initially decreased until the third (DRP and DUP; Tab. 2) or
the fourth (TDP; Tab. 2) simulated rainfall event. The potential
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The data in Fig. 1 shows that the P-response factor for TDP,
DRP, and DUP in the first 5 d after application is higher for
the FLF application than WS and CSF, suggesting that per
mg of P applied by means of this slurry treatment FLF more
dissolved P is leached from the grassland in our experimental
setup. Beyond day 5, no significant differences were observed in the P-response factor between the three slurry
treatments. The initial differential difference in P response between the three slurry treatments is probably related to the
fact that the FLF is a more liquid amendment than the other
P response factor
36
for TDP, DRP, and DUP loss is therefore greatest for initial
events, but declines with time, the latter probably due to the
stabilization of slurry-derived P through interactions with soil
constituents. Application of the WS and FSF would promote
rapid infiltration of the smaller slurry-derived particles into
soil, increasing the transfer of the dissolved P to greater soil
depth and enhancing the possibility of P leaching. However,
the more rapid microbial degradation of these smaller organic
particles may also contribute to the overall release of P, causing a further localized enrichment of P concentrations in the
deeper soil and ultimately in the leachates. Studies carried
out by Fangueiro et al. (2007, 2010), using the greatest CO2
production as an indicator, also showed a rapid biodegradation of the smaller particles (< 45 lm) of slurry applied to the
soil surface. The authors suggested that the rapid biodegradation is probably a direct result of the higher amount of N
contained in this slurry fine fraction.
18
WS
30
CSF
FLF
24
18
12
6
0
1
5
12
Days after slurry application
19
WS
26
CSF
FLF
15
12
9
6
3
0
1
5
12
Days after slurry application
24
19
WS
26
CSF
FLF
20
16
12
8
4
0
1
5
12
Days after slurry application
19
26
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Table 2: Concentrations of dissolved P in leachates from the control-amended soils with slurry and slurry fractions during the experimental
period, for total dissolved P (TDP), dissolved reactive P (DRP), and (c) dissolved unreactive P (DUP).
TDP / lg L1
Treatment day
WS
CSF
CSF*
FSF
CON
2173 223
385 97
966 243
657 108
120 36
1367 199
271 53
680 132
579 111
187 40
617 36
143 17
360 43
173 51
170 75
12
298 54
184 22
461 56
60 17
128 18
19
237 38
140 18
352 45
87 17
104 18
26
303 97
142 46
357 115
71 20
179 70
WS
CSF
CSF*
FSF
1212 78
143 32
360 81
300 49
77 27
118 29
296 72
209 24
103 26
90 20
226 49
95 18
87 29
DRP / lg L1
Treatment day
1
CON
723 110
333 16
12
180 42
88 8
221 21
32 13
45 10
19
163 24
100 11
252 27
60 7
84 18
26
199 53
102 35
256 89
45 8
116 40
WS
CSF
CSF*
FSF
961 147
242 128
607 321
358 86
44 11
645 94
153 31
385 78
370 96
85 16
284 30
53 14
134 35
79 36
83 46
12
118 31
96 26
240 66
28 7
83 11
19
74 16
40 10
100 26
27 11
20 3
26
104 43
40 11
101 28
26 13
64 31
DUP / lg L1
Treatment day
CON
DOC / mg L1
Treatment day
1
WS
CSF
CSF*
FSF
38.7 4.8
19.4 5.7
48.6 14.3
16.7 3.1
CON
4.1 0.5
36.8 5.2
14.1 1.7
35.4 4.2
21.2 5.1
4.5 0.2
21.4 2.0
11.1 1.4
27.9 3.4
9.3 2.9
4.4 0.4
12
10.8 1.2
6.6 0.6
16.6 1.6
5.6 1.0
18.4 11.0
19
9.8 0.7
10.6 1.4
26.7 3.4
7.8 1.2
7.4 0.5
26
11.2 2.5
6.9 0.5
17.3 1.3
4.6 0.7
7.4 0.5
(1)
(2)
(3)
Table 3 shows the results from the solution 31P-NMR analyses of the leachate, and Fig. 2 shows a typical NMR spectrum obtained on the samples. The gross proportion of the
The presence and variation in organic P content among treatments and sampling times also seems to exclude the possibi-
WS > FSF = CSF > CON). The quantities of DOC in leachates tend to decrease with rain events. The addition of
whole slurry resulted in a sevenfold increase in DOC in leachates compared to the control soil. Similar results were
reported by Bol et al. (1999), who pointed out that 50% of
the C present in leachate was native soil C, suggesting
mechanisms such as priming effects, displacement
effects, or pool substitution. Dissolved organic C is an
important fraction of the soil OM and originates mainly from
the degradation of large organic molecules, root exudates,
and organic compounds from microbial biomass. The linkages of P to organic C in soil are known to play a key role in
the mobilization of P and act directly to increase organic P in
leachate. Earlier studies by Bol et al. (2006) had already
demonstrated that the proportions of dung-derived P and
dung-derived C in grassland soils are correlated.
Table 3: Distribution of P compounds in leachates from slurry-amended and control soils during the six rain events. Values in italics and
subscript in the > 425 lm section are calculated based on 313 g amendment (CSF value 2.51); di-ester P (6 lg L1) was only detected in the
> 425 treatment in rain event 6.
Treatment
Rain event
Total P
Phosphate
Monoester
Pyro-P
%TP
/ lg L1
whole slurry
< 45 lm
> 425 lm
Control
Organic P
2173
2070
46
57
1367
1191
147
30
11
617
508
81
28
13
298
298
237
179
59
25
303
272
23
657
597
36
25
579
469
76
34
13
174
143
18
12
10
60
60
87
75
71
61
10
385
966
346
868
31
271
681
197
495
62
143
360
143
360
184
461
184
461
140
352
129
324
10
142
357
125
314
13
121
90
14
16
12
187
141
37
10
20
170
170
128
128
104
104
179
179
77
10
155
12
24
30
23
0
0
25
32
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Acknowledgments
lity that some organic P forms did not enter solution when
preparing the samples for NMR analysis. Clearly the amounts
and transfers of slurry- and soil-derived organic P following
rainfall are driven by a mix of physico-chemical and biological
soil processes that on a daily to weekly temporal time frame
show complex behavior of organic-P patterns in leachates.
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