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JECE 588 1–6

Journal of Environmental Chemical Engineering xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

1 Synthesis, characterization and application of hydrogel derived from

2 cellulose acetate as a substrate for slow-release NPK fertilizer and
3 water retention in soil
4 Q1 André M. Senna a, * , Janaina Braga do Carmo b , José Mauro Santana da Silva b ,
5 Vagner R. Botaro a,b
6 a
Universidade Federal de Ouro Preto – REDEMAT, Ouro Preto, 35400-000 Minas Gerais, Brazil
7 b
Universidade Federal de São Carlos – UFSCAR, Sorocaba, 18052-780 São Paulo, Brazil

A R T I C L E I N F O A B S T R A C T

Article history: Hydrogels were prepared from cellulose acetate with a degree substitution (DS) 2.5 dissolved in
Received 5 November 2014 dimethylformamide using esterification crosslinking with ethylenediaminetetraacetic dianhydride
Q2 Accepted 9 March 2015 (EDTAD) catalyzed by triethylamine. Thus followed by the subsequent conversion of the unreacted
carboxyl groups to sodium carboxylates with the addition of aqueous NaHCO3 was performed to enhance
Keywords: the water affinity of the hydrogels. The hydrogel derived from cellulose acetate and EDTAD (GEDTA) was
Hydrogel immersed in an aqueous solution containing 47.66 g/l of KCl (2.5% K+) and 159.7 g/l of NH4H2PO4 (NH4+
Cellulose acetate
2.5% and 13.5% H2PO4
1) at room temperature for 2 h. The results of the chemical analysis showed that
Slow-release
Water-retention
the product contained 120.5  1.5 mg of potassium/g, 104.3  1.1 mg of phosphate/g, and 84.0  1.5 mg of
NPK compound fertilizer ammonium/g. The product we prepared not only has slow-release property but could also absorb a large
amount of water and preserve the soil moisture at the same time. The results indicated that the GEDTA
could be used in agriculture and horticulture, especially in drought-prone regions where the availability
of water is limited.
ã 2015 Published by Elsevier Ltd.

8 Introduction eutrophication. On the other hand, the slow-release fertilizer can 25

be synchronized with plant uptake and then, soil nitrification and 26

9 The world’s population depends on modern agriculture and the denitrification rates can decrease reducing losses and environ- 27
10 use of synthetic fertilizers to grow their food supply. However, the mental impacts [5]. The slow-release of nutrients from fertilizer 28
11 overuse of synthetic fertilizers and excess leaching from soils can also reduce operational costs. 29
12 has generated serious environmental impacts worldwide such as According to Wang et al. [6], cellulose has been widely studied 30
13 the eutrophication of estuaries and other coastal regions. While during the past decades because of attractive properties such as 31
14 reducing fertilizer application can compromise crop productivity, biodegradation, nontoxicity and renewable capacity. The hydrogels 32
15 reducing nutrient losses in fertilizer application by using derived from cellulose exhibit unique properties such as biode- 33
16 substrates that perform controlled-release or slow-release while gradability and biocompatibility which could be beneficial for 34
17 conserving soil moisture is considered a promising alternative bioengineering and agricultural purposes [7]. 35
18 [1,2]. Due to the increase of the environmental problems associated 36
19 According to Carmo et al. [3] and Nogueira et al. [4] the overuse with synthetic polymers, there is a tendency toward the use of 37
20 of mineral fertilizers, mainly fertilizers with nitrogen (ammonium polymers derived from renewable sources. Among the polymers 38
21 and nitrate), can cause environmental impacts. The mineral derived from renewable sources, the cellulose is highly desirable as 39
22 fertilizers are inefficient; therefore, it is necessary to apply several a raw material in the production of biodegradable superabsorbent 40
23 times, especially when it comes to highly mobile nutrients such as polymers because it is the most abundant natural polymer on earth 41
24 N and K. Thus, they may be leached into rivers and lakes to cause and not expensive [7]. 42

Senna et al. [8] have reported that hydrogels can be produced 43

from a cellulose solution by esterification crosslinking. However, 44

because cellulose is very difficult to dissolve in common solvents, 45

* Corresponding author. Tel.: +55 15 3229 6167.
E-mail address: [email protected] (A.M. Senna). Chang and Zhang [9] have proposed the use of new solvents, such 46

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2213-3437/ ã 2015 Published by Elsevier Ltd.

Please cite this article in press as: A.M. Senna, et al., Synthesis, characterization and application of hydrogel derived from cellulose acetate as a
substrate for slow-release NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.008
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47 as N-methylmorpholine-N-oxide (NMMO), ionic liquids (ILs), and after starting the reaction. The GEDTA was prepared from CA 100
48 alkali/urea (or thiourea). However, other methods for the according to the scheme presented in Fig. 1. 101
49 preparation of cellulose hydrogels are being developed [9]. Esterification was carried out at room temperature for 48 h 102
50 For instance, cellulose acetate (CA) is a well known derivative of (cure) and the reaction product was triturated. A subsequent 103
51 cellulose that has been as cigarette filters, film base in photograph, conversion of the unreacted carboxyl groups to sodium carbox- 104
52 industrial filters, filtering and reverse osmosis. Cellulose acetate is ylates in the product with the addition of aqueous NaHCO3 was 105
53 produced either by heterogeneous or homogeneous acetylation of performed to enhance the water affinity. Finally, the product was 106
54 cellulose, and the crystalline structure of the CA is less crystalline purified, washed with distilled water and ethanol, dried, and then 107
55 than the crystalline structure cellulose. Thus, CA is soluble in screened through a 60 mesh (250 mm) sieve to obtain a white 108
56 common solvents [10,11]. granular product. Samples of GEDTA that were used in the FTIR 109
57 The aim of this work is to reveal the synthesis conditions, analysis were not neutralized with NaHCO3. More details of the 110
58 controlled-release, and water-retention properties of the GEDTA. synthesis and characterization of hydrogel derived from cellulose 111
59 This paper aims to highlight the development in cellulose acetate- acetate are presented by Senna et al. [8]. 112
60 based hydrogels with an emphasis on the application as a substrate
61 for slow release NPK fertilizer and water retention in the soil. Fourier transform infrared spectroscopy (FTIR) 113
62 Recent literature has been cited to summarize work on cellulose
63 acetate-based hydrogel [8] but no reports in the literature on The FTIR spectrum was obtained after grinding the sample into 114
64 application of hydrogel derived from cellulose acetate and EDTAD a powder and mixing with KBr powder. The powder mixture was 115
65 Q3 in the slow release of NPK fertilizer and water retention in soil. compressed into a transparent disk and scanned from 4000 to 116

500 cm
1 using an average 32 scans. 117

66 Experimental
Determination of total amount of crosslinker in the GEDTA 118
67 Materials
In this procedure the tetrasodium EDTA, which was produced 119
68 The cellulose acetate (CA) with a degree of substitution (DS) by the alkaline hydrolysis, was titrated with a standard solution of 120
69 2.5 that has been used in this study was acquired commercially CaCl2. 0.5 g of hydrogels samples was weighed accurately and 121
70 from the RHODIA1 group (CA used in the production of cigarette transferred to a 250 ml flask; 20 ml of 75% aqueous ethanol was 122
71 filters). Dimethylformamide (DMF), which has been used as added to each sample and then heated for 30 min at 60  C. Then 123
72 solvent and triethylamine as a catalyst, potassium chloride (KCl) 20 ml of 0.5 M NaOH solution was added to each sample and again 124
73 and ammonium phosphate monobasic (NH4H2PO4) were obtained heated at 60  C for 15 min. The same procedure was also carried out 125
74 commercially, both with a purity of 99%. A sample of cellulose for a control system (not containing hydrogels). The flasks were 126
75 acetate, with DS 2.44 and an average molecular weight equal to stoppered and allowed to stand at room temperature for 72 h. The 127
76 50,000 g/mol has been used as a standard for the analysis in solutions were filtered, transferred to a 100 ml volumetric flask and 128
77 determining the degree of substitution (DS). This CA was supplied filled up to the mark with distilled water then 10 ml was 129
78 by Sigma–Aldrich1. CA has been immersed in ethyl ether at room transferred to Erlenmeyer’s flasks and 10 ml of ammoniacal buffer 130
79 temperature for 1 h and 30 min in ethanol and after it was dried in pH 10 was added with indicator Eriochrome Black. The samples 131
80 an oven at 80  C for 24 h. This procedure has been used to remove were then titrated with a standard solution of 0.01 M CaCl2 to the 132
81 impurities from the surface of cellulose acetate. The predominant end point (the color changed from blue to burgundy). 133
82 soil used in this study was classified as a Typical Red Oxisol [12]. This titration allowed the weight of EDTA in the polymeric 134
83 The soil collection was performed in the region of Sorocaba in São network to be measured. The percentage of EDTA crosslinked and 135
84 Paulo State, Brazil (23 340 4000 S and 47 31017.800 W). The soil grafted in the hydrogel sample could be determined using Eq. 136
85 characterization was performed from a sub-collection of 40 soil (1)–(3):
86 samples from the study area that were taken at depths of 0–0.2 m
87 EEDTA ¼ ET
acetyl (1)
and were combined to yield a composite sample, which was
88 analyzed for its fertility status (Table 1). Before analysis, the soil
89 was dried up to constant weight of 40  C in an oven and sieved in   
EEDTA
90 mesh-10 and details should be found in De Urzedo et al. [13]. %Cr ¼
1  100 (2)
mmEDTA
91 The sodium polyacrylate (SPA) (Forth1) was provided by
92 Tecnutri do Brasil, Tietê, Brazil (this product is used in planting
93 eucalyptus). %Gr ¼ ð100
%CrÞ (3)
94 Hydrogels synthesis 138
137
where EEDTA is the amount of ester formed by EDTAD and CA (in
mmol), ET is the total amount of ester (acetate, EDTAD-crosslinked 139
95 The preparation of GEDTA derived from CA was performed in 140
and EDTAD-grafted) in mmol, acetyl is the amount of acetyl in
96 homogeneous medium and triethylamine as an esterification 141
mmol (results obtained from the degree of substitution of CA), %Cr
97 catalyst. The reaction mixture became increasingly viscous soon 142
is the percentage of EDTAD-crosslinked, mmEDTA is the concen-
98 after adding EDTAD as a crosslinker, and the morphology of 143
tration of EDTA in hydrogels in mmol and %Gr is the percentage of
99 mixture gradually changed from a solution to gel about 10–20 min 144
EDTAD-grafted [8].

Table 1
Soil chemical composition from a sub-collection of 40 soil samples from the study area that were taken at depths of 0–0.2 m and were combined to yield a composite sample. Q10

+
OM pH (CaCl2) P K Ca Mg Al H Al SB CEC V S B Cu Fe Mn Zn

g/dm3 mg/dm3 mmol/dm3 % mg/dm3 mg/dm3

16.0 5.0 1.0 0.4 13.0 1.0 1.0 31.0 14.0 45.0 32.0 41.0 0.06 0.1 6.0 0.6 <0.1

OM: organic matter; CEC: cation exchange capacity; SB: sum of bases; V%: base saturation.

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substrate for slow-release NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.008
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Fig. 1. Reaction of EDTA dianhydride (EDTAD) and cellulose acetate (DS 2.5) in DMF/triethylamine. Esterification crosslinking and grafting occur simultaneously [8]. Q9

145 Preparation of GEDTA immersed in the solution of NPK at room temperature until the 152

equilibrium swelling. The GEDTA was vacuum filtered and stored. 153
146 The GEDTA was immersed in a solution of NPK (47.66 g/l of KCl;
147 2.5% K+) and 159.7 g/l NH4H2PO4 (NH4+ 2.5% and 13.5% H2PO4
). Slow release behavior of GEDTA in soil 154
148 The pH of the solution was adjusted with NH4OH solution (20%) to
149 approximately 7.00. The neutralization was necessary because at To study the slow release behavior of GEDTA in soil, the following Q4 155
150 acid pH may occur protonation of the carboxylate groups and experiment was carried out: (1) The GEDTA (with NPK) was placed in 156
151 hence the absorption capacity decreases. The GEDTA remained envelopes (filter paper) (note: the use of an envelope in the test was 157

Please cite this article in press as: A.M. Senna, et al., Synthesis, characterization and application of hydrogel derived from cellulose acetate as a
substrate for slow-release NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.008
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158 to prevent particle loss of hydrogel in the soil after the test). (2) controlled experiment, without GEDTA, was also carried out. The 198
159 40 cm3 of dry soil (below mesh-10) were placed in a cylindrical tube samples were placed in an oven with air circulation in a 199
160 and enveloped sample was placed onto soil and added 10 cm3 of dry temperature regulated precisely in 40  C and from time to time 200
161 soil. Fig. 2 shows the scheme of the system used in the study of the sample was removed and weighed (W1). The same procedure 201
162 controlled release. To quantify the irrigation of the soil, the diameter was used for samples GEDTA (with NPK) and sodium polyacrylate 202
163 of the cylindrical tube was 5.72 cm2, therefore, 0.57 ml of water is (SPA). The water evaporation ratio (W%) of soil was calculated 203
164 equivalent to 1 mm/m2 of irrigation. The total volume of the tube was using the following equation: 204
165 65 cm3. The soil used was dry, however, after contact with the water,  
166 ðW o
W 1 Þ
the volume had decreased slightly and occurred a natural compres- W% ¼  100 (5)
167 Wo
sion performed by water (about 2%).
168 The system had a burette for measuring the volume of water to
Results and discussion 205
169 drip. For each point in the curve a sample was used, where 10 cm3
170 of soil above the envelope was discarded, the envelope with GEDTA
Hydrogels synthesis 206
171 was removed and 40 cm3 of soil were dried, homogenized and
172 analyzed. The irrigation volumes were distributed over 158 days.
For the elucidation of the structural features of GEDTA, the Q5 207
173 The total volume of irrigation was equivalent to 500 mm/m2.
number of molecules of EDTA per repeat unit and the percentages 208

of crosslinked-EDTAD and grafted-EDTAD (%Cr and %Gr, respec- 209

174 Component analysis
tively) were determined by the titration method for the estimation 210

of the total amount of ester contents. In 1 cm3 of the hydrogel, it 211

175 Contents of ammonium and phosphate in the GEDTA and in the
was supposed that there was X mmol of crosslinked EDTAD and 212
176 soil were determined by spectrophotometry (visible region) and
Y mmol of grafted EDTAD. As shown in Fig. 1, one diester and two 213
177 potassium was determined by flame photometry. The extraction of
carboxylic acid groups are formed during crosslinking, whereas the 214
178 K+ and H2PO4
1 was taken with Mehlich 1 solution (0.05 M 215
179 graft reaction resulted in the formation of one ester and three
HCl + 0.0125 M H2SO4) and NH4+ was taken with 2 M KCl solution 216
180 carboxylic acid groups. In comparing the results in Table 1 with
[14]. 217
results obtained by Kono and Fujita [7] and Senna et al. [8] it is
possible to conclude that the results of percentage of EDTAD- 218
181 Determination of the water absorbency
crosslinked and the percentage of EDTAD-grafted are similar. The 219

following equations were used to obtain the results of Table 2. Q6 220

182 The samples of GEDTA were immersed in distilled water at a
183 temperature of 25  C and 50  C after a set time and then samples WCA ¼ ðr
AT2 Þ (6)
184 were collected and filtered under vacuum. The determination of
185 the percentage of absorption was performed with a thermobalance WCA
nCA ¼ (7)
186 with a programmed heating up to 105  C. To calculate the M1 RU
187 percentage of absorption of water Eq. (4) was used. Absorbency
188 measurements were taken for three samples of each product and  
WCA
189 the average of the three values was plotted against the absorbency %CA ¼  100 (8)
190
r
time.
   
ðW
W o Þ mmol EDTA
S% ¼  100 (4) AT1 ¼ (9)
Wo SV
192
191 where: S% is the percentage of swelling, W is the final weight and  
193 Wo the initial weight. mmol EDTA
AT2 ¼ (10)
SV
194 Measurement of the water-retention of GEDTA in soil
M1RU = molar weight of repeat unit (534.5 g/mol), r = density of 222
221
hydrogel (g/cm3), SV = sample volume (cm3). 223
195 A 0.8 g sample of GEDTA was well-mixed with 40 g of dry soil
196 (below Mesh-10) and kept in a plastic tube and then 30 g of
197 Table 2
distilled water was slowly added into the tube and weighed (Wo). A Reaction conditions and results of the esterification cross-
linking of cellulose acetate with EDTAD.

Gel parameters Results

WCA (g) 1.144
nCA (mol) 0.0021
%CA (%) 83.6
%Cr (%) 98.26
nEDTA (mol) 0.36
AT1 (mmol/cm3) 0.7663
AT2 (g/cm3) 0.224
AEDTA (molecules) 4.61  1020
%Gr (%) 1.74

WCA: grams of CA per cm3 of gel; nCA: mol of repeat unit; %

CA: percentage of CA; AT1 (mmol/cm3): mmol of EDTA per
cm3 of gel; AT2 (g/cm3): grams of EDTA per cm3 of gel;
AEDTA: number of EDTA molecules per cm3 of hydrogel; %Cr:
percentages of the crosslinked EDTA molecules in total
esterified EDTA in the GEDTA; %Gr: percentages of the
grafted EDTA molecules in total esterified EDTA in the
GEDTA; nEDTA: number of EDTA molecules per repeat unit of
Fig. 2. Scheme of the system used in the study of controlled release. CA.

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substrate for slow-release NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.008
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224 FTIR analysis 1100

4
1000
225 Following the crosslinking esterification reaction of cellulose o
226 900 1 CA-(25 C)
acetate (DS 2.5) with EDTAD, the obtained product showed several o
2 CA-(50 C)
227 new absorption bands in the FTIR spectrum, in addition to the 800 o
3 GEDTA-(25 C)

Water absorbency %
228 original peaks from pure cellulose acetate as shown in Fig. 3. o
700 4 GEDTA-(50 C)
229 The increase in the absorption band at 1755 cm
1 was assigned to 3
600
230 the C¼O stretching vibration of the carboxylic acid (EDTA acid),
231 and the absorption appearing at 1643 cm
1 was assigned to the 500
232 C¼O asymmetric stretching vibration of the carboxylic acid. 400
233 Formation of the carboxylic acid in the products was also 300
234 confirmed by the typical absorption at 1385 cm
1 arising from
235 the carbonyl symmetric stretching vibration [15]. 200

236 The IR analysis indicates that the hydroxyl group of cellulose 2

100 1
237 acetate (DS 2.5) may have esterified with EDTAD, resulting in the 0
238 formation of carboxylic acid as well as crosslinking between 0 50 100 150 200 250 300 350
239 the cellulose acetate chains. The results of FTIR corroborate with Time (minutes)
240 results obtained by Kono and Fujita [7], and Senna et al. [8].
Fig. 4. Water absorbency: temperature 25  C and 50  C.
241 Determination of the water absorbency
irrigation water that passes through the GEDTA elutes the ions of 266

242 3 NPK. (3) The elution rate is controlled by the interaction between Q7 267
A potentiometric titration was performed in 1 cm of GEDTA 268
243 the ions and GEDTA. Proportionately with the output of NPK ions of
with 100 ml of distilled water to find the pH value that all of the 269
244 the polymeric network there is an increase in water absorbency
carboxylic acid groups are neutralized completely. The value found 270
245 and GEDTA begins to turn into a water retention substrate in soil.
was 8.5, and this value was used as a reference in the neutralization
246 A commercial fertilizer sample (Hydrofert1) containing 271
in the hydrogels used in testing water absorbency. 272
247 104.1  0.3 mg of ammonium/g, 162.2  0.4 mg of phosphate/g
Water absorbency is dependent on the temperature and also on
248 the amount of carboxylate groups in the hydrogels. In the
249 comparison between hydrogels and CA; it was concluded that
250 the hydrogels are more hydrophilic than the CA and thus absorb 18 9
251 17
more water (Fig. 4). With the presence of carboxylate groups in the 16 Ammonium-1 A 8
252 GEDTA, the ionic character along the polymer chain increases. Potassium-2

Release (%) (Phosphate and Potassium)

15
253 With increasing temperature, the diffusion of water increases into 14 Phosphate-3 1 7
254 13
the hydrogel and thus the absorption of water increases. 6
Release (%) Ammonium

12
11
255 Slow release behavior of GEDTA in soil 10
5

9 2 4
256 8
The GEDTA showed a good absorption of ions K+, NH4+ and 7
257 H2PO4
. The GEDTA absorbed 120.5  1.5 mg of K+, 104.3  1.1 mg of 6
3

258 H2PO4
and 84.0  1.5 mg of NH4+ (mg/g of dry GEDTA). One of the 5 2
259 most important characteristics of GEDTA we prepared was its 4
3 3
controlled-release property. Fig. 5 represents the NH4+, H2PO4
1
260 1
2
261 and K+ slow release behaviors of GEDTA in soil. 1 0
262 The nutrient release mechanism of GEDTA in soil can be 0
263 -1 -1
described using the following steps: (1) The GEDTA swells slowly 0 50 100 150 200 250 300 350 400 450 500
264 by the water in the soil and a dynamic exchange between the free 2
265 Irrigation (mm/m )
water in the GEDTA and the water in soil will develop. (2) The
24 Ammonium-1 250

22
Potassium-2 B 1 225
(potassium and ammonium)mg/dm of soil

Phosphate-3
1755 20
200
(1) GEDTA 1 1653 18
mg of phosphate/dm of soil

(2) CA
175
1385 16
3

150
14
Transmitance

2 12 2 125

10 100

8 3 75
6
50
3

4
25
2
0
0
0 50 100 150 200 250 300 350 400 450 500
4000 3500 3000 2500 2000 1500 1000 500 2
Irrigation (mm/m )
-1
wavenu mbe r (cm )
Fig. 5. Release behaviors of ammonium, phosphate and potassium. (A) % released
Fig. 3. FTIR spectra of GEDTA (1) and cellulose acetate (2). and (B) increase of ammonium, phosphate and potassium in soil.

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100
o
Tempe rature 40 C (1) GEDTA withou t NPK
(2) GEDT A with NPK
80 (3) SPA
(4) Pure soil

Water evaporation ratio (%)

60
1
2
40
3
4
20

0
0 10 20 30 40 50 60 70 80
Time(hou r)

Fig. 6. Water retention behaviors of soil with GEDTA without NPK (1), GEDTA with NPK, SPA and pure soil.

273 and 340.1  0.4 mg of potassium/g, was analyzed by the same References 314
274 procedure. After irrigation (500 mm/m2), the percentage of release
275 were: 96.1% (NH4+), 90.4% (H2PO4
) and 97.2% (K+), considering [1] L. Wu, M. Liu, R. Liang, Preparation and properties of a double-coated slow-
315
276 release NPK compound fertilizer with superabsorbent and water-retention,
samples in triplicate (n = 3). Comparing these results and results Bioresour. Technol. 99 (3) (2008) 547–554, doi:http://dx.doi.org/10.1016/j. 316
277 obtained by Wu et al. [1] with Fig. 5, it is possible to conclude that 317
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278 the slow release performed by GEDTA is slower. Thus, the release of [2] K. Zhong, Z.T. Lin, X.L. Zheng, G.B. Jiang, Y.S. Fang, X.Y. Mao, Z.W. Liao, Starch
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279 NPK in soil is more controlled. controlled-release fertilizers, Carbohydr. Polym. 92 (2) (2013) 1367–1376, doi: 319
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280 Measurement of the water-retention of GEDTA in soil [3] J.B.d Carmo, C. Neill, D.C. Garcia-Montiel, M. de Cássia Piccolo, C.C. Cerri, P.A.
Steudler, C.A. de Andrade, C.C. Passianoto, B.J. Feigl, J.M. Melillo, Nitrogen 321
dynamics during till and no-till pasture restoration sequences in Rondônia, 322
281 The results in Fig. 6 show that the soil with GEDTA (with or 323
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without NPK) the evaporation was slower in relation to the soil 10.1007/s10705-004-2213-8.
283 [4] F.G.E. Nogueira, N.T. Do Prado, L.C.A. Oliveira, A.R.R. Bastos, J.H. Lopes, J.G. De
without GEDTA. The analysis was performed in triplicate. Each 325
284 Carvalho, Incorporation of mineral phosphorus on leather waste (collagen): A
point found in the curve is the average of the measured values. new Ncollagen PK-fertilizer with slow-liberation, J. Hazard. Mater. 176 (1–3) 326
285 327
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286 environment at 40  C does not retain water in the soil for a long 20005039.
[5] J.B. Carmo, M.C. Piccolo, A.A. Cristiano, C.E.P. Cerri, J.B. Feigl, F.S. Neto, C.C. Cerri,
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288 ability to retain water in the soil decreases considerably. The microbial biomass after tillage during pasture re-establishment in Rondônia, 330
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Please cite this article in press as: A.M. Senna, et al., Synthesis, characterization and application of hydrogel derived from cellulose acetate as a
substrate for slow-release NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. (2015), http://dx.doi.org/10.1016/j.jece.2015.03.008