EP3442339A1 - Metal oxide based soil conditioner - Google Patents
Metal oxide based soil conditionerInfo
- Publication number
- EP3442339A1 EP3442339A1 EP17773454.8A EP17773454A EP3442339A1 EP 3442339 A1 EP3442339 A1 EP 3442339A1 EP 17773454 A EP17773454 A EP 17773454A EP 3442339 A1 EP3442339 A1 EP 3442339A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- soil
- metal oxide
- availability
- iron
- oxide based
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
Definitions
- the present invention relates to nano metal oxide based soil conditioners. More specifically, the present invention relates to nano metal oxide based soil conditioners comprising iron oxalate capped metal oxide(s).
- the said soil conditioners are capable of enhancing the iron availability to plants from soil without increasing soil acidity and hindering phosphorous availability in soil.
- the iron oxalate capped metal oxides of the present invention is directed to increase the nitrogen and phosphorus availability in such treated soil
- the present invention provides an industrially scalable process for the production of environmentally safe iron oxalate capped metal (Fe, Mn, and Cu) oxide nanomaterials as solid conditioners.
- the synthesized [ Fe(ox)-Fe(0)] nanomaterial is capable of producing iron oxalate capped Fe 3 0 4 [Fe(ox)-Fe 3 0 4 ] from the aerial oxidation of Fe(0) at room temperature.
- the iron content and iron release profile of [Fe(ox)-Fe 3 0 4 ] material is found to be 19% and 58 mg L "1 respectively.
- the basic object of the present invention is thus directed to provide nano metal oxide based soil conditioner which would be simple and cost-effectiveto enhance iron availability to plants from soil.
- Another object of the present invention is to provide the said metal oxide based soil conditioner for sustained availability of Fe, Mn, and Cu in the soil for plant assimilation.
- Another object of the present invention is to provide iron oxalate capped metal oxides to increase the nitrogen and phosphorus availability in treated soils.
- Another object of the present invention is to enhance iron availability to the plants without hindering phosphorous availability in soil.
- Another object of the present invention is to provide Fe as a micronutrient without increasing soil acidity.
- Another object of the present invention is to enhance crop growth and yield under field condition using in the said metal oxide based soil conditioner of the present invention.
- Another object of the present invention is to provide for method of treatment of soil with the said metal oxide based soil conditioner to enhance growth and favourable production of plants including the enhancement of expression of GS1 and GOGAT genes that are responsible for primary nitrogen assimilation in plants.
- metal oxide based soil conditioner comprising nano iron oxalate capped metal oxide(s) wherein the nano iron oxalate capped metal(s) oxide comprise selectively (i) Fe(Ox)-Fe 3 0 4 with Fe sourced from Fe salts other than Mohr salt with atleast four folds enhanced Fe release capability in soil with respect to Fe(Ox)- Fe 3 0 4 with Fe sourced from Mohr salt and (ii) mixed metal oxides selected from Fe(ox) Fe-MnO x and Fe(ox) Fe-CuO x involving said Fe(Ox)- Fe 3 0 4 with Fe sourcedfrom Fe salts other than Mohr salt.
- metal oxide based soil conditioner which is a reaction product of iron salts other than Mohr's salt, oxalic acid followed by reduction with Sodium Borohydride, and optionally other metal salts at elevated temperature providing said caped metal oxide with its said selective Fe source with or without other metal micronutrients favouring enhancing sustained availability of metal micronutrients, N, P for plant assimilation and stabilisation in pH of treated soil in the range of 5.0 to 6.0.
- metal oxide based soil conditioner wherein the ratio of iron oxalate to Fe 3 0 4 are in the range from 1:0.1 to 1:1.
- the present invention provides metal oxide based soil conditioner comprising porous structure connected with nano ribbon like structures with uniform particle size in the range of 2-16 nm and average particle size in the range of 9 to 32 nm.
- the present invention provides metal oxide based soil conditioner wherein the aspect ratio of the particles of Fe(ox)-Fe304 is 15-20, Fe(ox)Fe-MnOx is 1 - 4 and Fe(ox) Fe-CuOx is 10-15.
- the present invention provides metal oxide based soil conditioner wherein surface area, pore radius and pore volume of the particles are as hereunder:
- Another aspect of the present invention provides mMetal oxide based soil conditioner further characterised by: i) The XRD pattern of Fe(ox)-Fe304, Fe(ox) Fe-CuOx, and Fe(ox) Fe-MnOx showing presence of orthorhombic iron oxalate and magnetite Fe304; orthorhombic Fe(C204), 2H20, Fe304, and CuO; and orthorhombic Fe(C204).2H20, Fe304, and MnO; ii) FT-IR having peaks of 1685, 1412, and 563 cm-1 for Fe(ox)-Fe304, 1691, 1360, 1319 and 502 cm-1.
- Fe(ox)Fe-MnOx i. enhances Fe availability by 10.0 - 14.5 mg kg "1 in 5 to 90 days and Mn content increases by 35.0 - 40.0 mg kg "1 in 5 to 90 days; ii. increases N and P availability in soil from 1.3 % to 5.3 % and 46 mg kg-1 to 90 mg kg-1 iii. enhances activity of soil enzymes urease and Phosphatase from 18.0 to 27.0 ⁇ g g-1 and 11.0 to 21.0 ⁇ g g-1 respectively. and
- the present invention relates to metal oxide based soil conditioner when used for treatment of soil enhances the Fe availability in the range of 19 to 29 %.
- Yet another aspect of the present invention provides metal oxide based soil conditioners which significantly reduces the bulk density of soil treated by the said metal oxides at least by 7%.
- the present invention provides metal oxide based soil conditioner wherein soils treated with the said metal oxides increase tomato yields at least by 80 to 90% as compared to FeS04 and 70 to 80 % as compared to Fe-EDTA with concomitant increase in carotenoid and chlorophyll content at least by 85 to 90% and 90 to 95%, respectively as compared to soil conventionally treated with Ferrous Sulphate and Fe-EDTA.
- the present invention provides metal oxide based soil conditioner wherein the soils treated with the said metal(s) oxide enhances the expression of GS1 and GOGAT genes in tomato as compared to conventional Fe- EDTA treated soils.
- Another aspect of the present invention provides use of Metal oxide based soil conditioner as claimed in anyone of the preceding claims for conditioning soil including selectively one or more of : i) stabilising soil pH, ii) increasing iron availability in soil without increasing the acidity, iii) reduction of soil bulk density, iv) increasing N and P availability in soil ; v) enhancing activity of soil enzymes such as urease and phosphatise.
- a further aspect of the present invention provides a process for enriched availability of plant nutrients in soil for enhanced plant growth comprising treating the soil with nano metal oxide based soil conditioners of the present invention.
- a still further aspect of the present invention provides a process comprising steps of: (i) preparing the field by light secondary ploughing followed by levelling of the soil surface prior to planting;
- the present invention provides a process for treating soil for tomato cultivation with said soil conditioners selected from one or more of [Fe(ox)-Fe304, Fe(ox)Fe-MnOx, and Fe(ox) Fe-CuOx] for enhanced conditioning of soil as compared to Fe-EDTA and control including i. Fe(ox)Fe-MnOx treatment for raising the expression of GOGAT genes in tomato by 0.12 units as compared to Fe-EDTA treatment. ii. Fe(ox)-Fe304 treatment for raising the expression of GOGAT genes by 0.05 unit as compared to Fe-EDTA . iii. Fe(ox) Fe-CuOx and Fe(ox)-Fe304 treatment for raising the xpression of GS1 gene by 0.23 and 0.19 units respectively as compared to Fe-EDTA treatment.
- said soil conditioners selected from one or more of [Fe(ox)-Fe304, Fe(ox)Fe-MnOx, and Fe(ox) Fe
- Another aspect of the present invention provides for a process for manufacture of the said metal oxide based soil conditioner comprising steps of:
- the present invention provides for a process wherein the molar ratio of ferrous salt : oxalate is in the range of 0.3 to 3, and said optional step for providing mixed metal oxide comprise further reacting with copper sulphate and potassium permanganate for the preparation of Fe(ox) Fe-CuOx and Fe(ox)Fe-MnOx respectively and wherein the molar ratio of ferrous salt : copper in mixed Fe(ox) Fe-CuOx is 0.5 to 3, and molar ratio of ferrous salt : manganese in mixed nano Fe(ox)Fe-MnOx is in the range of 0.5 to 3.
- Fig. 2 Comparative FT-IR of prepared materials: (a) Fe(ox)-Fe(0)and Fe(ox)- Fe 3 0 4 with Iron oxalate complex; (b) FT-IR spectrum of Fe(ox) Fe-CuO x and Fe(ox)Fe-MnO x .
- Fig. 3 (a) and (b) HR-SEM and EDS of Fe(ox)-Fe 3 0 4 nanomaterial; (c) and (d) HR-TEM of Fe(ox)-Fe(0) nanomaterial and of Fe(ox)-Fe 3 0 4 nanomaterial.
- Fig.6 EDS Analysis: (a) Fe(ox) Fe-CuO x ; (b) Fe(ox) Fe-MnO x .
- Figure 7(a) Effects on pH, BD and Fe content in soil.
- Figure 7(b) Effects on Mn and Cu content in soil.
- FIG. 9 Changes in phosphate & Fe availability and pH status with time Figure 10:RT-PCR using GS1 and GOGAT gene-specific primers where gapdh served as an internal control.
- T1 Control
- T2 Fe(ox) - Fe 3 0 4!
- T3 Fe(ox)Fe- ⁇
- T4 Fe(ox)Fe-CuO x
- T5 Fe-EDTA
- the present advancement resides in the surprising finding that soil treated with iron oxalate capped nano metallic oxides of the present invention are unexpectedly and significantly capable of enhancing the iron, manganese, and copper availability to plants from treated soil. Further, the N and P availability in such treated soil also significantly increased in soils treated with nano metal oxide based soil conditioners of the present invention.
- the scale up is cumbersome.
- the present invention overcomes the problems of the prior art and provides a commercially scalable process for the preparation nano metal oxide based soil conditioners of the present invention.
- the Fe(ox) containing metal(s) oxide nanomaterial is prepared as per the scheme depicted below:
- ferrous salt Any ferrous salt may be used. However ferrous sulphate is preferred.
- the iron content of [ Fe(ox)-Fe 3 0 4 ] material prepared from FeS0 4 is higher than (28.6%) the previously prepared material (19.2%) from Mohr salt [prior art route] .
- Fe(ox) containing metal(s) oxide nanomaterial is found to be high yielding (84%) compared to Mohr salt method (63%) [prior art route].
- the overall yield of [ Fe(ox)- Fe 3 0 4 ] nanomaterial synthesized from other ferrous salts such as FeCI 2 .4H 2 0 and Fe(N0 3 )2.9H 2 0 is 75 % and 71%, respectively.
- the iron content of [Fe(ox)-Fe 3 0 4 ] nanomaterial prepared from FeCI 2 .4H 2 0 and Fe(N0 3 ) 2 is 23.5 % and 24.1%, respectively.
- the release of Fe from the nano metal oxide based soil conditioners of the present invention exhibits 5 fold increase in Fe release (286.8 mg L “1 ) as compared to the Fe release (58 mg L “1 ) from Fe(ox)-Fe 3 0 4 prepared from Mohr salt observed in prior art.
- Fe(ox)Fe-MnO x nanomaterial is
- Feiox ⁇ Fe ⁇ MnQ x The process of the present invention includes the reaction of ferrous salt and oxalic acid in aqueous medium at room temperature followed by reduction with Sodium Borohydride to obtain Fe(ox)-Fe(0).
- Fe(ox)-Fe(0) material is in situ reacted with Copper sulphate (if the Fe(ox) Fe-CuO x is required) or with Potassium Permanganate solution (if the Fe(ox)Fe-MnO x is required).
- the product is separated and dried at about 80°C. This preparation does not involve any high temperature calcination.
- the amount of oxalic acid and iron in the synthesized [ Fe(ox) -Fe 3 0 4 ] nanomaterial was determined by titration of potassium permanganate solution (KMn0 4 ) and spectrophotometric determination of iron by reacting with o- phenanthroline.
- the ratio between oxalate and iron in nano [Fe(ox)-Fe 3 0 4 ] obtained from ferrous sulphate is higher than (1:3) the material (1:5) obtained from mohr's salt.
- the ratio of iron oxalate and Fe 3 0 4 of nano [ Fe(ox)-Fe 3 0 4 ] material prepared from FeS0 4 is lower than (1:0.7) the previously prepared material (1 : 1.3) from Mohr salt.
- Example I Synthesis of the Fe(ox) capped metal(s) oxide nanomaterial a) Preparation of Fe(ox)-Fe 3 0 4 nanomaterial
- the volume of oxalic acid consumed during the course of the reaction i.e., the amount of oxalic acid binding with the formed nanoparticles is determined by titrating against aqueous solution of potassium permanganate solution (KMn0 4 ).
- the amount of iron in the oxalate capped nanomaterial was determined by reacting iron(ll) with o-phenanthroline to form an orange-red complex, which was monitored with UV-vis spectrum.
- the ratio between oxalate and iron in nano [Fe(ox)-Fe 3 0 4 ] obtained from ferrous sulphate is higher than (1:3) the material (1:5) obtained from mohr's salt.
- the ratio of iron oxalate and Fe 3 0 4 of nano [Fe(ox)-Fe 3 0 4 ] material prepared from FeS0 4 is lower than (1:0.7) the previously prepared material (1:1.3) from Mohr salt. b) Process for the preparation of Fe(ox) -Fe-CuO x nanomaterial
- reaction mixture was kept at 80°C under stirring for 12 h to produce yellow-brown color nanomaterial, which was centrifuged from the reaction mixture, washed with distilled water for several times to remove un- reacted metal salt and dried in oven at 80 °C for 8 h. Finally, 47 g yellow-brown Fe(ox) Fe-CuO x nanomaterial was collected from the reaction.
- the similar procedure may be applied to synthesize the said material from other ferrous salts like; FeCI 2 .4H 2 0 and Fe(N0 3 ) 2 .9H 2 0 with 42g and 40g yield, respectively.
- the said procedure may be applied for other ferrous salts like; FeCI 2 .4H 2 0 and Fe(N0 3 ) 2 .9H 2 0 to synthesize nano Fe(ox)-Fe-MnO x with 38g and 41g yield, respectively.
- Example 11 Characterization of synthesisedmetal oxide based
- the XRD of the prepared material [ Fe(ox)-Fe(0)] shows the presence of orthorhombic Fe(C 2 0 4 ). 2H 2 0 (Fig. 1a). As the peaks for Fe(ox) and Fe(0) overlap, it is difficult to detect them separately. However, [ Fe(ox)-Fe(0)] (the black material) reduces methylene blue to its corresponding leuco methylene blue and after this reaction, the black material transforms into brown material because of the oxidation of Fe(0) to its corresponding oxide.
- the XRD pattern of oxidized material shows the presence of both orthorhombic iron oxalate and magnetite Fe 3 0 4 ( Fig.1 b) [Aragon, M. J., et.al.
- the FT-IR of the prepared materials are shown in Fig. 2.
- Ferrous Oxalate [Fe(C 2 0 4 ). 2H 2 0] shows two peaks at 1640 and 1362 cm “1 for typical metal carboxylate, in which oxalic acid acts as a bidentate ligand. The other two peaks at 1320, 820 cm “1 are due to the C-0 and C-C stretching vibration of coordinated oxalate in Fe(C 2 0 4 ).2H 2 0.
- the comparative FT-IR of the prepared [ Fe(ox)-Fe(0)] and Fe(C 2 0 4 ). 2H 2 0 clearly shows the presence of iron oxalate in synthesized [Fe(ox)-Fe(0)].
- the HR-TEM as represented in Figs. 3 and 4 of Fe(ox)-Fe(0) characterises the material as porous connected with several nano ribbon like structure, which are similar to the HR-TEM of Fe(ox)-Fe 3 0 4 .
- the SEM of Fe(ox) Fe-CuO x and Fe(ox)Fe- MnO x also shows porous structures.
- Fig. 5 presents the particle size distribution profile of all the synthesized materials from HR-TEM images using Image J software. The materials exhibit uniform particle size having narrow distribution in the range of 2-16 nm. The profiles are fitted with Gaussian distribution to obtain the average particle size.
- the average particle size of Fe(ox)-Fe(0) and Fe(ox)- Fe 3 0 4 are found to be 39 and 32 nm respectively. On the other hand, the average particle size are 12 and 9 nm respectively in Fe(ox) Fe-CuO x and Fe(ox) Fe-MnO x material. It is worthwhile to mention that the aspect ratio of Fe(ox)-Fe(0) and Fe(ox)-Fe 3 0 4 materials (19 and 17) is greater than the Fe(ox) Fe-CuO x and Fe(ox)Fe-MnO x (11 and 2) materials.
- EDS Energy Dispersive Spectroscopic Analysis
- Fig. 6 presents the EDS analysis of Fe(ox) Fe-CuO x and Fe(ox) Fe-MnO x which is consistent with respect to the wt % of carbon, oxygen, iron, Cu and Mn in the prepared materials.
- Table 1 presents the results of BET Analysis of prepared materials. These textural characteristics are consistent with the results of HR-SEM and HR-TEM.
- Example-Ill Improvement in Soil Quality using Fe(ox)-Fe30 4 , Fe(ox)Fe-CuO x , and Fe(ox)Fe-MnO x
- Table 2a Fe release from the two preparation pathways [Mohr salt (prior art) and FeS0 4 ( present invention)] of Fe(ox)-Fe 3 0 4 in aqueous solution
- the soil samples were incubated with Fe(ox) - Fe 3 0 4 , Fe(ox) Fe-CuO x and Fe(ox)Fe- MnO x @ 10 mg kg "1 .
- Soil samples were also incubated with 3% FeS0 4 and 10 mg kg "1 Fe-EDTA respectively which were used as controls.
- the study was conducted for 90 days.
- the soil pH increased by from 5.5 to 5.7as compared to the initial value (5.5 ⁇ 0.1) under 10 mg kg "1 Fe(ox)- Fe 3 0 4 in 90 days (Fig. 7a).
- the soil pH also was 5.55 ⁇ 0.09 and 5.58 ⁇ 0.02 under 10 mg kg "1 application of Fe(ox) Fe-CuO x and Fe(ox) Fe-MnO x respectively.
- soil pH was reduced by 1.27 times from 5.5 ⁇ 0.1 to 4.3 ⁇ 0.2 after 90 day due to application of FeS0 4 .
- Fe(ox)Fe-MnO x is 10.0 - 14.5 mg kg "1 in 5 to 90 days and by Fe(ox) Fe-CuO x is 6 -10 mg kg "1 in 5 to 90 days respectively ]
- Mn content in the soil increased from 81.39 ⁇ 1.5 mg kg "1 to 154.45 ⁇ 4.2 mg kg "1 during 45 days due to application of Fe(ox)Fe- MnO x and then decreased to 119+3.6 mg kg "1 during 90 days (Fig. 7b).
- Mn content increases by 35.0 - 40.0 mg kg- 1 in 5 to 90 days]
- Cu content increased in the soil from 13.15+ 1.1 mg kg "1 to
- N and P availability in soil significantly increased from 1.34+ 0.11 % to 7.38 ⁇ 0.5 % and 49.64 ⁇ 0.8 mg kg "1 to 105.54 ⁇ 1 mg kg "1 due to application of Fe(ox)-Fe 3 0 4 (P 0.000). • P availability reduced from 44.15 ⁇ 1.1 mg kg "1 to 40.12 ⁇ 1.1 mg kg "1 in soil due to 3% FeS0 4 application.
- Example IV Demonstration of the effect of Fe(ox) -Fe 3 0 4 , Fe(ox)Fe- MnO x , and Fe(ox) Fe-CuO x to maintain balance in soil pH and P availability in treated soils.
- pH of the weakly acid, neutral and alkaline solutions (pH 6, 7, 8, and 8.5) noticeably shifted towards high acidity (pH: 6 reduced to 5.4 ⁇ 0.02; 7 reduced to 5.5 ⁇ 0.02; 8.5 reduced to 5.2 ⁇ 0.02) on addition of FeS0 4 to the solutions (Table 4).
- Example V Field Trials of soil treated with Fe(ox) -Fe 3 0 4 , Fe(ox) Fe-MnO x and Fe(ox) Fe-CuO x and their impact on crop productivity
- Fe(ox)- Fe 3 0 4 , Fe(ox) Fe-MnO x and Fe(ox) Fe-CuO x were field tested on tomato.
- Three doses of three prepared compounds were selected for the study and compared with FeS0 4 @ 20 kg ha "1 (recommended dose) used as control. All other agronomic management practices such as seed treatment, land preparation, fertilizer (NPK) application, and intercultural operation and pest control measures were uniformly conducted for all the treatments following the package of practice recommended by the Department of Agriculture, Govt, of Assam. The study was conducted in a randomized block design with four replicates.
- Chlorophyll content in tomato leaves was significantly high when Fe(ox)- Fe 3 0 4 was applied as 2 kg ha "1 (48.59 ⁇ 0.13 mg g "1 ). • The 10 kg ha "1 dose for Fe(ox)-Fe 3 0 4 also showed good chlorophyll content (47.65 ⁇ 0.52 mg g "1 ).
- Table 5 Representation of Chlorophyll and carotenoid data in various doses of synthesized compounds in field trial
- the effect of the Fe-ox capped metal oxide nanomaterialsof the present invention on the physiological metabolism of the treated tomato plants and one of the most vital nutrient mediated metabolic pathways (i.e., Nitrogen assimilation pathway) was targeted.
- the expression of GS1 and GOGAT genes essential in nitrogen assimilation in tomato leaves [treated with Fe(ox)-Fe 3 0 4i Fe(ox) Fe-MnO x and Fe(ox) Fe-CuO x ] was evaluated in comparison with control and Fe-EDTA treated plants (Fig. 10).
- the Fe-EDTA was taken as positive control because it is a well known eco-friendly and effective iron fertilizer.
- the expressions of GS1 and GOGAT genes were assessed against a house keeping gene gapdh which are constitutive genes for the maintenance of basic cellular function; and they express in all cells of any organism under normal conditions (Kon Butte et al., 2001).
- the said nanomaterials as exemplified above according to the advancement Fe(ox)- Fe 3 0 4 , Fe(ox) Fe-MnO x and Fe(ox) Fe-CuO x not only enhance the Fe availability in the soil for the assimilation by plants, but also positively impacts the N and P availability, improves phosphate release, controls pH of soil, reduces the bulk density of the soil thereby improving porosity as compared to conventional Ferrous Sulphate or Fe-EDTA treated soils.
- novel soil conditioners comprising capped metal oxide nanomaterials which enhance the iron availability to the plants along with improved nitrogen and phosphorus availability to the plants over the conventional Fe fertilizers or soil conditioners.
- the said iorn oxalate capped metal oxide nanomaterials also activate genes for nitrogen assimilation, have positive impact on the soil health and maintain balance in soil pH. Hence the application of the said nanomaterials improves the crop yields significantly.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IN201631010727 | 2016-03-29 | ||
PCT/IN2017/050114 WO2017168446A1 (en) | 2016-03-29 | 2017-03-29 | Metal oxide based soil conditioner |
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EP3442339A1 true EP3442339A1 (en) | 2019-02-20 |
EP3442339A4 EP3442339A4 (en) | 2019-12-11 |
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EP17773454.8A Withdrawn EP3442339A4 (en) | 2016-03-29 | 2017-03-29 | Metal oxide based soil conditioner |
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CN109650974B (en) * | 2019-01-14 | 2021-07-09 | 湖南大学 | Method for reducing nitrogen loss in composting process and improving fertilizer efficiency of compost product by using iron oxide nano material |
LU500680B1 (en) | 2021-09-23 | 2023-03-23 | Behrouz Mohammad Einolllahi | Nano-chelated complexes |
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DE10248022B4 (en) * | 2002-10-15 | 2008-11-13 | Lanxess Deutschland Gmbh | Use of chelated plant trace nutrients |
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- 2017-03-29 WO PCT/IN2017/050114 patent/WO2017168446A1/en active Application Filing
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