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1 First International Workshop on Alternative Potash Massachusetts First International Workshop on Alternative Potash Massachusetts Institute of Technology Cambridge, Massachusetts 02139 U.S.A. Tuesday, November 10, 2015 Closed Session Chipman Room (6‐104) Afternoon Program 3:00‐4:00 Registration 4:00‐4:30 Fertilizer from Feldspar, Introductory presentation Prof. Antoine Allanore 4:30‐5:00 Informal greetings, finalization of sessions and chairs, logistics, etc. Evening Program 6:00‐8:00 Dinner Catalyst Restaurant, 300 Technology Square, Cambridge, MA Telephone: (617) 576‐3000 Wednesday, November 11, 2015 Plenary Sessions Room 4‐237 Morning Program 9:00‐9:15 Opening remarks – The global situation (Profs. David Manning and Antoine Allanore) 9:15‐9:45 Weathering of K‐bearing minerals and the geochemical cycle of potassium (Prof. Lisa Stilllings) 9:45‐10:30 Rocks for Crops: New developments related to K silicate research and development (Prof. Van Straaten) 10:30‐10:45 Break 10:45‐11:30 Novel sources of potash for plant and crop nutrition (Prof. Manning) 1 11:30‐12:00 Unlock K from feldspar by root activities (Prof. Le Cadre) 12:00‐1:00 Lunch ‐ Chipman Room (6‐104) Jules Catering Afternoon Program Room 4‐237 1:00‐1:45 K‐fertilizers developments in Brazil (Prof. De Souza Martins) 1:45‐2:30 20 years of silicate fertilizers in China: production technology and agro‐applications (Prof. J. Liu) 2:30‐3:15 Hydrothermal processing of K‐feldspar as a source of potash (Prof. Allanore) 3:15‐3:30 Break Closed Session Chipman Room (6‐104) 3:30‐5:00 Discussion and brainstorming on the issues of alternative fertilizers (Chairs: Andrew Msolla and Annock Chiwona) Evening Program 6:00‐8:00 Dinner Legal Seafoods, 5 Cambridge Center, Cambridge, MA Telephone: (617) 864‐3400 2 Thursday, November 12, 2015 Closed sessions Room E90‐1283 Morning Program 8:30‐10:00 Nexus economy‐alternative fertilizers (Chair: Benedict Kanu) 10:00‐10:15 Break 10:15‐11:45 Nexus soil‐alternative fertilizers (Chairs: Edith Le Cadre and Eder Martins) 11:45‐1:00 Nexus private sector‐alternative fertilizers (Chairs: Ingo Wender and David Manning) Afternoon Program 1:00‐1:15 Farewell (Prof. Antoine Allanore) Optional MIT campus and laboratory visit 3 Program Abstracts HYDROTHERMAL PROCESSING OF K‐FELDSPAR AS A SOURCE OF POTASH Allanore, A. Soluble potassium salts used as fertilizers (potash) are a key commodity necessary to develop agriculture in the Global South. Unfortunately, all sources of potash are located at a far distance from the tropics, which is where they are needed the most in order to maintain an adequate soil fertility. Poor infrastructure and cost for transportation make potash both physically and economically inaccessible to the poorest farmers. Therefore, new materials derived from local and inexpensive sources are needed. In this contribution, we discuss one such material called hydrosyenite, which is obtained as a product of hydrothermal processing of K‐feldspar (KAlSiO3) at 200 °C and ~1,500 kPa, in presence of CaO (molar ratio Ca/Si in the initial mixture equal 0.3). We characterize the hydrosyenite material determining i) its mineralogical composition by X‐rays powder diffraction, ii) its specific surface area by isothermal nitrogen adsorption and iii) its morphology by observations with both a standard and a Scanning Electron Microscope (SEM). The mobility of potassium ions in hydrosyenite is greatly enhanced with respect to that one in K‐feldspar, which is explained, at least partially, by the formation of a calcium silicate amorphous phase during the hydrothermal treatment. Our preliminary results show that a comprehensive understanding of this phase will permit to engineering a new generation of affordable fertilizers with tunable release of potassium. Our research highlights both the opportunity and necessity to link knowledge on traditional processes and materials (e.g., formation of C‐S‐H phases in cement pastes) and the needs of tropical agricultures. [1] Skorina T. and Allanore, A. (2015). Aqueous alteration of potassium‐bearing aluminosilicate minerals: from mechanism to processing. Green Chemistry, 17(4), 2123‐2136. [2] Ciceri D., Manning D.A. and Allanore A. (2015). Historical and technical developments of potassium resources. Science of the Total Environment, 502, 590‐ 601. [3] Rao J.R., Nayak R., & Suryanarayana A. (1998). Feldspar for potassium, fertilisers, catalysts and cement. Asian J. Chem, 10(4), 690‐706. [4] Jeyabaskaran, K.J., Pandey S.D. and Gomadhi, G. (2003). Effect of potassium‐rich cement kiln flue dust and distillery effluent as substitute for potassium fertilizer on growth, yield and quality of “Ney Poovan” banana (Musa × paradisiaca). Indian journal of agricultural science, 73(12), 645‐648. 6 K‐FERTILIZERS DEVELOPMENTS IN BRAZIL De Souza Martins, E. Conventional fertilizers sources are commodities which are limited to tropical agriculture, due to scarce reserves and high costs. Brazil depends at least 70% of imported NPK sources, and is greater than 90% for the K requirement. Meanwhile, fertilizer use efficiency is decreasing in the last twenty years. This challenge leads to some initiatives to increase nutrient efficiency in agriculture by coating NPK fertilizers with polymers, clay minerals and agro‐industrial wastes [1]. Other strategies seek to use regional sources of nutrients such as bio‐fertilizers, biochar, and stonemeal [2]. Industrial processes can transform these regional sources to increase their agronomic efficiency, for example, hydrothermal processes [3]. Regulatory processes are moving forward with the Soil Remineralizers Law and allowing the development of new sources. The Embrapa research program developed in the last fifteen years on alternative sources of nutrients shows that some silicate rocks are K sources, especially biotite/phlogopite or feldspathoids rich rocks. Alkali feldspar‐rich rocks generally have low agronomic efficiency. However, our studies show that the degree of crystallographic disorder can greatly enhance the K availability derived from alkali feldspars. Hydrothermal industrial processes also lead to reduction of crystallographic order of the alkali feldspars and increases the K availability. The efficiency of utilization of nutrients silicate derivatives hangs on demand of plants by bioweathering processes, since the water solubility is very low. The transformation of silicate minerals in agricultural tropical soils increases permanent Cation Exchange Capacity (CEC) and the efficiency of management cationic nutrients [4]. The agronomic residual effect of silicate sources is high and can be extended for up to three cycles of crops. The performance indexes of these K sources indicate that the economic viability varies 100‐500 km radius of its production origin to the agricultural areas. These sources of regional nutrients still has the potential to intensify carbon sequestration in agricultural soils and increase the sustainability of food production [2]. [1] Benites V., Oliveira Júnior A., Pavinato P.S., Teixeira P.C., Moraes M.F., Leite R.M.V.B.C. and Oliveira R.P. (eds.) (2014). Proceedings of 16th World Fertilizer Congress of CIEC, Rio de Janeiro‐RJ, p. 410. [2] Goreau. T.J., Larson R.W and Campe J. (eds.) (2015). Geotherapy: innovative methods of soil fertility restoration, carbon sequestration, and reversing CO2 increase. CRC Press, p. 589. [3] Skorina T. and Allanore A. (2015). Aqueous alteration of potassium‐bearing aluminosilicate minerals: from mechanism to processing. Green Chemistry, 17(4), 2123‐2136. [4] Martins E.S., Silveira C.A.P., Bamberg A.L., Martinazzo R., Bergmann M. and Angélica R.S. (2014). Silicate agrominerals as nutrient source and as soil conditioners for tropical agriculture. In: V.M. Benites et al. (eds.), Proceedings of 16th World Fertilizer Congress of CIEC, Rio de Janeiro‐RJ, p. 138. 7 UNLOCK K FROM FELDSPAR BY ROOT ACTIVITIES Le Cadre, E. in collaboration with Simon, B., Aznar, J.L., Arnal, D. and Hinsinger P. In the manufacture of ceramics, feldspars are an important ingredient. Mining of feldspars deposits generates co‐mining products, which can be used as direct application K fertilizers. Agronomic efficiency of the co‐mining products depends on their intrinsic chemical reactivity defined by particle size and elementary composition but also by the soil‐plant compartiment. In particular, root activities can modify the dissolution rate of feldspars by modifying the surrounding soil known as a “rhizosphere effect”. Consequenty, the availability of nutrient in root vicinities, or environmental availability, is often larger than estimated in bulk soils. When considering the bioavailability of K to plants, more interactions that occur in the rhizosphere have to be considered. Our research project is to compare the dissolution rates of albite, syenite, micas and K‐Feldspars with different granulometry (<80 to <5000 micrometers) in batch systems during 13 days in presence of cationic exchange resin as a plant proxy. Syenite, albite and K Feldspars are the most promising K fertilizers with 3.49, 3.59 and 2.73% of total K released after 13 days. Within the first 24h, we measure an important release of K probably ascribable to the dissolution of very fine particles. We also measured in a devoted crop devices the bioavailability of K with and without soil. In these experiments, plants accumulated more K than estimated by batch experiments. The % of K accumulated in plants/K total from syenite is greater compared to K Feldspar and in a lesser extent albite. Our findings suggest that dissolution can be promoted in the field by placement near roots to benefit root activities on dissolution and perhaps by some management practices or plurispecific crop designs. 8 20 YEARS OF SILICATE FERTILIZERS IN CHINA: PRODUCTION TECHNOLOGY AND AGRO‐APPLICATIONS. Liu, J. in collaboration with Han, C., Liu, S. and Sheng, X. Potassium has an element abundance of 2.47%, but only a very small part of potassium is in the form of water‐soluble salts. Over 98% of K is found in silicate rocks, in the form of water‐insoluble and plant unavailable silicate minerals, such as K‐ feldspar and mica.
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