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September 2008

Study on the Rapid Method to Predict Longevity of Controlled Release Fertilizer Coated by Water Soluble Resin

DAI Jian-jun1, 2, FAN Xiao-lin2, YU Jian-gang2, LIU Fang2 and ZHANG Qiao2

1 2

College of Resources and Environment, Northeast Agricultural University, Harbin 150030, P.R.China Fertilizer and Balanced Fertilization Research Lab, College of Resources and Environment, South China Agricultural University, Guangzhou 510642, P.R.China

Abstracts

The study discussed the rapid method to test and predict the longevity of controlled release fertilizers (CRFs) coated by water soluble resin by using the short-term leaching under higher temperature. Pure water dissolving incubation and higher temperature leaching were used to study the patterns of the nutrient release of the CRFs. The correlation analysis between the days at 25C and the hours at 80C of Trincote 1 and Trincote 2 for the same cumulative release rates were conducted. Patterns of cumulative nutrient release curve followed one factor quadratic regression equation at each given temperatures, and each of relative coefficient was bigger than 0.995. As the temperature increased, nutrients release of the CRFs increased. The longevity of resin coated CRFs were predicted by use of both the cumulative nutrients release equation at 80C and the regression equation of release time needed for the same cumulative release rates between 25 and 80C. There were only 0.3-6.9% relative errors between the tested longevity and predicted one. In conclusion, the longevity of resin coated CRFs could be predicted more quickly and precisely by use of the higher temperature short-term leaching method than that of the traditional differential release rate. The longevity of resin coated CRF could be rapidly and precisely predicted in a few hours by application of the higher temperature shortterm leaching method. Key words: controlled release fertilizer (CRF), water soluble resin coating, longevity of CRF, rapid test method

INTRODUCTION

The methods of longevity predicting and nutrient release test of controlled release fertilizers (CRFs) have been studied since the CRF emerged in the early 50s of the 20th century. However, there is not any uniform standard method for the longevity predicting and nutrient release of CRFs (Li et al. 2005). Based on the definition of slow and CRF by Europe Standard Committee, pure water dissolving incubation at 25C is the conventional method to describe the release

This paper is translated from its Chinese version in Scientia Agricultura Sinica.

characteristics, and the days for 75% release rate of CRFs were defined as the longevity (Trenkel 1997). For instance, in Japanese Chisso-Asahi Fertilizer Corporation, the nutrient release of 75% at 25C is considered as the criteria of its polymer coated fertilizer products, such as Nutricote and Meister (Li et al. 2005); whereas the time needed for nutrient release test is too long to be suitable for the rapid test of commercial CRFs and its production online. Since nutrient release through the polymer membrane of CRFs primarily depends on temperature, increasing temperature would geminate nutrient release of CRFs (Chen et al. 2002; Zhang

DAI Jian-jun, Associate Professor, E-mail: daijianjunj@126.com; Correspondence FAN Xiao-lin, Professor, Tel: +86-20-85288325, E-mail: xlfan@scau.edu.cn

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et al. 2005). Hence, the author has reported the work of rapid test of CRFs longevity at higher temperature (Dai et al. 2006). It was found that some of the coating membranes were broken or agglomerated when temperature rose too high to cause abnormal nutrient release, which would affect the longevity of CRFs predicted precisely. In addition, this method was unsatisfactory for the CRFs predicting of very long longevity. In this article, based on the previous studies of author, higher temperature leaching experiment was conducted, the optimal test temperature was selected from 50 to 90C, correlation analysis of the time at the optimal test temperature and 25C for the same nutrient release rate was made, the feasibility of the longevity of CRFs predicted by use of this higher temperature leaching method was discussed. These results have significant implication and provide valuable information for development of rapid test method of CRF.

Materials

Granular superstar compound fertilizer (22-6-12) was coated in fluidized bed with water soluble resin of 80 g m-2 called as Trincote 1 and of 100 g m-2 as Trincote 2. The nitrogen sources of the superstar compound fertilizer (22-6-12) were ammonium-N and nitrate-N.

Methods

Longevities determination of the CRFs 12.500 grams of fertilizer samples were accurately weighed, transferred into nylon bags (1 mm), and then placed in plastic bottles containing 250 mL distilled water. The bottles were incubated at (25 0.5)C. Every week, the solutions were analyzed using Orion 105A electric conductivity meter, the bags were taken out of the bottles, and transferred into new plastic bottles containing 250 mL distilled water, until the cumulative nutrients release rate from CRF reached 75%. Each fertilizer sample had 3 replicates. The release rates of the CRFs were calculated using the standard curves (Dai et al. 2005, 2006). Experiments of higher temperatures leaching 5.000 grams of fertilizer samples were placed into separatory

funnels at leaching temperatures of (50 0.5)C, (60 0.5)C, (70 0.5)C, (80 0.5)C, and (90 0.5)C, respectively. The leaching solutions were collected in 250 mL Paris:l volumetric flasks for electric conductivity analysis. The dropping velocity of leaching was 250 mL per 15 min. Each fertilizer sample was leached for 6 hours and had 3 replicates. Analysis of the optimal temperature and rapid test at the optimal temperature The cumulative release rate curves of the 2 CRFs at 50, 60, 70, 80, and 90C were obtained from above results, respectively. Then, these cumulative release rate curves at higher temperatures were compared with that at 25C to select the optimal temperature. The criteria of the optimal temperature were supposed as follows: (i) The curve pattern was similar to that of 25C; (ii) the release rate was the most among the treatments during the leaching; and (iii) there were no phenomenon of abnormal release appeared, such as coating membrane broken and fertilizer agglomerated. The standard curve 12.500 grams of fertilizer samples were accurately weighed, triturated in a mortar, washed with distilled water, transferred into a 250 mL volumetric flask, filtered, and collected to be tested. Then, the fertilizer solutions with concentrations of 0, 0.002, 0.004, 0.006, 0.008, 0.01, 0.02, 0.04, 0.06, 0.08, and 0.10%, were prepared in 100 mL volumetric flasks, respectively, for the electric conductivity analysis of the standard curve. Using the electric conductivity of the solution as the independent variable, and the fertilizer content (%) or nutrients release rate (%) as the dependent variable, the standard curve equations were obtained after regression analysis of above data. The fertilizer content (%) and nutrients release rate (%) of CRFs incubation solution could be calculated using this standard curve equation (Dai et al. 2005). Regression analysis between the release time at 25C and optimal temperature for the same cumulative release rate The regression analysis between the release time at 25C and that at the optimal temperature for the same cumulative release rate was conducted, and a one factor quadratic equation was constructed, where x represented the time needed for cumulative release rate of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, and 75% at the optimal

Study on the Rapid Method to Predict Longevity of Controlled Release Fertilizer Coated by Water Soluble Resin

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RESULTS

Nutrient release characteristic and longevity of CRFs

Results showed that the cumulative nutrients release curve of Trincote 1 and Trincote 2 followed one factor quadratic regression equation at 25C (Table 1, Fig.1). The relative coefficients r were all bigger than 0.993 and showed very significant correlations between the days of incubation and cumulative nutrients release rate. The time for 75% release rate of Trincote 1 and Trincote 2 were 280 and 353 d, respectively.

Table 1 The regression equations of cumulative nutrients release rate from controlled release fertilizer at 25C

CRF tested Trincote 1 Trincote 2 Regression equations y =-0.0006x2 + 0.3929x + 11.855 y =-0.0006x2 + 0.3954x - 0.7084 Correlation coefficient 0.9972 ** 0.9989 ** n 41 51

release rate was the biggest one, the curve pattern was similar to that of 25C, and there was no abnormal release. Thus, the optimal temperature for Trincote 1 and Trincote 2 rapid test was selected at 80C.

50C 70C

60C 80C

Trincote 1

50C 70C

60C 80C

Trincote 2

x stands for days of incubation and y for cumulative release rate (%). ** indicates very significantly positive correlations.

Fig. 2 Cumulative nutrients release curves of Trincote 1 and Trincote 2 at 50, 60, 70, and 80C, respectively.

Regression analysis between the release time at 25 and 80C and predicting of the longevity

Correlation analysis showed that the cumulative nutrients release curve followed one factor quadratic regression equation at 80C, each relative coefficient was bigger than 0.995, and there were very significant correlations in the regression equations (Table 2). By calculating from the equations in Table 1, the days for nutrient release rates of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, and 75% could be obtained; using the same procedure, based on the regression equations in Table 2, the hours for the same release rates of above could also be obtained. After the regression analysis of above 2 sets of data, the regression equations between the days at 25C and the hours at 80C of Trincote 1 and Trincote 2 were then obtained (Table 3). Results showed that there were very significant posi-

Fig. 1 Cumulative release rate curves of Trincote 1 and Trincote 2 CRFs at 25C.

As the temperature increased, nutrients release of the CRFs increased (Fig.2). At 50 and 60C, for the leaching time there were only 6 hours and lower temperatures, the release rate appeared very slow, and the curve patterns were close to be straight lines, unlike the quadratic curve at 25C. However, at 90C, the phenomenon of abnormal release appeared, such as coating membrane broken or fertilizer agglomerated. At 80C, because the

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tive correlation between the days at 25C and hours at 80C for the same cumulative release rates. Thus, the leaching method at 80C could be used to predict the longevity of the CRFs, i.e., the time needed for nutrient release rate of 75%. The longevities of Trincote 1 and Trincote 2 predicted by use of above method were given in Table 4. Results showed that the longevities predicted by use of this method were more accurate with relative errors of only 0.3-1.1% (Table 4).

Correlation analysis between short-term leaching at 80C and incubation at 25C and predicting of the longevity

As indicated above, the time needed for the cumulative release rate of 75%, or the longevity of the CRFs, was precisely predicted using the 80C leaching method. However, this method needed very long time such as 16 to 24 hours, which, in turn, would cause the rapid test work not to be finished during a working day. Thus, the author investigated the correlation relation between the patterns of the short-term leaching of 6 hours at 80C and the incubation at 25C, which would be considered as the rapid test method with greatly

condensed time needed for the test of CRFs. The regression equation of cumulative nutrient release of Trincote 1 and Trincote 2 at 80C is shown in Table 5, respectively. The release patterns at 80C leaching for 6 hours were quadratic curves, whose correlation coefficient r were all above 0.996, and showed very significant correlations (Table 5). By calculating the regression equation in Table 5, the hours needed for the release rate of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, and 75% of Trincote 1 and Trincote 2 at 80C were obtained. Analyzing these two sets of data of Trincote 1 and Trincote 2, i.e., the days of incubation at 25C and the hours of leaching at 80C, expressed as a quadratic equation of day and hour respectively needed for the same cumulative release at 25C and 80C. There were very significant positive correlations in the regression equations (Table 6). Using the regression equation in Table 6, the longevities of Trincote 1 and Trincote 2 were predicted and listed in Table 7. The relative errors between the predicted and observed longevities were 0.3 and 6.9%, which were accurate enough for agricultural fertilizer (Table 7). The time needed for determination was reduced to only 6 hours.

Table 2 Regression equations of cumulative release rate of Trincote 1 and Trincote 2 at 80C

CRF tested Trincote 1 Trincote 2 Test duration (h) 16.5 24.0 Regression equation y = -0.2208x2 + 8.1228x - 0.0361 y = -0.0809x2 + 4.9021x + 2.0528 Correlation coefficient 0.9959 ** 0.9982 **

x stands for hours of incubation; y stands for cumulative release rate (%); n equals to 24 for both Trincote 1 and Trincote 2. Each datum is average of 3 replications.

Table 3 Regression equations of release time (hour) reached to the same cumulative release rate between 25 and 80C

CRF tested Trincote 1 Trincote 2 Test duration (h) 16 24 Regression equation of release time y = 0.2841x2 + 12.333x - 0.0423 y = 0.1015x2 + 12.226x + 4.1799 Correlation coefficient 0.9994 ** 0.9999 **

x stands for days of incubation at 25C and y for hours of incubation at 80C.

Table 4 Comparison of the observed and the predicted longevity for the CRF studied

CRF tested Trincote 1 Trincote 2 Longevity observed (d) 280 353 Longevity predicted (d) 283.0 354.1 Difference (d) - 3.0 - 1.1 Relative error (%) 1.1 0.3

Table 5 Regression equation of cumulative nutrients release of Trincote 1 and Trincote 2, respectively, at 80C

CRF tested Trincote 1 Trincote 2 Test duration (h) 6 6 Regression equation y = -0.6933x2 + 12.033x - 5.7468 y = -0.411x2 + 7.7288x - 2.3752 Correlation coefficient 0.9970 ** 0.9996 ** Cumulative release rate (%) 40.73 29.40

x stands for hours of incubation; y for cumulative release rate (%); n equals to 24 for both Trincote 1 and Trincote 2. Each datum is average of 3 replications.

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Table 6 Regression equations of release time (hour) reached to the same cumulative release rate between 25 and 80C by use of short-term leaching method

CRF tested Trincote 1 Trincote 2 Test period (h) 6 6 Regression equation of release time y = 0.2805x2 + 14.681x - 14.328 y = 0.0844x2 + 11.924x + 4.9888 Correlation coefficient 0.9995 ** 0.9999 **

x stands for hours of incubation at 80C and y for days of incubation at 25C.

Table 7 Comparison of the longevity of the observed and the predicted by short-term leaching method

CRF tested Trincote 1 Trincote 2 Method Predicted in 6 hours Predicted in 6 hours Longevity observed (d) 280 353 Longevity predicted (d) 299.4 354.0 Difference (d) - 19.4 - 1.0 Relative error (%) 6.9 0.3

DISCUSSION

Longevity is an important quality index of slow/CRF. Based on the definition of slow/CRF by Europe Standard Committee, pure water dissolving incubation at 25C is the conventional method to describe the release characteristics. The longevity is always evaluated by the differential release rate, i.e., Longevity = (75% Preliminary release rate)/Differential release rate. There were huge errors of the longevity evaluated by the differential release rate compared with the observed one. To predict the longevity accurately and quickly, increasing the incubation temperature could make the CRFs dissolve quickly. Thus, the optimal incubation temperature was selected as 80C from 25-90C in this experiment. Trenkel (1997) proposed that under a temperature of 25C, the nutrient or nutrients of slow/CRF should meet each of the following three criteria: No more than 15% released in 24 hours; no more than 75% released in 28 days, at least about 75% released at the stated release time. Thus, the longevity of CRFs was proposed to be the time needed for the release rate of 75% in 25C water. However, it is unsatisfactory for the longevity predicting online of commercially scaled CRFs because of the tedious time needed. Furthermore, so far, there is no method for predicting the longevity of CRFs. Many researchers constructed the digital model of nutrient release to predict the release characteristics (Hara 2000; Yang et al. 2005). Friedman and Mualem (1994) and Al-Zahrani (1999) studied the digital model of nutrient release rate, respectively. Two years experiments by Gandeza et al. (1991) showed that the cumulative N release of polyolefin coated urea with time

between 10C and 30C was described as a quadratic equation corresponding to the mean air or soil temperature. It was found that cumulative N release of polyolefin coated urea could be determined by using the corresponding relation between cumulative temperature and cumulative N release. Thus, using digital models can quickly predict nutrient release of CRFs and should be one of the quality test methods online of CRFs. The author observed the release rate at 25C and higher temperature water of CRFs and found the optimal incubation temperature as 80C, at which there was no abnormal release, and the time needed for test was greatly shortened. The results showed that 80C was proper temperature for the rapid test, at which the release rate was possible to be determined and the longevity of CRFs can be predicted precisely and quickly in a few hours. This method is accurate, convenient, timesaving, and suitable for the longevity predicting online of commercially scaled CRFs. However, further studies are required for the CRFs with complex release curve.

CONCLUSION

In this article, pure water dissolving incubation and higher temperature leaching were used to study the pattern of the nutrients release of the CRFs coated with water soluble resin and the rapid method to test and predict the longevity of CRFs was discussed. Results showed that as the temperature increased, nutrients release of the CRFs increased. It was found that 80C was optimal temperature for the rapid test of the CRF samples. The regression between the time for reaching the same cumulative release rates at 25C and 80C followed one factor quadratic equation by which the

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longevity of resin coated CRFs could be more quickly and precisely predicted other than that of the normal differential release rate. The longevity of water soluble resin coated CRF could be rapidly predicted in a few hours by the method of higher temperature short-term leaching. Compared with the traditional method, this new method would greatly shorten the time needed for testing and is suggested to be the candidate method for the rapid test of CRFs.

predicting longevity of controlled release fertilizer coated with thermoset resin. Plant Nutrition and Fertilizer Science, 12, 431-436. (in Chinese) Friedman S P, Mualem Y.1994. Diffusion of fertilizers from controlled-release sources uniformly distributed in soil. Fertilizer Research, 39,19-30. Gandeza A T, Shoji S, Yamada I. 1991. Simulation of cropresponse to polyolefin coated urea I. Field dissolution. Soil Science Society of America Journal, 55, 1462-1467. Hara Y. 2000. Application of the richards function to nitrogen realease from coated urea at a constant temperature and relationships among the calculated parameters. Soil Science and Plant Nutrition, 46, 683-691. Hara Y. 2000. Estimation of nitrogen release from coated urea using the Richards function and investigation of the release parameters using simulation models. Soil Science and Plant Nutrition, 46, 693-701. Li D P, Xu X C, Wang H B. 2005. Review on the standards of slow controlled release fertilizer at home and abroad. Phosphate and Compound Fertilizer, 20, 41-42. (in Chinese) Trenkel M E. 1997. Contrelled-Release and Stabilized Fertilizers in Agriculture. International Fertilizer Industry Association, Paris. Yang X D, Cao Y P, Jiang R F, Zhang F S. 2005. Evaluation of nutrients release feature of coated controlled release fertilize. Plant Nutrition and Fertilizer Science, 11, 501-507. (in Chinese) Zhang M, Yang Y C, Song F P, Shi Y X. 2005. Study and industrialized development of coated controlled release fertilizers. Journal of Chemical Fertilizer Industry, 32, 7-12. (in Chinese) (Edited by ZHAO Qi)

Acknowledgements

The study was supported by the National Key Technologies R&D Program during the 11th Five-Year Plan period of China (2006BAD10B02), and the National Natural Science Foundation of China (39870433, 30270769).

References

Al-Zahrani S M. 1999. Controlled-relesse of fertilizers: modeling and simulation. International Journal of Engineering Science, 37,1299-1307. Chen J H, Cao Y P, Xu H, Fang Z G, Mao D R. 2002. Appraisal of nitrogen releasing characteristics of organic polymer coating controlled release fertilizer. Plant Nutrition and Fertilizer Science, 8, 44-47. (in Chinese) Dai J J, Fan X L, Liang Y L, Sun L X. 2005. Study on calibration of standard regression curve of fertilizer solution concentration by conductivity method. Phosphate and Compound Fertilizer, 20, 15-17. (in Chinese) Dai J J, Fan X L, Yu J G, Wu F L. 2006. The method of quickly

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