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標題: Phosphate release from ferrihydrite-humic acid coprecipitates as affected by citric aicd
作者: Fang-Yu Tsao
關鍵字: 磷酸根
Citric acid
Humic acid
引用: 宋睿哲。2016。磷酸根在水合鐵礦與自然有機物共沉澱上之吸持,碩士論文,東海大學,台中,台灣。 孫嘉福,駱尚廉。1994。氧化鐵之特性與應用,自來水會刊雜誌,第49期:47-56頁。 陳炳濤。1991。土壤地理與生物地理,華東師範大學出版社。 陳彥宇。2015。施用磷肥之概念-磷在土壤中的特性,台肥季刊,第五十五卷第四期。 Aiken, G.R., and R.L. McKnight. 1985. Humic substances in soils, sediment and water: geochemistry, isolation, and characterization. New York (N.Y.): Wiley, 1985, 585-682. Anderson, M.A., M.I. Tejedor-Tejedor, and R.R. Stanforth. 1985. Influence of aggregation on the uptake kinetics of phosphate by goethite. Environ. Sci. Technol. 19: 632–637. Andraski, T.W., and L.G. Bundy. 2003. Relationships between phosphorus levels in soil and in runoff from corn production systems. J. Environ. Qual. 32: 310–316. Axt, J.R., and M.R. Walbridge. 1999. Phosphate removal capacity of palustrine forested wetlands and adjacent uplands in Virginia. Soil Sci. Soc. Am. J. 63: 1019–1031. Baldock, J.A., and J.Q. Skjemstad. 2000. Role of the soil matrix and minerals in protecting natural organic materials against biological attack. Org. 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摘要: 磷是植物三大必要元素之一,因其在土壤中的低有效性及低移動性,常仰賴磷肥的施用以供植物所需,但磷為一有限資源,將在未來幾十年內開採殆盡,故如何從有限的資源中,提高磷利用率值得被探討。磷在土壤常被鐵鋁氫氧化物固定,其中包含常見之弱結晶性的水合鐵礦。環境中水合鐵礦常與有機物質(例如;腐植酸)共沉澱,其可能影響磷和水合鐵礦之間的作用進而影響磷的有效性。而在缺磷環境下,植物會分泌小分子有機酸(例如:檸檬酸、草酸),其可藉由配位基交換或是溶解鍵結在礦物表面的磷。在過去的研究中都針對這些有機酸提升土壤中有效性磷的效果作探討,對於有機酸影響磷酸根在水合鐵礦特別是與腐植酸共沉澱下的吸持研究是缺乏的。故本實驗的研究目的為先探討小分子有機酸-檸檬酸在水合鐵礦-腐植酸共沉澱物(FH-HA)上的吸持作用,進而在探討檸檬酸對於磷酸根在FH-HA上吸持的影響。研究中發現檸檬酸在FH-HA上的最大吸附量會隨共沉澱物中腐植酸比例增加而下降,藉由鐵的延伸X光吸收細微結構(EXAFS)分析發現,水合鐵礦在有腐植酸共沉澱下,檸檬酸的加入會使其結構變差,進而可能對陰離子吸附量有所影響。   此外,不同加入順序的檸檬酸和磷酸根對檸檬酸與磷酸根在FH-HA上的吸附結果指出:先加入檸檬酸再加入磷酸根(C-P)至FH-HA下磷酸根的吸附量約只有磷酸根在FH-HA上最大吸附量的50%,比先加入磷酸根再加入檸檬酸(P-C)下的磷酸根吸附量(約最大吸附量之80% )明顯低許多;而共沉澱物中腐植酸的比例越高磷酸根的吸附量也會有些微下降的趨勢,都有助於磷酸根有效性的提升。從檸檬酸的吸附量來看,不同的加入順序對於檸檬酸的吸附差異不大,推測若檸檬酸先吸附的情況下,其分子較大較不利於擴散至礦物內部故對於後來加入磷酸根之吸附有所影響。而從鐵溶出量來看,發現相同的加入量P-C處理的鐵溶出會明顯高於C-P處理,推測原因為雖然磷酸根溶解鐵能力不如檸檬酸,但在先加入的情況下,磷酸根大量吸附到水合鐵礦團粒表面產生靜電排斥力,使得大團粒的鐵礦形成小團粒顆粒,而後加入的檸檬酸能快速且溶出較多的鐵,故反而P-C的鐵溶出會比C-P多。   隨時間變化來看C-P及P-C處理下檸檬酸和磷酸根吸附量的變化,C-P處理下檸檬酸在FH-HA上之吸附量受後加入磷酸根影響小,吸附量下降小,而P-C處理下,磷酸根的吸附量會受檸檬酸的加入影響尤其在初始的8小時內,磷酸根吸附量會急遽下降,但之後磷酸根會有再吸附的現象發生,可能的原因有:(1)鐵被溶出後又有新的吸附位置裸露,此時檸檬酸與磷酸根可以行競爭吸附;(2)鐵離子的溶出可做為有機物質與磷酸根的橋接金屬形成有機陰離子-Fe-磷酸根錯合物,進而使得磷酸根又被吸附回去,對照鐵離子的溶出吻合一開始的磷酸根吸附量變化,雖然檸檬酸可藉由溶出鐵而釋出磷酸根但再吸附的情況下會使得磷酸根的有效性降低。   若以提升磷酸根的有效性為最終目的,先將水合鐵礦-腐植酸共沉澱物吸附檸檬酸後再加入磷酸根,磷酸根被固定在共沉澱物上的吸附量最低;而共沉澱中的腐植酸對於磷酸根有效性的提升雖不如先加入檸檬酸的情況,但腐植酸比例的提升確實可以稍微降低磷酸根的吸附,此外鐵礦中腐植酸的增加也會使鐵溶出增加。本實驗除了解檸檬酸對於磷有效性的提升以達到磷的永續利用外,鐵的溶出只要適量也對於作物吸收及根圈土壤有正面效益。 關鍵字:磷酸根、檸檬酸、水合鐵礦、腐植酸、共沉澱
Phosphorus (P) is a major essential nutrient of plants, but P fertilization for plant growth is inevitable due to its low mobility and availability in soils. Phosphorite, a limited resource, will be exhausted in a few decades, and it is an important issue to increase the long-term P availability in the agricultural soils. In soils, P is commonly fixed by hydrous oxides of Fe and Al, especially for a poorly crystalline ferrihydrite. Ferrihydrite could be formed coprecipitates with organic matters, e.g. humic acid, in the environments, resulting in the effects of interactions between P and ferrihydrite on P availability. To increase the bioavailability of P in soils, plant roots would secrete some small molecular weight organic acids, e.g., citric acids and oxalic acids, to exchange or dissolve the fixed P from soil minerals. The previous studies were focused on the P availability in soils improved by organic acids, however, it is rare to understand the effects of organic acids on P sorption on the coprecipitates of ferrihydrite and humic acids (FH-HA). Therefore, the aims of this study were to investigate that the effects of citric acid sorption on the coprecipitates structure of FH-HA and to evaluate the P adsorption on FH-HA in presence of citric acid. According to our results, we found that the maximum adsorption capacity of citric acid on FH-HA decreased with the increasing ratio of humic acid in FH-HA coprecipitates. The Fe K-edge extended X-ray absorption fine structure (EXAFS) results indicated that citric acid sorption made the structures of FH-HA coprecipitates poorly, contributing to affect the anion adsorption capacities.   The PO4 adsorption capacities of FH-HA coprecipitates were greatly affected by the order of citric acid or PO4 addition. When PO4 was firstly added (entitled as P-C) into the systems, the PO4 adsorption capacities of FH-HA coprecipitates were reduced to about 80% of the maximum adsorption capacity of PO4 on FH-HA without citric acid, but the PO4 adsorption capacities were decreased to about 50% with the addition of citric acid prior to PO4 (C-P). As the ratio of humic acid in the FH-HA coprecipitates increased, the adsorption capacities of PO4 would be decreased, leading to the improvement of P availability. However, the addition order of PO4 had no significant effect on the adsorption capacities of citric acid on FH-HA coprecipitates. It suggested that citric acid would be the diffusion barrier of PO4 to the interior of FH-HA coprecipitates. We also found that the dissolved irons of the P-C treatment were more than those of the C-P treatment because a number of PO4 adsorbed on FH-HA developed to electrostatic repulsive forces making large particle FH-HA aggregate become small particles, and thus citric acid could rapidly dissolve more iron form FH-HA coprecipitates..   Based on the results of the C-P and P-C treatment changed with time, it showed that the PO4 addition in the C-P treatments had unobvious effects on the citric acid adsorption capacity of FH-HA. However, the PO4 adsorption capacity of FH-HA had obvious effects by citric acid addition on P-C treatment. The PO4 adsorption capacity was dropped during the addition of citric acid for 8 hours in the P-C treatment, and then PO4 would be adsorbed on FH-HA again. We hypothesized that: (1) new adsorption sites were exposed after iron being dissolved; (2) the dissolved Fe could be the bridging metal between organic substances and PO4, and so the formation of the organic anion-Fe-phosphate complex caused PO4 re-adsorbed on FH-HA. The dissolved iron increased results were in accord with the change of PO4 adsorption capacities on FH-HA in the C-P treatment, but PO4 re-adsorption would reduce the P availability due to the dissolved iron.   For the improvement of P availability, we suggested that the PO4 adsorption capacity of the FH-HA coprecipitates was the lowest as citric acid added firstly, the increased ratio of humic acid in the FH-HA coprecipitates would reduce the PO4 adsorption capacity and promote the dissolved Fe. Thus, we understood that citric acid improved the availability of PO4 for the sustainable use of phosphorus in soils, and of the appropriate dissolved Fe also have positive effects on crop growth and rhizophere soils. Key words: Phosphate、Citric acid、Ferrihydrite、Humic acid、Coprecipitates
文章公開時間: 2020-08-02
Appears in Collections:土壤環境科學系



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