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|標題:||Dissolution of Phpsphate-adsorbed Geothite by Desferrioxamine B
Desferrioxamine B 對磷吸附後針鐵礦之溶解機制
|關鍵字:||no;無||引用:||Adegoke, H.I., F.A. Adekola, O.S. Fatoki and B.J. Ximba. 2013. Sorptive interaction of oxyanions with iron oxides: a review. Pol. J. Environ. Stud. 22: 7-24. Afonso, M.D. and W. Stumm. 1992. Reductive dissolution of iron( Ⅲ )(hydr)oxides by hydrogen-sulfide. Langmuir 8: 1671-1675. Albrecht-Gary, A.M. and A.L. Crumbliss. 1998. Coordination chemistry of siderophores: Thermodynamics and kinetics of iron chelation and release. Met. Ions Biol. Syst. 35: 239 327. Arai, Y. and D.L. Sparks. 2007. Phosphate reaction dynamics in soils and soil components: A muiltiscale approach. Adv. Agronomy 94: 135-179. Atkins, P. and J. de Paula. 2009. Chemical kinetics: the rates of reactions.Elements of physical chemistry. Oxford University Press. p. 232-236. Belelli, P.G., S.A. Fuente and N.J. Castellani. 2014. Phosphate adsorption on goethite and Al-rich goethite. Comput. Mater. Sci. 85: 59-66. Biber, M.V., M.D. Afonso and W. Stumm. 1994. The coordination chemistry of weathering .4. 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Desferrioxamine B(DFOB) is one of microbial trihydroxamate siderophores, which is excreted by soil microbes and plant rootunder iron (Fe) deficientconditions.It can dissolveFe oxide minerals and increase the Fe availability in soil.Phosphate (P) is well known to be easily fixed by Fe minerals in soil. Because P and DFOB may compete the same surface binding sites, it is unclear whether P availability is increased when Fe oxide minerals are dissolved by DFOB. The aim of this research is to investigate the effects of DFOB on the releasing rates of P and Fe from P-adsorbedgoethite. P-adsorbed goethites were prepared with 0, 40 and 100% P loading amountsat pH 5 and 9. DFOB-promoted dissolution experiments were conducted at pH 5 and at different temperatures (5, 25 and 45℃). The corresponding dissolution rate constants were obtained and subsequently used to calculate the pre-exponential factor (A) and activation energy (Ea) through Arrhenius equation. The results showed that the calculated activation energyfor the dissolution reaction increased with the P adsorptionincrease, as there was stronger bonding interaction between Fe and P. Although theactivation energy increases , the dissolution rate of Fe is also increased. It is because more P adsorbed on goethite, Eap become lower than EaFe and thus Fe dissolution is chemically controlled by P. The complex species of P also control Fe dissolution. Fe dissolution is more significantly enhanced by mononuclear bidentate complex. The enhancement of Fe dissolution with more adsorbed P can be explained by increased A value, which means that DFOB was more accessible to the surface of goethite. The increase in the accessibility of DFOB to the goethite surface with increasing P adsorptionresults from the increasing negative charge of goethite surface. Moreover, the dissolution-readsorption mechanism may play a significant role in enhancement of Fe and P dissolution.
Desferrioxamine B (DFOB)是一種由微生物分泌的載鐵物質，它含有三個醯基羥胺官能基。鐵是生物生表的重要元素之一，但在土壤環境中，微生物和植物根系常處於缺乏鐵的情況下。為了攝取足夠的鐵元素，它們會分泌對鐵親和力高的載鐵物質，把鐵礦物上的鐵溶解，增加土壤中的有效鐵。除了鐵之外，土壤磷的有效性很低，它很容易被固定在鐵礦物上。由於磷酸鹽和DFOB會競爭針鐵礦上相同的反應位置，目前還不瞭解磷的吸附對DFOB溶解鐵的影響。因此，本研究的目的是探討DFOB對針鐵礦上磷和鐵
溶解的影響，從而了解DFOB對土壤中磷及鐵有效性的影響。實驗中先準備在pH5 和pH9 下不同含量( 0，40，100％磷 ) 磷吸附的含磷針鐵礦，並
在pH 5 下加入DFOB在不同溫度下（5，25 和 45℃）進行溶解實驗。計算出的溶解速率常數，隨後通過Arrhenius equation來計算指前因子A和活化能Ea。結果顯示，磷會阻擋DFOB吸附在針鐵礦上。由於鐵和磷之間的鍵結強度增加，活化能也隨磷吸附增加而增加。然而，鐵的溶解速率卻隨磷吸附增加而增加。當磷吸附增加，由於溶解鐵之活化能較溶解磷之活化能高，磷成為鐵溶解的控制因子。磷在針鐵礦上的鉗合型態對鐵溶解也有影響，單核雙配位的鉗合型態有促進鐵溶解的效果。另外，磷的吸附導致表面負電荷的增加，讓DFOB更容易跟針鐵礦的表面鐵反應，進一步促進鐵溶解。磷的重新吸附機制亦為促進鐵和磷溶解的原因之一。
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