镁铁层状双金属氢氧化物对磷酸盐的吸附作用及对内源磷释放的控制效果及机制

为确定镁铁层状双金属氢氧化物(Mg/Fe-LDH)添加对水体内源磷释放的控制效果及机制,本文首先研究了Mg/FeLDH对水中磷酸盐的吸附特征和机制,再研究了其添加对底泥磷吸附能力的影响以及对上覆水和间隙水中磷的影响进而评估了吸附磷酸盐后Mg/Fe-LDH中磷的稳定性.结果发现,与准一级和准二级动力学模型相比,Mg/Fe-LDH对水中磷酸盐的吸附动力学过程更好地满足Elovich模型;与Langmuir模型相比,Freundlich和Dubinin-Radushkevich模型更加适合用于描述Mg/Fe-LDH对水中磷酸盐的等温吸附行为;当溶液pH值为4～10时,吸附容量相对较高,而当pH值由10增加到11时,吸附容量则显著下降;共存Ca~(2+)和Mg~(2+)对吸附起促进作用,Na~+和Cl~-的影响可以忽略不计,而SO_4~(2-)和HCO_3~-则对吸附起负面影响.阴离子交换、静电吸引、配位体交换和内层配合物形成是Mg/Fe-LDH吸附水中磷酸盐的主要机制.Mg/Fe-LDH添加不仅会降低上覆水中溶解性活性磷(SRP)浓度而且会降低间隙水中SRP浓度.Mg/Fe-LDH添加也会显著增强底泥对水中磷酸盐的吸附能力,且投加量越大,促进效果越明显.被Mg/Fe-LDH所吸附的磷酸盐主要以NH_4 Cl提取态磷(NH_4Cl-P)、氧化还原敏感态磷(BD-P)和金属氧化物结合态磷(NaOH-rP)形态存在,分别占总磷的13.7%、34.0%和52.3%.被Mg/Fe-LDH所吸附的磷酸盐中大约有一半的磷会以较为稳定的形式存在不容易被重新释放.考虑到被Mg/Fe-LDH所吸附磷酸盐中大约有一半的磷会以不稳定的形式存在,存在重新释放的风险,因此将吸附饱和后的Mg/Fe-LDH进行回收是非常必要的.

Adsorption of Phosphate on Mg/Fe Layered Double Hydroxides (Mg/Fe-LDH) and Use of Mg/Fe-LDH as an Amendment for Controlling Phosphorus Release from Sediments

We determine the efficiency and mechanism of Mg/Fe layered double hydroxides (Mg/Fe-LDH) addition for the control of phosphorus (P) release from sediments by studying the adsorption behavior and mechanism of phosphate from an aqueous solution on Mg/Fe-LDH. The impact of Mg/Fe-LDH addition on the mobilization of P in sediments as well as the adsorptive removal of phosphate by sediments is investigated, and the stabilization of P bound by Mg/Fe-LDH is also evaluated. Results showed that the kinetics data of phosphate adsorption onto Mg/Fe-LDH fitted better with the Elovich kinetics model than with the pseudo-first-order and pseudo-second-order kinetics models, and that the Freundlich and Dubinin-Radushkevich models were more suitable for describing the adsorption isotherm behavior of phosphate on Mg/Fe-LDH than the Langmuir model. Phosphate adsorption possessed a wide effective pH range of 4-10. Coexisting Ca²⁺ and Mg²⁺ enhanced phosphate adsorption onto Mg/Fe-LDH, while coexisting Na⁺, K⁺, and Cl^- had negligible impacts on the phosphate adsorption. The presence of SO₄^2- and HCO₃^- in aqueous solution inhibited the adsorption of phosphate on Mg/Fe-LDH. The phosphate adsorption mechanisms were deduced to be anion exchange, electrostatic attraction, ligand exchange and inner-sphere complex formation. The addition of Mg/Fe-LDH into sediments not only greatly reduced the concentration of reactive soluble P (SRP) in the overlying water, but also significantly decreased the level of SRP in the pore water. In addition, Mg/Fe-LDH addition also increased the adsorption capacity for the sediments, and the phosphate adsorption ability for the Mg/Fe-LDH-amended sediments increased with increased amendment dosage. Almost half of the phosphate bound by Mg/Fe-LDH existed in the form of relatively stable P, i.e., metal oxide-bound P (NaOH-rP), which was difficult to release back into the water column under normal pH and anoxic conditions. Nearly half of the phosphate bound by Mg/Fe-LDH existed in the form of easily released P, i.e., NH₄Cl extractable P (NH₄Cl-P) and redox-sensitive P (BD-P), which had a high risk of re-releasing into the water column. We conclude that it is very necessary for Mg/Fe-LDH to be recycled from the sediments after the application of Mg/Fe-LDH as an amendment to control sedimentary P liberation.