Abstract
The adsorption of Cu(II), Mn(II), and U(VI) ions by mesoporous silica nanoparticles (NPs) was investigated by batch experiments to assess the potential using NPs to remediate acid mine drainage (AMD) contaminated water. Adsorption reactions were found to be rapid, attaining equilibrium within 5 min for Cu and less than a minute for Mn and U. Calculated adsorption rates based on the pseudo-second order model (R 2 = 0.99) showed that Mn adsorption was >3 times faster than Cu and 7 times faster than U. Adsorption increased with pH and temperature, and ∆G° and ∆H° values indicate that the process was spontaneous and endothermic. Isotherm data were best described by the Freundlich and Temkin models (R 2 = 0.99), with chemisorption responsible for the removal of Cu and Mn, and adsorption and precipitation for U removal. Importantly, Fe3+, Mn, and SO4 2− ions increased adsorption from 52, 56, and 49 % to 77, 66, and 76 % for Cu, Mn, and U, respectively. Cu removal was, however, inhibited in 1:2 Cu:Mn solutions. NPs were then applied to actual AMD-contaminated ground and surface water. As in simulated AMD, adsorption was higher for Mn than Cu and removal efficiencies of up to 60 % for Mn and 34 % for Cu were attained. These NPs therefore offer an alternative for Mn removal that precludes pH adjustment and the copious amounts of lime required for that. Importantly, they can be used for cost-effective treatment of AMD-contaminated water.
Zusammenfassung
Die Adsorption von Cu(II)-, Mn(II)- und U(VI)-Ionen durch halbporöse Siliziumdioxid-Nanopartikel (NPs) wurde in Batch-Versuchen untersucht, um die potentielle Nutzung der NPs für die Reinigung saurer Grubenwässer zu bewerten. Es wurde festgestellt, dass die Adsorption schnell verläuft und das Gleichgewicht für Cu innerhalb von fünf Minuten und die Gleichgewichte für Mn und U in weniger als einer Minute erreicht wurden. Mit einem pseudo-zweiter Ordnung Modell (R2=0,99) berechnete Adsorptionsraten zeigten, dass Mn mehr als dreimal schneller als Cu und siebenmal schneller als U adsorbiert wurde. Die Adsorption stieg mit dem pH-Wert und der Temperatur an. Die Werte für ∆G° und ∆H° zeigten, dass der Prozess spontan und endotherm verläuft. Die Adsorptionsisothermen konnten am besten mit dem Freundlich- und Temkin-Modell beschrieben werden (R2=0,99). Dabei war Chemisorption für die Entfernung von Cu und Mn verantwortlich und Adsorption und Fällung für die Entfernung von U. Wichtig ist, dass Fe3+-, Mn- und SO 2-4 -Ionen die Adsorption von 52, 56 und 49% auf 77, 66 und 76% erhöhten. Die Cu-Entfernung wurde jedoch in Lösungen mit einem Cu:Mn-Verhältnis 1:2 behindert. Die Nps wurden dann in durch saure Grubenwässer kontaminierten Grund- und Oberflächenwässern angewendet. Wie im künstlichen sauren Grubenwasser war die Adsorption für Mn größer als für Cu. Entfernungsraten von bis zu 60% für Mn und bis zu 34% für Cu wurden erreicht. Damit stellen diese NPs eine Alternative für die Mn-Entfernung dar, die die pH-Anhebung und die dafür nötigen Mengen an Kalk vermeidet. Die NPs können für eine kostengünstige Behandlung saurer Grubenwässer benutzt werden.
Resumen
La adsorción de Cu(II), Mn(II) y U(VI) por nanopartículas mesoporosas de sílica (NPs) se investigó a través de experimentos en batch para determinar el potencial de utilizar NPs para remediar agua contaminada con drenajes ácidos de mina (AMD). Las adsorciones fueron rápidas alcanzando el equilibrio dentro de los 5 minutos para Cu y menos de 1 minuto para Mn y U. Las velocidades de adsorción calculadas utilizando un modelo de pseudo segundo orden (R2 = 0,99) mostraron que la adsorción de Mn fue >3 veces más rápido que Cu y 7 veces más rápido que U. La adsorción se incrementó con el pH y la temperatura y los valores de ∆G° y ∆H° indican que el proceso fue espontáneo y endotérmico. Las isotermas fueron mejor descriptas por los modelos de Freundlich y Temkin (R2 = 0,99), indicando quimiosorción para la remoción de Cu y Mn y adsorción y precipitación para la remoción de U. Es significativo que Fe3+, Mn y SO4 2− incrementaron la adsorción desde 52, 56 y 49 % a 77, 66 y 76 % para Cu, Mn y U, respectivamente. La remoción de Cu fue, sin embargo, inhibida en soluciones 1:2 Cu: Mn. Las NPs fueron aplicadas en aguas superficiales y subterráneas contaminadas con AMD. Como en el AMD artificial, la adsorción fue mayor para Mn que para Cu y se obtuvieron eficiencias de remoción de hasta 60 % para Mn y 34 % para Cu. Estas NPs ofrecen una alternativa para la remoción de Mn que evita el ajuste de pH y las grandes cantidades de lima requeridas para eso. En definitiva, las NPs pueden ser usadas para un tratamiento rentable del agua contaminada con AMD.
抽象
批次试验评价了介孔氧化硅颗粒(NPs)对酸性矿山废水中铜(Cu2+)、锰(Mn2+)和铀(U6+)离子的吸附能力。研究发现吸附反应速度较快,铜达到反应平衡时间为5分钟,比锰和铀达到反应平衡时间短1分钟。基于假二级模型(pseudo-second order model ,R2= 0.99)的计算吸附速率表明,锰吸附速度比铜快3倍,比铀快7倍。吸附率随pH值和温度增大而升高。计算∆G值和∆H值表明吸附反应为自发的吸热反应。弗罗因德利希吸附等温曲线(Freundlich)和Temkin模型(R2= 0.99) 很好地刻画了该吸附反应特征。铜(Cu)和锰(Mn)的去除以化学吸附作用为主;同时,硫酸根离子(SO42-)增多使铜(Cu2+)、锰(Mn2+)和铀(U6+)的吸附去除率分别由52%、56%、77%提高到77%、66%和76%。在Cu: Mn=1:2的溶液的中,铜的去除受到抑制。之后,将介孔氧化硅纳米颗粒应用到实际的地表和井下酸性矿山废水的处理中。与模拟酸性矿山废水结果相似,锰的吸附高于铜,锰的去除率达60%,铜的去除率达34%。介孔氧化硅纳米颗粒为在不改变pH值和消耗大量石灰的前提下去除锰提供了可能。更重要的是,介孔氧化硅纳米颗粒为酸性矿山废水处理提供了一种经济有效方法。
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Acknowledgments
Funding for this work was provided by the Global Change and Sustainability Research Institute (GCSRI) of the University of Witwatersrand in the form of a Ph.D. fellowship to A.E. We acknowledge the contributions of Kirstin Olsen with field sampling, Siyethemba Mabaso with ICP-OES analyses, and Jacques Gerber of the Microscopy and Microanalysis Unit.
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Etale, A., Tutu, H. & Drake, D.C. Mesoporous Silica Nanoparticles for the Adsorptive Removal of Cu(II), Mn(II), and U(VI) from Acid Mine Drainage. Mine Water Environ 34, 231–240 (2015). https://doi.org/10.1007/s10230-014-0311-7
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DOI: https://doi.org/10.1007/s10230-014-0311-7