Liu Ruiqiang, Zhao Dongye
Department of Civil Engineering, 238 Harbert Engineering Center, Auburn University, Auburn, Alabama 36849, USA.
Chemosphere. 2007 Aug;68(10):1867-76. doi: 10.1016/j.chemosphere.2007.03.010. Epub 2007 Apr 25.
This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.
本研究测试了使用一类新型的磷酸铁(蓝铁矿)纳米颗粒的可行性,该纳米颗粒以羧甲基纤维素钠(NaCMC)作为稳定剂合成,用于原位固定土壤中的Cu(II)。透射电子显微镜测量表明,粒径约为8.4±2.9 nm。批次试验表明,在0.61和3.01 mg PO(4) g(-1)土壤的低剂量下,纳米级蓝铁矿颗粒可有效降低三种代表性土壤(钙质土、中性土和酸性土)中Cu(II)的浸出性和体外生物可及性。通过毒性特征浸出程序评估Cu的浸出性,通过基于生理学的提取试验评估体外生物可及性。在土壤中添加3.01 mg PO(4) g(-1)土壤的纳米颗粒进行改良的情况下,在这些土壤改良56天后,Cu的浸出性降低了63 - 87%,TCLP提取物中的Cu浓度从1.74 - 13.33 mg l(-1)降至0.23 - 2.55 mg l(-1)。同时,Cu的生物可及性降低了54 - 69%。连续提取程序表明,在用纳米颗粒改良土壤后,水溶性/可交换Cu(II)和碳酸盐结合部分显著减少,而Cu残留部分相应增加,这表明通过沉淀和吸附形成磷酸铜矿物可能是土壤中Cu有效性降低的原因。Visual MINTEQ建模进一步揭示,在蓝铁矿 - 固体Cu(II)体系中形成了Cu(3)(PO(4))(2)和Cu(5)(PO(4))(3)OH,导致酸性pH范围内Cu(II)的溶解度降低。