纳米Pd/Fe催化甲醇/水中2,2',4,4'-四溴联苯醚(BDE-47)还原脱溴

构建了纳米Pd/Fe催化还原甲醇/水中2,2’,4,4’-四溴联苯醚(BDE-47)反应体系,常压下采用单因素实验系统考察了纳米Pd/Fe催化还原甲醇/水中2,2’,4,4’-四溴联苯醚(BDE-47)的主要影响因素,并分析了BDE-47还原反应的中间产物及终产物.结果表明,纳米Pd/Fe的反应活性随Pd负载率的提高而先升后降;甲醇-水体积比高于50∶50后,BDE-47去除率随甲醇-水体积比升高而降低;在25～40℃内,BDE-47去除率随反应温度的升高而升高,随BDE-47初始浓度的增加而降低,增加纳米Pd/Fe量可提高反应速率;酸性及弱碱性条件有利于BDE-47还原.BDE-47还原主要为脱溴反应,是一个从n溴到(n-1)溴联苯醚的逐步脱溴过程,反应进行90min后,BDE-47分子中溴原子完全被脱除,反应终产物为二苯醚.     

EDTA和铁对铜绿微囊藻和四尾栅藻生长和竞争的影响

铁限制不但会影响浮游植物的种群密度,而且会影响浮游植物的群落结构.为了探讨有机配体和铁的作用对湖泊中浮游植物的种群竞争,采用批量培养的方法,研究了不同EDTA及Fe浓度下,太湖蓝藻铜绿微囊藻和绿藻四尾栅藻的生长和竞争.结果表明,较高浓度的EDTA（≥13 .5 μmol/L）可以抑制铜绿微囊藻的生长,但不抑制四尾栅藻,因而有利于四尾栅藻占据优势;铁的浓度由3 μmol/L增大至18 μmol/L时,可缓解较高浓度EDTA（13 .5～27 μmol/L）对铜绿微囊藻的抑制作用,而增大其它微量元素浓度（B、Mn、Zn、Cu、Mo等）则无此作用;说明高浓度EDTA与铁的螯合作用能抑制铜绿微囊藻而不抑制四尾栅藻.高浓度EDTA对2种藻具有不同影响的原因可能是2种藻对铁的吸收机制不同.     

聚硅酸铁(PSF)混凝剂硅铁反应过程研究

以水玻璃、硫酸亚铁及氯酸钠为原料,用共聚法制备不同Si/Fe比的聚硅酸铁(PSF)混凝剂(PSF0.5、PSF1、PSF3分别指Si/Fe摩尔比为0.5、1、3),同时监测制备过程中pH的变化,并就不同共聚反应时间的样品,分别采用X-射线衍射法(XRD)、紫外吸收(UVA)扫描法、透射电镜法(TEM)、光子相关光谱法(PCS)及红外光谱法(IR)对其反应过程的微观品质进行多方面表征.结果表明,PSF是硅铁反应的共聚物,而不是简单的原料复配.不同Si/Fe比的PSF具有不同的硅铁成键速度、成键方式及成键稳定性,低Si/Fe比主要生成以Si—O—Fe—O—Fe—O—Si键络合的物种,而高Si/Fe比主要生成以Si—O—Fe—O—Si—O—Si键络合的物种,Fe—O—Fe键的形成速度快并且与Si—O—Fe键的形成可能有相互促进作用,而Si—O—Si键(硅酸聚合)形成速度慢并且与Si—O—Fe键的形成可能有相互阻碍作用,Fe—O—Fe键的稳定性比Si—O—Fe或Si—O—Si键差.对于PSF中硅铁不同成键模式的分析为合成高性能、高稳定性的硅酸铁类混凝剂以及为优势形态控制提供了一定的理论基础.     

黄棕壤铁铝氧化物与土壤稳定性有机碳和氮的关系

用6%NaOCl氧化不同粒级的黄棕壤,得到稳定性有机碳和氮的样品.用选择性溶提技术提取铁铝氧化物的含量,与稳定性有机碳和氮的关系表明:在2～250μm粒级上,游离铁、无定形铁和络合态铁含量的变化范围分别为6～60.8g/kg、0.13～4.8g·kg-1和0.03～0.47g·kg-1,在2μm粒级上分别为43.1～170g·kg-1、5.9～14.0g·kg-1和0.28～0.78g·kg-1.在2μm粒级上,无定形铝和络合态铝含量变化范围分别为0.08～1.34g/kg和0.11～0.47g/kg,在2μm粒级上分别为2.96～6.20g·kg-1和0.38～0.78g·kg-1.水稻土黄棕壤的选择性溶提铁的含量一般高于旱地黄棕壤,而选择性溶提铝的含量低于旱地黄棕壤.在2～250μm粒级上,土壤稳定性有机碳和有机氮含量变幅分别为0.93～6.0g·kg-1和0.05～0.36g·kg-1,在2μm粒级上分别为6.05～19.3g·kg-1和0.61～2.1g·kg-1,水稻土的稳定性有机碳和氮的含量高于旱地黄棕壤.在2～250μm粒级上,稳定性有机碳与有机氮比值(C稳/N稳)的变幅为9.50～22.0,在2μm粒级上分别为7.43～11.54.在2～250μm粒级上,土壤有机碳(氮)的稳定性指数SIC和SIN的变化分别为14.3～50.0和11.9～55.6,在2μm粒级上分别为53.72～88.80和40.64～70.0;旱地黄棕壤的SIC和SIN一般低于水稻土的,水稻土黄棕壤有利于有机碳和氮的保存.各种形态的铁铝氧化物含量与稳定性有机碳(氮)含量呈极显著正相关,且氧化物铁铝含量和稳定性有机碳(氮)含量在黏粒部分最高,即细粒级能保护土壤有机碳(氮).     

铁对铜绿微囊藻生长活性及产毒的影响

以MA培养基为基础,向无铁培养基中添加不同质量浓度的FeCl3,对对数生长期的铜绿微囊藻进行接种培养,比较不同Fe3+浓度下,铜绿微囊藻的生长、活性及产毒状况.结果表明,无Fe3+时,藻的生长、细胞活性和产毒受到抑制;Fe3+浓度增大时,有利于藻的生长,且当Fe3+质量浓度为0.42 mg/L时,培养42 d后细胞密度达到最大(4.5×1010个/L).过高或过低浓度的Fe3+均会抑制藻细胞活性和毒素的产生.Fe3+质量浓度为0.04 mg/L时,脱氢酶活性较好;质量浓度为0.10 mg/L时,适宜藻毒素MCLR的生成,且单位生物量藻细胞的MCLR产量可达0.32 mg.研究表明,Fe3+浓度对藻细胞完整性的影响不大,而且藻细胞的最佳生长条件并不是其最佳产毒条件.     

Pd/Fe催化脱氯水中PCE的动力学研究

以GC-MS为分析方法，采用Pd／Fe双金属对水溶液中四氯乙烯（PCE）进行了催化还原脱氯处理，考察了PCE初始浓度、钯含量、Pd／Fe用量和溶液初始pH值等各因素对脱氯效果影响及还原动力学规律。结果表明，Pd／Fe双金属对PCE有较好的还原脱氯效率，反应遵循准一级反应动力学规律，以反应物PCE浓度为参照的反应速率常数K变化范围为0．019min^-1～0．16min^-1，对应的PCE半衰期从6min到36min，揭示反应有可能是在过量的Pd／Fe双金属表面进行。当PCE溶液初始浓度为1mmol／L，投加1．2g钯含量为0．03％的Pd／Fe双金属，在25℃下反应60min，PCE的脱氯率达到95％以上。增大钯含量和Pd／Fe用量可有效提高脱氯率，在初始pH值为弱酸性条件下有利于还原脱氯反应进行。     

土壤理化性质对Fe~0还原硝基苯的影响

采用零价铁（Fe0）还原降解土壤中的硝基苯,考察土壤理化性质对还原效果的影响。结果显示,当2 g土壤中NB含量约为2.5×10-6mol/g,铁粉用量为50 mg,土壤含水量为75%时,控温25℃条件下反应1 h,硝基苯在松砂土和中壤土中的还原率分别可达到82.9%和91.1%。硝基苯在2种土壤中的还原率表现出中壤土〉松砂土的规律;土壤微生物和土壤有机质含量升高有利于反应进行;粒径偏小的中壤土中硝基苯还原较彻底。NB在土壤中的老化时间对Fe0还原效果影响较小。     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

溶液环境对纳米Fe_2O_3/水界面NOM吸附过程中疏水效应的影响

以腐殖酸和纳米Fe2O3为对象,着重研究了腐殖酸分子在纳米Fe2O3表面的吸附过程中的疏水效应,借助红外光谱和热重等分析方法研究了腐殖酸吸附前后的疏水性随溶液环境变化的规律。结果表明,当离子强度为0、0.005、0.01和0.05 mol/kg,pH从7变到12时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着pH的升高先减小后增大。当pH从7升高到10时,亲水性降低,疏水性增强;当pH从10升高到12时,亲水性增强,疏水性降低。当离子强度为0.001 mol/kg,pH从7变到12时,复合体的热失重量随着pH的升高而减小,亲水性降低,疏水性增强。当pH为定值,离子强度变化时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着离子强度的增加不断变化,曲线呈现出波动趋势,亲、疏水性在交替变化。红外光谱分析结果说明,对纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的亲疏水性起主要影响的官能团可能是亲水性的羟基—OH、羰基CO和疏水性的CH2烷烃。     

Fe(II)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment

Schwertmannite is an important Fe(III)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements. The treatment and neutralization of AMD normally involve the use of lime, which leads to the discharge of abundant Ca in the mining area. Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred. Here, the Fe(II)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated. Results showed that adsorbed Ca had a weak inhibitory effect on Fe(II)-mediated schwertmannite transformation. Release of SO₄²⁻ and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca. XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(II). The end products of Sch notably contained both goethite and lepidocrocite; however, transformation products of SchCa only contained goethite all along. Approximately 33.5% of the surface adsorbed-Ca was released into solution within 6 hr after Fe(II) injection. Aqueous Ca behaved in a “first release and then im-mobilization” manner, which indicated dissolution and secondary mineralization drove Ca migration during the Fe(II)-mediated transformation of SchCa. Adsorbed Ca blocked the surface sites for subsequent Fe(II) adsorption, limited the Fe(II)-Fe(III) ETAE, and decreased the transformation rates. This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.