交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

针铁矿-富里酸复合材料对铅镉污染土壤的钝化修复性能

珠三角地区作为粤港澳大湾区的重要经济区域,工矿企业多,土壤重金属污染状况较为严重,且多以铅镉复合污染为主,研发安全高效的重金属修复材料与技术对保障区域环境质量和人居安全具有重要意义.本文拟采用钝化修复技术,以南方红壤中典型矿物针铁矿为主体,制备了针铁矿-富里酸复合材料,并将其应用于铅镉复合污染土壤的钝化修复.结果表明,复合材料中富里酸所占的质量分数越高,对铅镉钝化作用效果越好;土壤中铅镉的钝化率(IE)随钝化时间的延长而增加,并趋于稳定;钝化修复后可交换态及碳酸盐结合态Pb含量降低,残渣态Pb含量增加,土壤中Cd可交换态含量降低,铁锰氧化态及残渣态含量显著增加;钝化修复后土壤CEC、速效钾及铵态氮含量均有所提高;综合评价认为针铁矿-富里酸复合材料应用于红壤铅镉钝化修复有效可行.     

Effects of fulvic acid and humic acid on aluminum speciation in drinking water

This article focused on the influences of fulvic acid and humic acid on aluminum speciation in drinking water. Factors including the concentration of residual chlorine and pH value had been concerned. Aluminum species investigated in the experiments included inorganic mononuclear, organic mononuclear, mononuclear, polymer, soluble, and suspended forms. It was found that the e ects of fulvic acid and humic acid on aluminum speciation depended mainly on their molecular weight. Fulvic acid with molecular weight less than 5000 Dalton had little influence on aluminum speciation; while fulvic acid with molecular weight larger than 5000 Dalton and humic acid would increase the concentration of soluble aluminum significantly even at concentration below 0.5 mg/L (calculated as TOC). Aluminum species, in the present of fulvic acid with molecular weight larger than 5000 Dalton and humic acid, were more stable than that in the present of fluvic acid with molecular mass less than 5000 Dalton, and varied little with reaction time. Within pH range 6.5–7.5, soluble aluminum increased notably in water with organic matter. As the concentration of residual chlorine increased, the e ects of fulvic acid and humic acid became weak. The reactions between humic acid, fulvic acid with large molecular weight, and aluminum were considered to be a multi-dentate coordination process. With the consideration of aluminum bioavailability, reducing the concentration of fulvic acid and humic acid and keeping the pH value among 6.5–7.5 were recommended during drinking water treatment.     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic featureswhere hydrophobic effect and phase transfer are the primary adsorptionmechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption.When the soil organicmatterwas extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO₂ surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided newperspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

堆肥腐熟前后胡敏酸与富里酸的还原容量比较

采集腐熟前后的堆肥样品并提取和纯化出腐殖质(胡敏酸:HA;富里酸:FA),分别以柠檬酸铁(FeCit)和Fe(NO3)3作电子受体,测定了HA和FA的还原容量(RC).结果表明:以FeCit作为电子受体时,与未腐熟堆肥样品相比,腐熟后筛分样品HA的RC值增大,从22.85mmol e-/molC增大到26.84mmol e-/molC,而其对应FA的RC值减少,由37.67mmol e-/molC降低为33.68mmol e-/molC;对于两种不同形态的电子受体,以 FeCit为电子受体测定得到的RC值高于以Fe(NO3)3为电子受体测定得到的RC值;相对于本底还原容量,HA和FA经微生物还原后其RC值降低,降低幅度与微生物种类有关.结合紫外-可见光谱和三维荧光光谱分析发现,堆肥HA和FA的还原能力与其中类富里酸物质含量和醌基浓度成正相关,而与其本身的芳化度和分子量呈负相关.     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeO_xH_2x-3复合材料，研究了富里酸在UV/H₂O₂和UV/H₂O₂/Fe-FeO_xH_2x-3两种不同反应体系下的降解情况。结果表明，核-壳结构Fe-FeO_xH_2x-3的存在，提高了UV/H₂O₂降解富里酸的反应速率，TOC去除达到84%。采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征，结果表明，富里酸经反应后憎水酸（HoA）、弱憎水酸（WHoA）和憎水中性物质（HoN）都有所减少，进而转化为亲水性物质（HiM）；用超滤膜法对富里酸进行物理分级表征，考察了富里酸在反应前后分子量分布的变化情况。同时，富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势。     

Adsorption characterizations of fulvic acid fractions onto kaolinite

Fulvic acids extracted from a typical rice-production region near Taihu Lake of China were fractionated into three fractions including F4. 8, F7. 0 and F11. 0(eluted by pH4. 8 buffer, pH 7. 0bufferandpH 11. 0buffer, respectively). Sorption of fulvic acid(FA)fractions onto kaolinite was studied by batch adsorption experiments, and characterizations of kaolinite before and after adsorption were investigated using scanning electron microscopy(SEM). Adsorption isotherms of kaolinite for three FA fractions fit well with the Langmuir adsorption model. The adsorption density of the three fractions was positively correlated with the ratio of the amount of the alkyl carbon to that of carboxyl and carbonyl carbon in FA fractions and followed an order of F11. 0>F7. 0>F4.8.Hydrophobic interaction Was one of the control mechanisms for the sorption of FA fraction onto kaolinite. SEM images confirmed that compared to blank kaolinite samples, kaolinite samples coated by a FA fraction displayed an opener and more dispersed conformation resulting from the disruption of the floe structure in complex. Dispersion of kaolinite after adsorption was due to the repulsion between negatively charged FA. coated particles, which is closely related to the amount of FA fractions absorbed on kaolinite.     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

Effect of fulvic acid on the photochemical degradation of methylparathion

Photochemical degradation of methylparathion (O,O,–dimethyl O-4 nitrophenylphosphorothioate) in the presence of fulvic acid (FA) between pH 2 and 7 was studied by differential pulse polarography (DPP). Fulvic acid and its photoproducts were not electro-active under the experimental conditions used in this study, and only the pesticide exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by fulvic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 3.3 × 10^?3 to 8.8 × 10^?3min^?1.     

老化前后微塑料对富里酸的吸附

由于微塑料(MPs)在地表水环境中的广泛存在以及对水中有机污染物的较强吸附能力,其与地表水中天然有机物间的相互作用不容忽视.为深入了解微塑料对天然有机物的影响,开展了老化前后聚酰胺66(PA66)和聚丙烯(PP)两种微塑料吸附富里酸(FA)的研究.结果表明,老化前后的微塑料吸附富里酸的试验数据较好地拟合了准二级动力学模...