Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

剩余污泥对活性黑KN-B的吸附性能

用剩余污泥对活性黑KN-B进行吸附研究,考察了pH、吸附时间、温度、盐类和污泥量等对活性黑KN-B吸附的影响.结果表明,剩余污泥对活性黑KN-B的吸附是一个快速过程,吸附时间可控制在30 min;其吸附过程可以用准二级动力学模型进行描述和预测;温度对污泥吸附活性黑KN-B产生的影响较小;其吸附等温线,25℃、35℃时与Freundlich方程拟合良好,45℃时则可以由Langmuir方程更好地描述.未调pH的剩余污泥,对pH≤2的废水中活性黑KN-B吸附性能良好;剩余污泥pH为1时,对pH＜12的废水中活性黑KN-B均可有效吸附;氯化钠浓度低于500 mg/L或氯化钠和硫酸钠的混合盐浓度低于100 mg/L时,有利于吸附;氯化钠浓度高于500 mg/L、混合盐浓度高于100 mg/L或单独加入硫酸钠后,随盐浓度的增加,吸附量呈下降趋势.     

玄武湖蓝藻水华成因探讨

为了解南京玄武湖蓝藻水华的成因,对玄武湖长期监测资料进行了分析和现场调查。结果表明,玄武湖鲢鳙急剧减少中断了正常的食物链,使浮游植物的牧食压力降低,在东南湖回水的诱因作用下,发生了以微囊藻为优势种群的蓝藻水华。指出,玄武湖蓝藻水华的发生进程表明,东南湖回水可能是蓝藻水华发生的诱因,生态失衡是蓝藻水华发生的主要原因,蓝藻水华的暴发与富营养化程度无显著相关性,其暴发加重了玄武湖富营养化程度。     

Fenton法脱色降解活性黑5模拟废水

本研究对benton试剂脱色降解活性黑5模拟废水进行了初步的实验研究。在恒温条件下,分别以600nm和255nm波长下染料溶液吸光度为主要测定指标,对该种染料的脱色及其芳环结构的氧化降解进行了同步分析。考察了染料溶液初始pH值、Fe^2＋浓度、H2O2投加量、染料浓度等因素的影响。结果表明,在一定实验条件下,活性黑5的脱色效率可达到99％,染料芳环结构的降解可达30％,COD去除率达到57．5％。活性黑5的脱色降解过程分为两个阶段进行。在最佳pH范围内,H2O2投加量、Fe^2＋浓度、染料浓度对染料初始脱色速率影响不大,但对后续的芳环结构降解影响较大。     

不同波长紫外光催化降解活性艳蓝KN-R动力学研究

以蒽醌类染料活性艳蓝KN-R(以下简称KN-R)为对象,以TiO2为光催化剂,实验了不同波段紫外光条件下KN-R的降解过程。结果表明:365 nm和254 nm两种波段对于KN-R的光催化降解过程均符合假一级动力学方程,但是通过对比各初始浓度下活性艳红KN-R的反应速率常数(Kapp)可以发现,在相同紫外灯功率下,短波辐射下的Kapp平均为长波辐射下Kapp的3倍,说明短波紫外更有利于活性艳蓝KN-R的降解。     

微波辐射处理活性艳蓝KN-R染料溶液的研究

在活性炭存在下微波照射能使活性艳蓝KN－R溶液迅速脱色，每g活性炭处理浓度为300mg／L的活性艳蓝KN－R溶液50mL，微波辐射4min脱色率达97．1％。     

改性氧化铝微波诱导氧化处理雅格素蓝BF-BR染料废水的研究

采用微波诱导氧化工艺(MIOP)技术,以改性氧化铝为催化剂,对雅格素蓝BF-BR染料模拟废水进行氧化处理．优化了处理工艺条件,实验在固液质量比为1：10(50mL雅格素蓝BF-BR水溶液中投加5．0g改性氧化铝)、微波功率为400W的条件下微波辐照处理5min．在此工艺条件下,对水中雅格素蓝BF-BR的脱色率可达到98％,COD去除率为87．4％．改性氧化铝在重复使用9次后仍能保持很高的脱色率．进一步研究表明在微波辐射场中废水中的有机污染物在改性氧化铝表面通过吸附．氧化协同作用而被迅速降解．反应动力学研究表明,该氧化过程符合一级反应动力学规律,反应速率常数k=0995min^-1,反应半衰期t1/2=0．697min．实验结果显示,在本实验中改性氧化铝比颗粒活性炭具有更高的催化活性．     

Removal of 2-ClBP from soil–water system using activated carbon supported nanoscale zerovalent iron

We explored the feasibility and removal mechanism of removing 2-chlorobiphenyl(2-Cl BP)from soil–water system using granular activated carbon(GAC) impregnated with nanoscale zerovalent iron(reactive activated carbon or RAC).The RAC samples were successfully synthesized by the liquid precipitation method.The mesoporous GAC based RAC with low iron content(1.32%) exhibited higher 2-Cl BP removal efficiency(54.6%) in the water phase.The result of Langmuir–Hinshelwood kinetic model implied that the different molecular structures between 2-Cl BP and trichloroethylene(TCE) resulted in more difference in dechlorination reaction rates on RAC than adsorption capacities.Compared to removing2-Cl BP in the water phase,RAC removed the 2-Cl BP more slowly in the soil phase due to the significant external mass transfer resistance.However,in the soil phase,a better removal capacity of RAC was observed than its base GAC because the chemical dechlorination played a more important role in total removal process for 2-Cl BP.This important result verified the effectiveness of RAC for removing 2-Cl BP in the soil phase.Although reducing the total RAC removal rate of 2-Cl BP,soil organic matter(SOM),especially the soft carbon,also served as an electron transfer medium to promote the dechlorination of 2-Cl BP in the long term.     

活性染料染色模拟液的电化学混凝研究

本文以铁电极电解装置处理活性翠篮K-GL及活性红M-8B染料染色模拟液,研究了电流密度,溶液pH值同模拟液脱色率及COD去除率的关系,同时还考察了PVA对于模拟液脱色及去除COD的影响。     

纳米TiO_2膜的制备及其光催化性能

采用溶胶 凝胶法(Sol Gel)制备了负载型纳米TiO2膜,分别考察了原料配比、pH值、煅烧温度对薄膜性质的影响,并利用XRD对其结构进行了表征,同时,用负载型TiO2膜对活性艳红X 3B(X 3B)模拟染料废水进行了微波辅助光催化脱色的研究。结果表明,改变原料配比及pH值可以制备出不同粒径的纳米TiO2膜,在450℃煅烧时TiO2呈锐态矿结构,在650℃以上出现锐态矿与金红石混晶结构,750℃时完全转变为金红石结构。所制得的纳米TiO2薄膜对X 3B具有较好的光催化活性。