药物对A/A/O系统中NDMA及其总前体物去除的影响

在厌氧/缺氧/好氧(A/A/O)脱氮除磷系统中分别投加氯苯那敏和雷尼替丁,研究了这两种含有二甲胺基团的药物对A/A/O系统中N-亚硝基二甲胺(NDMA)及其总前体物去除效果的影响.结果表明, A/A/O系统对氯苯那敏和雷尼替丁的去除率较低,分别为32%和58%,且主要通过厌氧过程去除.外加氯苯那敏会导致系统对总氮的去除率从58%降至24%,同时引起出水氨氮浓度上升.雷尼替丁的投加会明显抑制系统对NDMA的去除,其去除率从90%降至66%.A/A/O反应器中NDMA的去除并不完全受生物脱氮过程的影响.由于具有较高的NDMA生成潜能,外加氯苯那敏,雷尼替丁会引起进水中NDMA总前体物浓度大幅增加,且导致A/A/O系统对NDMA总前体物的去除率明显下降 (从70%降到31%~33%).     

Elucidating the removal mechanism of N,N-dimethyldithiocarbamate in an anaerobic-anoxic-oxic activated sludge system

N,N-Dimethyldithiocarbamate （DMDTC） is a typical precursor of N-nitrosodimethylamine （NDMA）. Based on separate hydrolysis, sorption and biodegradation studies of DMDTC, a laboratory-scale anaerobic-anoxic-oxic （AAO） system was established to investigate the removal mechanism of DMDTC in this nutrient removal biological treatment system. DMDTC hydrolyzed easily in water solution under either acidic conditions or strong alkaline conditions, and dimethylamine （DMA） was the main hydrolysate. Under anaerobic, anoxic or oxic conditions, DMDTC was biodegraded and completely mineralized. Furthermore, DMA was the main intermediate in DMDTC biodegradation. In the AAO system, the optimal conditions for both nutrient and DMDTC removal were hydraulic retention time 8 hr, sludge retention time 20 day, mixed-liquor return ratio 3：1 and sludge return ratio 1：1. Under these conditions, the removal efficiency of DMDTC reached 99.5%; the removal efficiencies of chemical organic demand, ammonium nitrogen, total nitrogen and total phosphorus were 90%, 98%, 81% and 93%, respectively. Biodegradation is the dominant mechanism for DMDTC removal in the AAO system, which was elucidated as consisting of two steps： first, DMDTC is transformed to DMA in the anaerobic and anoxic units, and then DMA is mineralized to CO2 and NH3 in the anoxic and oxic units. The mineralization of DMDTC in the biological treatment system can effectively avoid the formation of NDMA during subsequent disinfection processes.     

UV/O_3对亚硝基二甲胺降解产物的控制研究

对CUV/O3和UV/H2O2 2种高级氧化工艺降解水中亚硝基二甲胺(NDMA)和控制二甲胺(DMA)生成的能力进行了比较研究.结果表明,UV/H202能够有效降解NDMA,但不能控制NDMA降解产物DMA的生成;UV/O3高级氧化技术不仅能够有效地去除NDMA,同时对DMA的生成量也有很好的控制作用.进一步考察了不同臭氧浓度、溶液pH值以及NDMA初始浓度对UV/O3工艺控制DMA生成量的影响.结果表明,臭氧浓度对UV/O3控制DMA的生成有一定的影响,DMA的生成量随着臭氧浓度的增大而减小,臭氧浓度为6.64 mg·L-1时,降解7.7 mg·L-1 NDMA生成DMA的量为O.98 mg·L-1.溶液pH值对UV/03控制DMA的影响较大,酸性和中性pH条件下,DMA的生成量随着pH的增大略有增加;碱性pH条件下,DMA的生成量明显减小,pH;11.0时降解初始浓度为7.7 mg·L-1的NDMA,DMA的生成量仅为0.3 mg·L-1.NDMA的初始浓度对UV/03控制DMA的生成也有影响,NDMA初始浓度较小时,UV/O3对DMA生成的控制更为明显.     

天然斜发沸石粉对溶液中NH4+的吸附机理研究

采用天然斜发沸石粉(平均粒径30μm)进行吸附溶液中NH4+的试验研究,并对系统中金属阳离子的液相和固相含量进行了全程跟踪测定.等温吸附试验、吸附动力学研究结果表明,天然斜发沸石对溶液中NH4+的吸附过程符合Freundlich线性模型(R2=0.996),该吸附过程属于优惠吸附;吸附动力学符合假二级方程(R2>0.99),且随着初始NH4+浓度的增加,吸附反应的优惠程度降低.沸石粉对NH4+的吸附过程中离子交换以Ca2+和Na+为主,Na+首先被交换出来,随着吸附过程进行,Ca2+交换量逐渐增加并超过Na+,两者交换当量分别占39%~60%和35%~57%.由于沸石粉粒径较小,其对NH4+的去除除了依靠离子交换作用外,物理吸附作用的贡献不容忽视.     

纳米零价铁去除水中微量N-亚硝基二甲胺的研究

采用纳米零价铁催化降解水中微量N-亚硝基二甲胺(NDMA),并研究了溶解氧、纳米铁投加量、NDMA初始浓度、初始pH值、温度对纳米铁降解NDMA的影响.结果表明,纳米铁可以在中性厌氧条件下有效降解NDMA,作用效果远胜于普通铁粉;其对NDMA的去除速率随着纳米铁投加量的增加而增大,但与NDMA初始浓度无关;pH值降低或温度升高均有利于NDMA的降解.纳米铁降解NDMA存在一个启动期,启动期的长短与pH值和反应温度有关,提前活化纳米铁能有效提高反应速率.NDMA的降解产物主要是DMA和NH4+,其他产物如UDMH需进一步确认.     

丽江-玉龙雪山不同区域大气降水化学特征

2008─2009年在丽江-玉龙雪山地区的丽江市区、玉龙雪山冰川公园索道下部站(索道地区)和白水1号冰川区(冰川区)3个采样点采集了113个降水样品,对其pH、电导率和主要离子(Cl-、SO42-、NO3-、Ca2+、Mg2+、Na+、K+和NH4+)质量浓度进行了分析.结果表明,所有样品实测pH均高于5.6.3个采样点ρ(总离子)平均值为丽江市区>索道地区>冰川区,其中ρ(SO4 2-)和ρ(Ca2+)均最高.丽江市区季风前后各离子质量浓度变化显著,其中海盐离子质量浓度〔ρ(Na+)和ρ(Cl-)〕从季风前期到季风期变化不大,在季风后期增加;ρ(NO3-)、ρ(SO42-)、ρ(NH4+)、ρ(Ca2+)、ρ(K+)和ρ(Mg2+)在季风前期显著高于季风期和季风后期.采用相关分析和主因子分析法对降水中离子来源进行研究,表明SO42-、NO3-和NH4+主要来自局地人类活动的贡献,Na+、K+和Cl-是海洋源贡献,Ca2+和Mg2+主要来源于地表粉尘.      

pH值和离子对诺氟沙星在胡敏酸上吸附特征的影响

根据OECD Guideline 106批平衡实验,研究了pH值、Ca2+浓度和离子类型对诺氟沙星在胡敏酸上吸附特征的影响.结果表明,吸附系数(Kd)随着pH值的增大有先增加后减小的趋势,在pH 4.0和pH 6.0时吸附系数较大.红外光谱表明,pH 3.0有利于诺氟沙星和胡敏酸形成氢键; pH6.0和7.0时胡敏酸的羧基可能与诺氟沙星的氨基形成了肽键.诺氟沙星在胡敏酸上的吸附量和Kd值随着溶液中Ca2+离子浓度的增加而逐渐减小,表明两者之间存在阳离子吸附和竞争吸附.不同类型的阳离子和阴离子的加入都能导致诺氟沙星在胡敏酸的吸附特性存在差异.阳离子的影响趋势主要为价态的影响,即价态越高,在胡敏酸表面吸附位点的吸附能力就越强,对诺氟沙星吸附阻碍作用越显著,表现在诺氟沙星的最大吸附量(Qm)为:M+ (Na+、K+、NH4+) >M2+ (Mg2+、Ca2+、Zn2+);其次受阳离子的离子半径和水解作用的影响.而只有能水解的阴离子才能对诺氟沙星在胡敏酸上的吸附产生明显的阻碍作用.     

Effects of simulated acid rain on cation release in soils of South China

This paper deals with the release of base cations and Al3+ at the treatment with simulated acid rain (SAR) in main soil types collected from South China. Results showed that the amounts of base cations increased obviously when the pH value of simulated acid rain was lower than 3.0 or 3.5. Compared with the leaching of K+ and Na+, the leaching of Ca2+ and Mg2+ was affected by the pH value of SAR. Only when the amounts of base cations leached from soils exceeded the cation exchange capacity, the pH value of leaching solutions decreased sharply and the amounts of released Al3+ increased. The H+ buffering mechanisms, which were affected notonly by the pH values of SAR, but also by the types and solid components of soils, were proposed for the main soils studied.     

Effects of simulated acid rain on cation release in soils of South China

This paper deals with the release of base cations and Al3+ at the treatment with simulated acid rain (SAR) in main soil types collected from South China. Results showed that the amounts of base cations increased obviously when the pH value of simulated acid rain was lower than 3.0 or 3.5. Compared with the leaching of K+ and Na+, the leaching of Ca2+ and Mg2+ was affected by the pH value of SAR. Only when the amounts of base cations leached from soils exceeded the cation exchange capacity, the pH value of leaching solutions decreased sharply and the amounts of released Al3+ increased. The H+ buffering mechanisms, which were affected notonly by the pH values of SAR, but also by the types and solid components of soils, were proposed for the main soils studied.     

混合液回流比和碳源对缺氧-好氧生物脱氮系统中NDMA总前体物去除的影响

在缺氧-好氧(A/O)脱氮系统中调节混合液回流比和外加碳源,研究了混合液回流比和不同碳源对低碳氮比城市污水中NDMA总前体物去除效果的影响.实验结果表明提高混合液回流比可以提高A/O系统对NDMA总前体物的去除效果,其作用主要通过影响缺氧池来实现;混合液回流比为400%时,可同时较大幅度提高常规指标和NDMA总前体物的去除率.外加碳源有利于A/O系统中NDMA总前体物的去除,当葡萄糖和蛋白胨作外加碳源时,A/O系统中缺氧池对NDMA的去除起主要作用;当乙酸钠作外加碳源时,缺氧池所起的作用下降;蛋白胨的加入会使进水中NDMA总前体物浓度大幅度增加;综合常规指标和NDMA总前体物的去除效果,选择葡萄糖作外加碳源比较合适.     

城市污水生物脱氮系统出水经氯胺消毒形成NDMA的影响因素研究

为了考察城市污水回用时氯消毒过程中NDMA的形成,以2套生物脱氮实验装置厌氧/缺氧/好氧(A/A/O)和缺氧/好氧(A/O)的二沉池出水为对象,研究了氯胺消毒过程中氯胺剂量、pH、NO2--N和NO3--N浓度对N-亚硝基二甲胺(NDMA)形成的影响.结果表明,二沉池出水中仍然含有微量的NDMA前体物,导致了氯胺消毒过程中NDMA的形成,而且NDMA的浓度会随氯胺浓度的增加呈线性增加;在中性或稍偏碱性(pH 7～8)的条件下,NDMA生成量最大;二沉池出水中NO2--N和NO3--N的浓度对NDMA的含量皆不会产生明显影响.     

锆改性沸石对水中磷酸盐和铵的吸附特性

采用锆对天然沸石进行改性,并研究了锆改性沸石对水中磷酸盐和铵的吸附特性.结果表明,锆改性沸石对水中磷酸盐和铵均具有很好的吸附能力.锆改性沸石对水中磷酸盐和铵的吸附动力学过程满足准二级动力学模型.Langmuir、Freundlich和Dubinin–Radushkevich(D–R)等温吸附模型可以很好地描述锆改性沸石对水中磷酸盐的等温吸附行为.Langmuir等温吸附模型可以很好地描述锆改性沸石对水中铵的等温吸附行为.由Langmuir等温吸附模型计算得到锆改性沸石对磷酸盐和铵的最大吸附容量分别达到26.2,7.82 mg/g.热力学参数表明锆改性沸石对水中磷酸盐的吸附是自发的吸热反应过程.锆改性沸石对水中磷酸盐的吸附能力随着pH值的增加而降低.当pH4~8时,锆改性沸石对水中铵的吸附能力较高;当pH低于4或高于8时,对铵的吸附能力下降.水中共存的Cl-、SO42-、HCO3-和NO3-等阴离子对锆改性沸石吸附磷酸盐的影响很小,而共存的SiO32-对磷酸盐的吸附则具有较强的负面影响.水中共存的Ca2+和Mg2+对锆改性沸石吸附铵的影响较小,而共存的K+和Na+对铵的吸附则具有较强的负面影响.锆改性沸石吸附水中磷酸盐的主要机制是阴离子配位体的交换,吸附水中铵的主要机制是与沸石中可交换阳离子的离子交换.     

Effect of activated sludge treatment on the formation of Nnitrosamines under different chloramination conditions

Municipal wastewater discharge is considered as one of the main sources of N-nitrosamine precursors which can impact the qualities of downstream source waters and reclaimed wastewaters for potable reuse. NNitrosamine precursors can be removed to various degrees during biological wastewater treatment (e.g., the activated sludge (AS) process). So far, little is known about the impact of the AS process on N-nitrosamine formation under practical disinfection condition (e.g., uniform formation condition (UFC)). In this study, N-nitrosamine UFC from selected model compounds, sewage components (i.e., blackwaters and greywaters) and sewage samples were comprehensively investigated during batch AS treatment tests. NNitrosodimethylamine (NDMA) formation from the tested precursor compounds (i.e., trimethylamine (TMA) and sumatriptan (SMTR)) under UFC chloramination decreased mostly after 6 or 24 hr treatment with different types of AS (i.e., domestic rural AS, domestic urban AS, and textile AS), and the reductions in NDMA UFC were comparable to their NDMA formation potential (FP) reductions. In urine and feces blackwaters, NDMA UFC increased after 6 or 24 hr treatment with the domestic (i.e., rural and urban) AS, while NDMA FP decreased substantially. The increases in NDMA UFC after AS treatment was presumably attributed to the removal of bulk organic matters (e.g., dissolved organic carbon (DOC)) which favored NDMA formation under UFC. On the other hand, in laundry greywaters having relatively abundant DOC, N-nitrosamine UFC was less affected by DOC removal before or after AS treatment, but decreased to similar degrees with N-nitrosamine FP. In sewage samples collected from wastewater treatment plants, N-nitrosamines UFC tended to increase or remain constant during AS treatment, despite the decreases in their FPs. These results suggest that biological wastewater treatment (e.g., the AS process) may not effectively reduce N-nitrosamine formation (e.g., measured under UFC) partially because the concurrent removal of bulk organic matters (e.g., DOC) favored N-nitrosamine formation in s econdary effluents.     

Experimental and density functional theory study of the adsorption of N2O on ion-exchanged ZSM-5: Part II. The adsorption of N2O on main-group ion-exchanged ZSM-5

The adsorption and desorption of N2O on main-group ion-exchanged ZSM-5 was studied using temperature-programmed desorption (TPD) and density functional theory (DFT) calculations. TPD experiments were carried out to determine the desorbed temperature Tmax corresponding to the maximum mass intensity of N2O desorption peak and adsorption capacity of N2O on metal-ion-exchanged ZSM- 5s. The results indicated that Tmax followed a sequence of Ba2+ > Ca2+ > Cs+ > K+ > Na+ > Mg2+and the amount of adsorbed N2O on main-group metal cation followed a sequence of Ba2+ > Mg2+ > Ca2+ > Na+ > K+ > Cs+. The DFT calculations were performed to obtain the adsorption energy (Eads), which represents the strength of the interaction between metal cations and the N-end or O-end of N2O. The calculation results showed that the N-end of the N2O molecule was favorably adsorbed on ion-exchanged ZSM-5, except for Cs-ZSM-5. For alkali metal cations, the Eads of N2O on cations followed the order which was the same to that of Tmax: Cs+ > K+ > Na+. The calculated and experimental results consistently showed that the adsorption performances of alkaline-earth metal cations were better than those of alkali metal cations.     

Pb(Ⅱ) biosorption using chitosan and chitosan derivatives beads: Equilibrium,ion exchange and mechanism studies

The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and different initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non-linear Langmuir isotherm for ch...     

南方土壤酸沉降敏感性研究Ⅶ——盐基淋溶与缓冲机理

研究了模拟酸雨对我国南方主要土壤类型盐基离子淋溶的影响,结果表明,ＰＨ低于３．０或３．５时,盐基离子淋溶总量明显增加,但ＰＨ高于３．５时,则影响不明显。     

水中污染物对阳离子交换膜分离去除Cu2+的影响

基于Donnan dialysis原理,在无外加电压作用下采用阳离子交换膜分离去除原水中的Cu2+,研究原水中可能出现的无机颗粒物,有机物质,EDTA酸、氨水、Fe3+、表面活性剂等对阳离子交换膜分离去除Cu2+效果的影响.研究表明:原水中添加二氧化硅、腐殖酸、EDTA酸、氨水、Fe3+、表面活性剂等物质,在长时间运行后均会对离子交换膜去除Cu2+有不同程度的影响;二氧化硅和非离子表面活性剂等污染物不会和膜及Cu2+发生物理化学反应,对膜去除Cu2+效果影响较小,相比空白样,Cu2+去除率下降约4%;氨水、阴离子表面活性剂等会导致Cu2+发生沉淀反应,腐殖酸会吸附Cu2+,使原水中游离态Cu2+浓度显著降低约50%;EDTA酸、氨水、阴离子表面活性剂等会与Cu2+形成络合物,对去除Cu2+有严重影响,相比空白样, Cu2+去除率分别下降约100%(EDTA酸)、78%(氨水)、56%(阴离子表面活性剂);阳离子表面活性剂存在时,其会大量占据膜内空间,Cu2+基本无去除;Fe3+在弱酸性或中性水中会水解生成氢氧化铁胶体,对去除Cu2+有一定影响,相比空白样, Cu2+去除率下降约12%.     

天然斜发沸石对溶液中NH4+的物化作用机理

选择中国浙江缙云天然斜发沸石为试验材料,以摇床试验和离子跟踪监测,研究了斜发沸石对溶质NH4+的物化作用机理.在天然斜发沸石对溶液中NH4+的作用过程中,离子交换作用决定了NH4+的全部转移量,沸石晶体内Na+和Ca2+与溶液中NH4+的交换量占总离子交换量的97%以上.对于粒径1.0~3.2mm的沸石,交换反应前3h时可完成83%的Na+交换量和50%的Ca2+交换量.     

Bacillus natto TK-2产γ-絮凝活性的研究

对γ-聚谷氨酸的絮凝活性进行了研究,得出了其最佳絮凝条件为:γ-聚谷氨酸投加浓度为10mg/L;絮凝体系的pH为7.0;γ-聚谷氨酸在80℃以下都能保持很高的絮凝活性;添加不同种类的K+,Na+,Ca2+,Mg2+,Fe2+,Fe3+,Al3+能不同程度地提高γ-聚谷氨酸的絮凝活性,其中添加Ca2+的助凝效果最好,最终选择Ca2+为最佳的助凝离子并确定添加浓度为100mg/L。     

阳离子改型蛭石的铵离子交换平衡特性

对经Na^＋，Ca^2＋、Mg^2＋等不同离子处理的改型蛭石在不同pH和温度条件下进行了铵离子交换性能的研究。结果表明，交换反应均在前60min速率最快，约120min就趋向于平衡：铵离子交换总量均随pH变化而波动，在pH=7点上取最大值，且全交换容量按镁型蛭石、钙型蛭石，钠型蛭石顺序依次增大，每100g蛭石分别为59.32，71.89、92.85mmol；改型蛭石对NH^＋4等温交换吸附与Langmuir方程相符。表明改型蛭石对NH^＋4的吸附主要是单分子层的化学吸附。