《大气污染防治行动计划》后期成都大气PM2.5中水溶性无机离子特征

为探究《大气污染防治行动计划》实施后期成都大气PM2.5中水溶性无机离子(WSIIs)季节变化及来源等特征,本研究于2016～2017年在成都城区进行了分季节PM2.5样品的连续采集,对其中WSIIs进行了全面分析.结果表明,成都市年均ρ(PM2.5)和ρ(WSIIs)分别为(114.0±76.4)μg.m-3和(41.2±31.3)μg.m-3,ρ(WSIIs)可占ρ(PM2.5)的36.1％,其季节贡献特征为:秋季(39.5％)＞冬季(38.2％)＞春季(32.5％)＞夏季(28.9％).全年及各季节P(PM2.5)和ρ(WSIIs)均值均表现为夜间高于白天,且昼夜差异幅度呈现出了明显的季节变化特征.SNA(SO42-、N03-和NH4+)是WSⅡs的重要组成,在春、夏、秋和冬这4季中可占到整体ρ(WSIIs)的84.2％、86.6％、86.3％和87.0％.秋和冬的ρ(NO3)/ρ(SO42-)比值分别为1.1和1.6,高于春和夏的0.96和0.57,移动源和固定源相对贡献随季节变化特征明显.观测期间WSIIs主要来源包括二次生成、扬尘源和燃烧源.后向轨迹分析表明,来自成都东部地区的近地气团对应的P(PM2.5)低于源自西部的高空气团,就WSIIs构成而言,东部气团对应的ρ(SO42-)占比高于西部气团,而西部气团对应的ρ(NO3-)占比则高于前者.     

不溶性腐殖酸对重金属离子的吸附研究

讨论了不溶性腐殖酸(IHA)对水中重金属pb2 、Cd2 、Cu2 的吸附去除作用.将可溶性腐殖酸进行改性处理,制备了不溶性腐殖酸,并应用差热分析(TG-DTA)、扫描电镜(SEM)等测试手段对其热性能及微观形貌进行了分析表征.研究了不溶性腐殖酸对水溶液中的Pb、Cd、Cu等重金属离子的吸附特征.吸附等温线分别以Linear,Frendlich和Langmuir方程进行拟合,结果显示吸附的最佳模型为Frendlich方程.利用该方程拟合的数据,由Clausius-Claperyon's方程计算出的pb2 、Cd2 、Cu2 吸附焓变值说明,重金属在不溶性腐殖酸上的吸附以物理吸附为主.同时考察了温度、酸度及吸附时间对吸附的影响.结果表明,随着温度的升高和pH值的增大,不溶性腐殖酸对pb2 、Cd2 、Cu2 的吸附量增加.随着pH的增加,在近中性条件下不溶性腐殖酸对重金属离子的吸附率高且稳定.当pH=7时,在实验浓度范围内pb2 、Cd2 、Cu2 在不溶性腐殖酸中的吸附率分别为98.73%,97.86%,99.25%.吸附进行12 h以后,吸附作用基本达到平衡.不溶性腐殖酸对重金属离子具有强烈的吸附作用且吸附率稳定,可以广泛用于去除污水中的重金属离子.     

酿酒酵母吸附Zn(Ⅱ)过程中阳离子(K+，Mg2+，Na+，Ca2+)的变化分析

研究了酿酒酵母无缓冲溶液体系吸附Zn(Ⅱ)的过程中各种阳离子的变化情况.研究结果表明,当Zn(Ⅱ)的初始浓度是0.08～0.8 mmol·L^-1,酵母浓度约1 g·L^-1,初始pH为5.65,反应38h内,酵母的Zn(Ⅱ)吸附量为74.8～654.8μmol·g^-1,去除率达到76.4%～92.8%,pH值升高0.55～1.28.吸附过程中酵母首先快速释放大量K⁺,其次是Mg²⁺和Na⁺,Ca²⁺的释放量较少,数量级一般可分别达到几百、几十和几个μmol·g^-1.以离子交换为基础计算的各阳离子释放量总和一般超过Zn(Ⅱ)的吸附量,证明酵母吸附Zn(Ⅱ)的机理之一是离子交换,但不唯一.无缓冲溶液体系酵母吸附Zn(Ⅱ)的过程中溶液pH值升高,H⁺被吸收,K⁺等阳离子释放,是生物体细胞的本质属性,与Zn(Ⅱ)是否存在无关,但是Zn(Ⅱ)可以促进阳离子的释放以及降低酵母对H+的吸收,也反映出Zn(Ⅱ)与H⁺之间可以竞争细胞表面吸附位.死酵母的吸附量低于未处理酵母,与阳离子交换能力关系不大,可能与细胞表面变形导致Zn(Ⅱ)吸附困难有关.     

Unravelling the effects of complexation of transition metal ions on the hydroxylation of catechol over the whole pH region

Catechol pollutants (CATPs) serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes. Little information is available on the effects of complexation of metal ions on CATPs degradation. This work presents a systematical study of •OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes (AOPs). Results show that the pH-dependent complexation of metal ions (Zn²⁺, Cu²⁺, Ti⁴⁺ and Fe³⁺) promotes the deprotonation of catechol under neutral and even acidic conditions. The radical adduct formation (RAF) reactions are both thermodynamically and kinetically favorable for all dissociation and complexation species, and OH/O⁻ group-containing C positions are more vulnerable to •OH attack. The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation. At pH 7, the apparent rate constant (k_app) values for different systems follow the order of catechol+Ti⁴⁺ ≈ catechol+Zn²⁺ > catechol+Cu²⁺ > catechol+Fe³⁺ > catechol. The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs. The toxicity assessment indicates that the •OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.     

Mg (OH)2@粉煤灰复合材料对重金属离子的去除研究

根据“粒子设计”思想，以粉煤灰为载体，采用非均匀形核法制备了一种核壳结构粉煤灰负载纳米氢氧化镁复合材料，并对其吸附废水中Cu （II）、Ni （II）和Pb （II）性能进行研究.采用扫描电子显微镜（SEM）、EDS能谱、比表面积分析仪（BET）、X射线衍射（XRD）、红外光谱（FTIR）等技术对包覆前后的复合粉体进行了表征.结果表明，复合粉体表面均匀包覆了大量纳米氢氧化镁和少量水合碳酸镁，比表面积增大到原来（粉煤灰1.79m²/g）的30多倍，平均孔径由11nm增加至14.7nm.平均孔隙宽度从12.8nm增加至15.4nm.粉煤灰表面的Si-O-Si、Si-O-C与氢氧化镁之间形成Si-O-C-O-Mg和Si-O-Mg-OH.复合粉体材料去除重金属的效率明显高于原粉煤灰和氢氧化镁，其单位饱和吸附量分别达到了216.30、116.50、160.96mg/g.根据Zeta电位、FTIR及模拟方程分析了复合粉体吸附重金属离子机理，结果表明复合粉体材料对重金属离子通过沉淀反应、静电吸引、离子交换等方式进行吸附，吸附过程等温线符合Langmuir等温模型，动力学符合颗粒内扩散模型，热力学符合自发吸热反应.通过解吸再生试验发现，经过5次循环再生利用后，复合粉体对重金属离子的去除率达到50%以上，这说明复合粉体在吸附过程中具有良好的再生性能.     

Insight into the formation of iodinated trihalomethanes during chlorination, monochloramination, and dichloramination of iodide-containing water

In this study, the formation of iodinated trihalomethanes (I-THMs) was systematically evaluated and compared for three treatment processes - (i) chlorination, (ii) monochloramine, and (iii) dichloramination - under different pH conditions. The results demonstrated that I-THM formation decreased in the order of monochloramination > dichloramination > chlorination in acidic and neutral pH. However, the generation of I-THMs increased in the dichloramination < chlorination < monochloramination order in alkaline condition. Specifically, the formation of I-THMs increased as pH increased from 5 to 9 during chlorination and monochloramination processes, while the maximum I-THM formation occurred at pH 7 during dichloramination. The discrepancy could be mainly related to the stability of the three chlor (am) ine disinfectants at different pH conditions. Moreover, in order to gain a thorough insight into the mechanisms of I-THM formation during dichloramination, further investigation was conducted on the influencing factors of DOC concentration and Br⁻/I⁻ molar ratio. I-THM formation exhibited an increasing and then decreasing trend as the concentration of DOC increased from 1 to 7 mg-C/L, while the yield of I-THMs increased with increasing Br⁻/I⁻ molar ratio from 5:0 to 5:10. During the three processes mentioned above, similar I-THM formation results were also obtained in real water, which indicates that the excessive generation of I-THMs should be paid special attention during the disinfection of iodide-containing water.