The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Invasive Species Research to Meet the Needs of Resource Management and Planning

Abstract: As zebra mussels (Dreissena polymorpha) continue to spread among inland lakes of the United States and Canada, there is growing interest from professionals, citizens, and other stakeholders to know which lakes are likely to be colonized by zebra mussels. Thus, we developed a classification of lake suitability for zebra mussels on the basis of measured or estimated concentrations of dissolved calcium in lake water and applied the classification to >11,500 lakes in Wisconsin and the Upper Peninsula of Michigan. The majority of lakes (58%) were classified as unsuitable (<10 mg/L Ca) for survival and reproduction of zebra mussels, 27% were identified as suitable (≥21 mg/L Ca), and 15% were classified as borderline suitable (≥10 and <21 mg/L Ca). Of the 77 inland lakes with confirmed zebra mussel records for which data on dissolved calcium were available, our method classified 74 as suitable and 3 as borderline suitable. To communicate this lake‐specific suitability information and to help prioritize regional efforts to monitor and prevent the expansion of zebra mussels and other invasive species, we developed a web‐based interface (available from http://www.aissmartprevention.wisc.edu/ ). Although we are still uncertain of how access to suitability information ultimately affects decision making, we believe this is a useful case study of building communication channels among researchers, practitioners, and the public.     

基于移动监测和土地利用回归模型的上海市近地面黑碳浓度空间模拟

黑碳(BC)是大气污染物的重要组成部分,对空气质量与人类生活健康产生重要的影响.本研究采用移动样带手段开展上海市近地面BC浓度监测,分析其基本统计特征和空间分异性.在此基础上,利用土地利用回归模型(LUR),探讨人口密度、经济产值和交通道路网密度等因素对上海市近地面BC浓度空间分异的影响.结果表明上海市近地面BC平均浓度为(9.86±8.68)μg·m~(-3),空间差异明显,郊区[(10.47±2.04)μg·m~(-3)]比市中心地区[(7.93±2.79)μg·m~(-3)]高32.03%(2.54μg·m~(-3)).气象要素(风速和相对湿度)和交通道路变量(路网长度、省道距离、高速距离等)显著影响上海市近地面BC浓度(r为0.5~0.7,P0.01).基于气象和交通道路变量的LUR模型能较好模拟上海近地面BC浓度(调整后R2为0.62~0.75,交叉验证R2为0.54~0.69,RMSE为0.15~0.20μg·m~(-3)),其中100 m和5 km缓冲距离的LUR模型相对较优,在一定程度上表明上海市近地面BC浓度主要受气象要素和交通源的影响.本研究有利于加深对上海市BC浓度空间分布格局及其影响因素的客观认识,可为模拟和预测BC对人类活动和自然环境的响应机制提供科学依据和理论支撑.     

南宁市一次污染过程大气颗粒物理化特性及来源

利用颗粒物粒径谱仪和单颗粒气溶胶质谱仪等,对南宁市2016年12月5~11日大气污染过程进行实时监测,分析颗粒物粒径分布特征、化学组分及其污染来源.结果表明,观测期间南宁市20 nm~10μm颗粒物数浓度粒径主要集中在23~395 nm之间,主峰值出现在100 nm左右.期间有3次新粒子生成现象,下午14:00~18:00有30 nm左右新粒子开始生成,晚20:00~次日06:00碰并长大到40~110 nm左右,3次新粒子生成过程受机动车尾气一次排放的污染影响.对污染期间细颗粒物化学成分在线溯源分析发现,污染期间有大量的二次反应颗粒物生成,判定颗粒物来源主要有生物质燃烧源、扬尘源和燃煤源,其中,远距离传输对生物质燃烧源有贡献.     

不同CDPF贵金属负载量对柴油公交车VOCs组分排放影响

基于重型底盘测功机,利用质子转移反应质谱(PTR-MS)研究了柴油公交车在中国典型城市公交车循环(CCBC)下,不同CDPF贵金属负载量对尾气中挥发性有机物(VOCs)组分排放特性的影响.结果表明,柴油公交车VOCs主要组分为含氧有机物(OVOCs)、芳香烃和烯烃等,且OVOCs占比达50%以上;在贵金属成分、配比相同时,VOCs减排率随CDPF贵金属负载量增加而增加:贵金属负载量为15 g·ft~(-3)(A型后处理装置)、25 g·ft~(-3)(B型)和35 g·ft~(-3)(C型)时,VOCs总量的减排率依次为36.2%、40.1%和41.4%.C型后处理装置对烷烃全循环减排率高达70.2%,且对OVOCs的催化有微弱优势;对于不饱和烃类,3种不同贵金属负载量的后处理装置均有一定催化效果,但无明显差异;A型对含氮有机物减排率可达50.5%,但减排率随贵金属负载量增加而降低.采用DOC+CDPF后能较好地降低公交车VOCs排放量进而降低臭氧生成潜势(OFP).同时考虑不同方案减排效果与成本因素,当加权系数分别为0.8和0.2时,B型为最优方案.     

AAO工艺低氧条件下的运行及其模拟

利用厌氧-缺氧-好氧(AAO)工艺探讨了在好氧池低溶解氧(DO)浓度条件下的水质指标变化情况.结果表明,当好氧池DO浓度从2.00 mg·L~(-1)降低到1.00 mg·L~(-1)和0.50 mg·L~(-1)时,系统仍然具有良好的除磷脱氮效果,出水水质指标均满足我国《城镇污水处理厂污染物排放标准》(GB 18918-2002)中的一级A标准.在此基础上,基于Bio Win 4.1软件建立了AAO工艺的活性污泥模型,对模型参数进行了灵敏度分析,并利用动态模拟对模型参数中的聚磷菌吸收乙酸或丙酸的聚羟基烷酸(PHA)产率系数(YP/PHA,seq)、聚磷菌好氧氧化PHA的储磷率(YP/PHA,aerobic)、氨氧化菌的最大单位生长速率(μmax,A)和亚硝酸盐氧化菌的最大单位生长速率(μmax,N)进行了校验.此外,对系统的曝气能耗进行了模拟评估,结果表明,与好氧池DO浓度为2.00 mg·L~(-1)时相比,好氧池DO浓度为1.00 mg·L~(-1)和0.50 mg·L~(-1)时的空气流量可分别节省23.8%和38.1%,氧转移效率可分别提高7.2%和11.7%.     

厌氧条件下砂壤水稻土N2、N2O、NO、CO2和CH4排放特征

了解厌氧条件土壤反硝化气体(N2、N2O和NO)、CO2和CH4排放特征,是认识反硝化过程机制的基础,并有助于制定合理的温室气体减排措施.定量反硝化产物组成,可为氮转化过程模型研发制定正确的关键过程参数选取方法或参数化方案.本研究选取质地相同(砂壤土)的两个水稻土为研究对象,通过添加KNO3和葡萄糖的混合溶液,将培养土壤的初始NO-3和DOC含量分别调节到50 mg·kg-1和300 mg·kg-1,采用氦环境培养-气体及碳氮底物直接同步测定方法,研究完全厌氧条件下土壤N2、N2O、NO、CO2和CH4的排放特征,并获得反硝化气态产物中各组分的比率.结果表明,在整个培养过程中,两个供试土壤的N2、N2O和NO累积排放量分别为6~8、20和15~18 mg·kg-1,这些气体排放量测定结果可回收土壤NO-3变化量的95%~98%,反硝化气态产物以N2O和NO为主,其中3种组分的比率分别为15%~19%(N2)、47%~49%(N2O)和34%~36%(NO);但反硝化气体产物组成的逐日动态均显现为从以NO为主逐渐过渡到以N2O为主,最后才发展到以N2为主.以上结果说明,反硝化气体产物组成是随反硝化进程而变化的,在以气体产物组成比率作为关键参数计算各种反硝化气体产生率或排放率的模型中,很有必要重视这一点.     

北方高盐景观水体氮磷时空分布特征及富营养化评价

为掌握北方高盐景观水体的水环境状况,选取天津市中新生态城3个景观水体(清净湖、蓟运河和蓟运河故道)为研究对象,于2013年12月—2014年11月对其进行定期取样监测,开展水体氮磷污染特征分析及富营养化评价。结果表明:1)蓟运河、清净湖和蓟运河故道的TDS均值分别为3.42,4.64,20.2 g/L,属于高盐景观水体;2)水体TN和TP浓度逐月变化显著,水质整体上冬春季优于夏秋季,其中蓟运河TP和TN的浓度最大,且波动较大;3)根据TN/TP比值判定,研究区水体除清净湖在短时间表现为氮限制外,水体大部分时间段内表现为磷限制,P为主要限制因子;4)富营养化评价表明:水体均处于富营养状态,且有蓟运河蓟运河故道清净湖;5)相关性结果表明:TDS与电导率、水温及EI呈显著正相关,相关系数分别为0.905、0.822和0.645,盐度也是影响富营养化的关键因素。     

成都市污染边界层高度的演变特征分析

基于2014年1月21日至2月5日成都市人民南路四段逐时PM_(2.5)质量浓度、大气能见度资料以及同期Mie散射激光雷达探测数据,遵循消光系数与细颗粒物质量浓度之间的关系,探讨污染边界层高度的演变特征。结果表明:污染时段内的污染边界层高度偏低,平均为221m;污染边界层高度与地面PM_(2.5)浓度的变化具有明显相关性,但污染边界层高度改变在前,地面PM_(2.5)浓度响应在后;污染边界层高度的日变化表现为单峰单谷型,峰值和谷值分别出现在08:00时和14:00时前后。     

浸没燃烧技术处理高浓度有机废水研究

针对现阶段高浓度有机废水处理困难的问题,提出了一种基于浸没燃烧技术的处理方法,设计制作了1台浸没燃烧装置,并开展了高浓度有机废水浸没燃烧实验研究,探究了过量空气系数、二次风量、燃烧温度等参数对燃烧尾气中CO、NOx排放的影响,以及浸没深度、燃烧温度对高浓度有机废水COD去除的影响。实验结果表明:该工艺对高浓度有机废水中的有机物去除效果明显,温度在900℃以上,浸没深度达到20 cm时,COD去除率可达90%以上。该方法可作为废水处理设备,与生物法等处理技术联用,应用前景广阔。