The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.     

Toxicological effect of MPA-CdSe QDs exposure on zebrafish embryo and larvae

Cadmium selenium (CdSe) quantum dots (QDs) are semiconductor nanocrystals that hold wide range of applications and substantial production volumes. Due to unique composition and nanoscale properties, their potential toxicity to aquatic organisms has increasingly gained a great amount of interest. However, the impact of CdSe QDs exposure on zebrafish embryo and larvae remains almost unknown. Therefore, the lab study was performed to determine the developmental and behavioral toxicities to zebrafish under continuous exposure to low level CdSe QDs (0.05-31.25 mg L⁻¹) coated with mercaptopropionic acid (MPA). The results showed MPA-CdSe exposure from embryo to larvae stage affected overall fitness. Our findings for the first time revealed that: (1) The 120 h LC₅₀ of MPA-CdSe for zebrafish was 1.98 mg L⁻¹; (2) embryos exposed to MPA-CdSe resulted in malformations incidence and lower hatch rate; (3) abnormal vascular of FLI-1 transgenic zebrafish larvae appeared after exposure to MPA-CdSe including vascular junction, bifurcation, crossing and particle appearance; (4) larvae behavior assessment showed during MPA-CdSe exposure a rapid transition from light-to-dark elicited a similar, brief burst and a higher basal swimming rate; (5) MPA-CdSe induced embryos cell apoptosis in the head and tail region. Results of the observations provide a basic understanding of MPA-CdSe toxicity to aquatic organisms and suggest the need for additional research to identify the toxicological mechanism.     

Harvesting of Chlorella sp. using hollow fiber ultrafiltration

Introduction

The suitability of the application of ultrafiltration (UF) to harvest Chlorella sp. from the culture medium was examined. We investigated the effects of two improved UF system, forward air?Cwater flushing and backwash with permeate, on the concentration process.

Materials and methods

Backwash with permeate was selected as an optimization of the improved UF system, which was more effective for permeate flux recovery. Moreover, the hollow fiber UF system by adding periodical backwash with permeate was examined for Chlorella sp. harvesting.

Results and discussion

It was found that Chlorella sp. could be concentrated with high recovery in a lab-scale experiment. An overall algal biomass recovery of above 90% was achieved when the volume concentration factor was 10. For an original biomass of 1.3?±?0.05?g/L, 1?min backwash followed by 20?min forward concentrating was more effective, which resulted in a recovery of 94% and a high average flux of 30.3?L/m²/h. In addition, the algal recovery was highly correlated to the volume concentration factor and the initial biomass. A high concentration factor or a high initial biomass resulted in a low biomass recovery.     

不同粒径零价铁（ZVI）对污水污泥H_2S和CH_4释放速率的影响

考察了不同粒径零价铁（ZVI）,包括200目普通铁粉（200m-ZVI）、800目超细铁粉（800m-ZVI）和纳米铁粉（nZVI,粒径=20 nm）,对污水污泥的硫化氢和甲烷释放速率的影响。研究发现：（1）在22 d内,添加0.1%的200m-ZVI使污泥的硫化氢释放速率提高48.0%,而添加0.1%的800-ZVI和nZVI,则使污泥的硫化氢释放速率分别降低33.1%和77.1%;（2）不同粒径ZVI均可以提高污泥沼气中的甲烷浓度,且依次为nZVI〉800m-ZVI〉200m-ZVI;（3）在23 d内,添加0.1%的200m-ZVI和nZVI使污泥的甲烷累计产生量分别提高了15.5%和40.6%,而添加0.1%800m-ZVI则使甲烷产生量降低了12.5%。nZVI可以有效控制污泥的硫化氢释放,并显著提升污泥在厌氧发酵过程的产甲烷速率。     

UV-Fenton体系预处理四氢呋喃废水实验研究

采用UV-Fenton体系预处理四氢呋喃废水,实验结果表明,pH值、反应时间、Fe2+和H2O2投加量等因素对处理效果有较大的影响。实验确定的最佳反应条件为:原水pH=5,Fe2+投加量2.5 mmol/L,H2O2投加量12 mmol/L,反应时间90 min,连续曝气,在此条件下,COD去除率可达85%左右。经UV-Fenton体系处理后,废水的B/C值由0.16增至0.47,可生化性提高,可满足后续生化处理的要求。     

活性艳橙K-7R分子印迹聚合物微球的制备及结合特性研究

以微米级聚苯乙烯微球为种球,活性艳橙K-7R为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用单步溶胀聚合法在水相中制得了分子印迹聚合物微球(MIPs),并用平衡吸附实验研究了其吸附性能。通过Scatchard分析,结果表明,MIPs在识别K-7R过程中存在两类结合位点,高亲和力结合位点的平衡离解常数Kd1=14.855μmol/L,最大结合量Qmax1=1.282μmol/g;低亲和力结合位点的平衡离解常数Kd2=70.939μmol/L,最大结合量Qmax2=3.930μmol/g。该MIPs对K-7R有较高的亲和性和选择性。     

应用表面活性剂-生物柴油微乳液去除污染土壤中多环芳烃

针对修复焦化厂高浓度多环芳烃污染土壤高成本的现实,采用以非食用性植物油、生物柴油、表面活性剂及其乳化合成的微乳液为淋洗剂,比较不同淋洗剂的淋洗效果。结果表明乳化合成的微乳液对焦化厂土壤中多环芳烃的总去除率高于单独使用表面活性剂为淋洗剂对土壤中多环芳烃的总去除率,说明生物柴油及植物油与表面活性剂乳化形成的微乳液对原污染土壤中的多环芳烃具有显著的增溶作用。1%TW-80和2.5%TW-80对土壤中多环芳烃总去除率分别为11%和14%;以2.5%TW-80为原料乳化合成的微乳液的淋洗去除率较以1%TW-80为原料乳化合成的微乳液高,总去除率分别为15%～30%和11%～18%;以生物柴油为原料乳化合成的微乳液的淋洗去除率较以植物油为原料乳化合成的微乳液高,分别为17%～30%和15%～23%,且对多环芳烃的去除率与其辛醇水分配系数(logKow)呈线性相关关系。     

晚期垃圾渗滤液的部分亚硝化

利用实验室小试SBR在(33±1)℃的条件下,通过动态调控溶氧浓度(DO)(2～7 mg/L)和水力停留时间(2～5 d),经过130 d的运行成功启动了晚期垃圾渗滤液(NH4+-N含量1 227～2 133 mg/L)的部分亚硝化,使出水NO2--N∶NH4+-N稳定维持在1∶1左右,为后续的厌氧氨氧化工艺创造了进水条件。利用实时荧光定量PCR研究启动过程中的特异微生物氨氧化细菌的含量变化表明,氨氧化细菌的含量与NO2--N的生成速率和出水NO2--N稳定性有着显著相关性。     

Properties of alkali-activated systems with stone powder sludge

This article investigates the effects of stone powder sludge on the microstructure and strength development of alkali-activated fly ash and blast furnace slag mixes. Stone powder sludge produced from a crushed aggregate factory was used to replace fly ash and granulated blast furnace slag at replacement ratios of 0%, 10%, 20%, and 30% by mass. The unit weight and compressive strength of the samples were measured, and scanning electron microscopy/energy dispersive spectroscopy and X-ray diffraction (XRD) analyses were performed. The test results indicated that the compressive strength of alkali-activated blast furnace slag mixes using stone powder sludge was higher than that of the alkali-activated blast furnace slag control mix, but the compressive strength of alkali-activated fly ash mixes decreased with increasing replacement ratio of stone powder sludge. Microscopy results indicated that for alkaliactivated blast furnace slag samples, broken surfaces were more evident than for the alkali-activated fly ash samples. For all XRD diagrams, broad and diffuse peaks were observed around 2θ = 35° (d = 2.96–3.03 Å), implying amorphous or short-ordering structure phases.     

连续流反应器中培养好氧颗粒污泥的运行效能研究

在连续流完全混合反应器(CSTR)中,采用不同进水方式,以乙酸钠作为碳源配制的人工配水作为原水,对好氧颗粒污泥的运行效能进行了试验研究。研究表明,采用不同进水方式运行的2个反应器在颗粒污泥出现后,运行效能差别不大;好氧颗粒污泥反应器运行高效稳定,在水力停留时间为1.5h、COD容积负荷为1.0kg/(m3·d)的条件下,对COD、TP、NH4+-N和TN的去除率分别为90%、85%、95%和60%,并具有明显的脱氮除磷效果;反应器中存在同步硝化反硝化现象。