Impact of pre-oxidation on the formation of byproducts in algae-laden water disinfection: Insights from fluorescent and molecular weight

Pre-oxidation has been reported to be an effective way to remove algal cells in water, but the released algal organic matter (AOM) could be oxidized and lead to the increment in disinfection by-product (DBP) formation. The relationship between pre-oxidation and AOM-derived DBP formation needs to be approached more precisely. This study compared the impact of four pre-oxidants, ozone (O₃), chlorine dioxide (ClO₂), potassium permanganate (KMnO₄) and sodium hypochlorite (NaClO), on the formation of nitrogenous (N-) and carbonaceous (C-) DBPs in AOM chlorination. The characterization (fluorescent properties, molecular weight distribution and amino acids concentration) on AOM samples showed that the characterization properties variations after pre-oxidation were highly dependent on the oxidizing ability of oxidants. The disinfection experiments showed that O₃ increased DBP formation most significantly, which was consistent with the result of characterization properties variations. Then canonical correspondent analysis (CCA) and Pearson's correlation analysis were conducted based on the characterization data and DBP formation. CCA indicated that C-DBPs formation was highly dependent on fluorescent data. The formation of haloacetic acids (HAAs) had a positive correlation with aromatic protein-like component while trichloromethane (TCM) had a positive correlation with fulvic acid-like component. Pearson's correlation analysis showed that low molecular weight fractions were favorable to form N-DBPs. Therefore, characterization data could provide the advantages in the control of DBP formation, which further revealed that KMnO₄ and ClO₂ were better options for removing algal cells as well as limiting DBP formation.     

The role of doped-Mn on enhancing arsenic removal by MgAl-LDHs

To meet the challenges posed by global arsenic water contamination, the MgAlMn-LDHs with extraordinary efficiency of arsenate removal was developed. In order to clarify the enhancement effect of the doped-Mn on the arsenate removal performance of the LDHs, the cluster models of the MgAlMn-LDHs and MgAl-LDHs were established and calculated by using density functional theory (DFT). The results shown that the doped-Mn can significantly change the electronic structure of the LDHs and improve its chemical activity. Compared with the MgAl-LDHs that without the doped-Mn, the HOMO-LUMO gap was smaller after doping. In addition, the -OH and Al on the laminates were also activated to improve the adsorption property of the LDHs. Besides, the doped-Mn existed as a novel active site. On the other hand, the MgAlMn-LDHs with the doped-Mn, the increased of the binding energy, as well as the decreased of the ion exchange energy of interlayer Cl⁻, making the ability to arsenate removal had been considerably elevated than the MgAl-LDHs. Furthermore, there is an obvious coordination covalent bond between arsenate and the laminates of the MgAlMn-LDHs that with the doped-Mn.     

Interactions between lead(II) ions and dissolved organic matter derived from organic fertilizers incubated in the field

This work was to study composition characteristics and the subsequent effect on the lead (Pb) binding properties of dissolved organic matter (DOM) derived from seaweed-based (SWOF) and chicken manure organic fertilizers (CMOF) during a one-year field incubation experiment using the excitation-emission matrix-parallel factor (EEM-PARAFAC) and two-dimensional correlation spectroscopy (2DCOS) analysis. Results showed that high aromatic and hydrophobic fluorescent substances were enriched in CMOF-derived DOM and SWOF-derived DOM and enhanced over time. And phenolic groups in the fulvic-like substances for SWOF-derived DOM and carboxyl groups in the humic-like substances for CMOF-derived DOM had the fastest responses over time, respectively. Moreover, both non-fluorescent polysaccharides and fluorescent humic-like substances or fulvic-like substances with aromatic (C=C) groups first participated in the binding process of Pb to SWOF-derived DOM on day 0 and 180 during the lead binding process. In contrast, humic-like substances associated with aromatic (C=C) and phenolic groups gave a faster response to Pb binding on day 360. Regarding CMOF-derived DOM, the fulvic-like substances associated with aromatic (C=C) and carboxylic groups displayed a faster response to Pb ions on day 0. Nonetheless, polysaccharides and humic-like associated with phenolic groups had a faster response on days 180 and 360. It is noteworthy that the polysaccharides, which participated in Pb binding to CMOF-derived DOM, posed a higher risk of Pb in the environment after 360 days. Therefore, these findings gave new insights into the long-term applications of commercial organic fertilizers for the amendment of soil.     

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe₃O₄/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO₂ extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.     

MoS2 quantum dots based MoS2/HKUST-1 composites for the highly efficient catalytic oxidation of elementary mercury

Due to the ever-tightening regulation on mercury emission in recent decades, there is an urgent need to develop novel materials for the removal of elemental mercury at coal-fired power plants. In this study, a series of MoS₂ quantum dots (QDs)-based MoS₂/HKUST-1 composite materials were prepared. It is found that MoS₂ QDs were encapsulated by HKUST-1 and enhanced the crystallinity and specific surface area of HKUST-1. The MoS₂/HKUST-1 showed excellent performance in catalytic oxidation of Hg⁰ as compared with pristine HKUST-1. It is found that surface layer of lattice oxygens is active and participates in Hg⁰ oxidation, while the consumption of surface oxygens then leads to the formation of oxygen vacancies on the surface. These vacancies are effective in the adsorption and dissociation of O₂, which subsequently participates in the oxidation of Hg⁰. Moreover, the study on the influence of commonly seen gas components, such as SO₂, NO, NH₃ and H₂O, etc., on Hg⁰ oxidation demonstrated that synergistic effects exist among these gas species. It is found that the presence of NO promotes the oxidation of Hg⁰ using oxygen as the oxidant.     

Ozone episodes during and after the 2018 Chinese National Day holidays in Guangzhou: Implications for the control of precursor VOCs

The impact of reducing industrial emissions of volatile organic compounds (VOCs) on ozone (O₃) pollution is of wide concern particularly in highly industrialized megacities. In this study, O₃, nitrogen oxides (NOx) and VOCs were measured at an urban site in the Pearl River Delta region during the 2018 Chinese National Day Holidays and two after-holiday periods (one with ozone pollution and another without). O₃ pollution occurred throughout the 7-day holidays even industrial emissions of VOCs were passively reduced due to temporary factory shutdowns, and the toluene to benzene ratios dropped from ∼10 during non-holidays to ∼5 during the holidays. Box model (AtChem2-MCM) simulations with the input of observation data revealed that O₃ formation was all VOC-limited, and alkenes had the highest relative incremental reactivity (RIR) during the holiday and non-holiday O₃ episodes while aromatics had the highest RIR during the non-pollution period. Box model also demonstrated that even aromatics decreased proportionally to levels with near-zero contributions of industrial aromatic solvents, O₃ concentrations would only decrease by less than 20% during the holiday and non-holiday O₃ episodes and ozone pollution in the periods could not be eliminated. The results imply that controlling emissions of industrial aromatic solvents might be not enough to eliminate O₃ pollution in the region, and more attention should be paid to anthropogenic reactive alkenes. Isoprene and formaldehyde were among the top 3 species by RIRs in all the three pollution and non-pollution periods, suggesting substantial contribution to O₃ formation from biogenic VOCs.     

功能化材料Zr@AC对水中难降解农药阿特拉津的去除特征

我国农药阿特拉津的污染十分严重,对生态系统造成了非常不利的影响. 为了实现对水环境中阿特拉津的高效去除和吸附剂的重复利用,该研究通过溶液浸渍和高温煅烧技术将金属锆负载到活性炭上,制备出功能化材料Zr@AC,使用扫描电镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外吸收光谱仪(FTIR)和比表面及孔径分析仪(BET)对材料的形貌和组成进行了表征,并考察了Zr@AC对水中阿特拉津的去除效果. 结果表明:①当浸渍液锆离子的质量分数为7.0%、浸渍时间为9.0 h、煅烧温度为500 ℃和煅烧时间为5.0 h时,制备的Zr@AC具有较大的比表面积、较多的中孔和微孔以及丰富的活性位点. ②对阿特拉津的去除研究表明,当溶液pH为4.0、温度为25 ℃、Zr@AC投加量为60.0 mg/L时,经过90 min的反应,Zr@AC对阿特拉津的吸附容量最大,达到93.8 mg/g. ③动力学模拟研究表明,该吸附过程遵循拟二级动力学模型,且Freundlich等温吸附模型的拟合结果要优于Langmuir等温吸附模型,说明Zr@AC对阿特拉津的吸附存在化学吸附和多分子层吸附的双重作用. ④经过5次重复试验后,Zr@AC对阿特拉津的去除率仍有83.9%. 研究显示,Zr@AC可作为水中去除阿特拉津的吸附剂,是一种很有前途、可重复多次使用的材料.      

旅游规划的发展历程与发展趋势

简要介绍了国内外旅游规划的发展历程,分析了旅游规划的现状和存在的问题,指出旅游规划的发展趋势是走向合成规划,走向社会实践,走向系统优化和走向可持续发展。     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.