Fate of a stilbene-type fluorescent whitening agent (DSBP) in the presence of Fe(III) aquacomplexes: from the redox process to the photodegradation

The behaviour of 4,4′-bis(2-sulfostyryl)biphenyl (DSBP), a fluorescent whitening agent, was investigated in the presence of Fe(III) aquacomplexes at room temperature. In the dark, a two-step reaction was observed when adding Fe(III) to a solution of DSBP: an initial fast redox reaction between DSBP and the monomeric species Fe(OH)²⁺ and a slower reaction leading to the coagulation of oxidised DSBP and iron. This phenomenon is due to the formation of a complex or an ion-pair between Fe(II) and/or Fe(III) with oxidised DSBP and it probably occurs by charge neutralisation in our experimental conditions. The precipitation of DSBP depends on the initial concentration in Fe(OH)²⁺ and is achieved for a ratio [Fe(OH) ²⁺]/[DSBP] of 5 approximately. Under irradiation at 365 nm, a complicated behaviour was observed: a complexation of iron by oxidised DSBP favoured by irradiation and a degradation of DSBP induced by an intramolecular electron transfer in the complex or by a photoredox of Fe(OH)²⁺ species generating OH radicals in the supernatant. The complete degradation of DSBP is reached four times faster in the presence of Fe(III) with respect to the direct photolysis of DSBP alone. Moreover, the total mineralization of DSBP obtained in less than 120 h upon irradiation at 365 nm is only observed in the presence of the ferric ions, enlightening the efficiency of the method involving Fe(III) and UV irradiation.     

Modeling patterns of breakdown (or archetypes) of human and organizational processes in accidents using system dynamics

Systems approaches to safety have received growing attention in modern accident investigation techniques (e.g., STAMP, Accimap) with the emphasis shifted to the organizational dynamics (or archetypes) that may lead to an erosion of defenses and a drift out of the safety margins. Although the literature contains many applications of archetypes and system dynamics to safety, this richness comes at a cost of learning. It has become very difficult for safety practitioners to integrate the diverse studies of system dynamics with their diverging models. To provide a practical tool of system dynamics in accident investigation, this article reviews earlier studies and integrates them as a classification of patterns of breakdown (or archetypes) of both human and organizational processes on the basis of two control models, that is, the Extended Control Model (ECOM) and the Viable System Model (VSM). In this article, archetypes are represented as variants of two generic templates of performance which exploit many elements of complexity theory and system control. Apart from providing a practical tool to safety practitioners to access the literature on archetypes, the generic templates of ECOM and VSM can be used in building simulators of individual and organizational processes for risk analysis.     

Modeling the seasonal autochthonous sources of dissolved organic carbon and nitrogen in the upper Chesapeake Bay

In this paper we investigate the seasonal autochthonous sources of dissolved organic carbon (DOC) and nitrogen (DON) in the euphotic zone at a station in the upper Chesapeake Bay using a new mass-based ecosystem model. Important features of the model are: (1) carbon and nitrogen are incorporated by means of a set of fixed and varying C:N ratios; (2) dissolved organic matter (DOM) is separated into labile, semi-labile, and refractory pools for both C and N; (3) the production and consumption of DOM is treated in detail; and (4) seasonal observations of light, temperature, nutrients, and surface layer circulation are used to physically force the model. The model reasonably reproduces the mean observed seasonal concentrations of nutrients, DOM, plankton biomass, and chlorophyll a. The results suggest that estuarine DOM production is intricately tied to the biomass concentration, ratio, and productivity of phytoplankton, zooplankton, viruses, and bacteria. During peak spring productivity phytoplankton exudation and zooplankton sloppy feeding are the most important autochthonous sources of DOM. In the summer when productivity peaks again, autochthonous sources of DOM are more diverse and, in addition to phytoplankton exudation, important ones include viral lysis and the decay of detritus. The potential importance of viral decay as a source of bioavailable DOM from within the bulk DOM pool is also discussed. The results also highlight the importance of some poorly constrained processes and parameters. Some potential improvements and remedies are suggested. Sensitivity studies on selected parameters are also reported and discussed.     

以HKUST-1为模板制备铜氧化物活化过一硫酸氢钾降解罗丹明B

以一种Cu-MOF(HKUST-1)为模板,将其经不同温度的热处理制备铜氧化物,研究了热处理温度对产物组成及形貌的影响,并通过产物在一系列条件下活化过一硫酸氢钾(PMS)降解水体中罗丹明B(Rh B)的实验探究了其催化性能.XRD、SEM、XPS等表征结果表明,随着热处理温度的升高,产物由Cu2O/CuO混合物逐渐转化为纯相CuO,且模板HKUST-1的原有正八面体结构坍塌加剧.Rh B降解实验的结果显示,催化剂对PMS的活化性能随热处理温度的升高而加强.在中性pH条件下,当PMS投加量为1.00 mmol·L~(-1),CuO-650用量为0.20 g·L~(-1)时,反应时间进行90 min基本可实现Rh B(浓度为0.10mmol·L~(-1))的完全降解.此外,CuO-650还具有pH适用范围较广,铜离子溶出量较低(pH=3条件下为1.309 mg·L~(-1),pH=7条件下为0.987 mg·L~(-1)),循环稳定性较佳的特点,进一步证明CuO-650是一种很有潜力的PMS催化剂.     

Comparison of UV and UV-LED activated sodium percarbonate for the degradation of O-desmethylvenlafaxine

As an active metabolite of venlafaxine and emerging antidepressant, O-desmethylvenlafaxine (ODVEN) was widely detected in different water bodies, which caused potential harm to human health and environmental safety. In this study, the comparative work on the ODVEN degradation by UV (254 nm) and UV-LED (275 nm) activated sodium percarbonate (SPC) systems was systematically performed. The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis (14.99%) than UV direct photolysis (4.57%) due to the higher values of photolysis coefficient at the wavelength 275 nm. Significant synergistic effects were observed in the UV/SPC (80.38%) and UV-LED/SPC (53.57%) systems and the former exhibited better performance for the elimination of ODVEN. The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes, and the pseudo-first-order rate constant (k_obs) increased with increasing SPC concentration. Radicals quenching experiments demonstrated that both ·OH and CO₃·⁻ were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO₃·⁻ (1.58 × 10⁸ (mol/L)⁻¹ sec⁻¹) was reported for the first time based on competitive kinetic method. The introduction of HA, Cl⁻, NO₃⁻ and HCO₃⁻ inhibited the ODVEN degradation to varying degrees in the both processes. According to quantum chemical calculation, radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by ·OH. In addition, the oxidation of ODVEN may involve the demethylation, H-abstraction, OH-addition and C-N bond cleavage. Eventually, the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process, although the UV/SPC process possessed a higher removal rate of ODVEN.     

基于过程分析的京津冀区域典型城市臭氧成因

随着京津冀区域臭氧（O₃）污染问题日渐突出,探究和分析京津冀区域O₃变化特征和污染过程形成原因对区域大气污染防治工作具有重要意义.观测结果显示,春夏季京津冀区域较高的O₃浓度呈现南高北低的分布,北京、天津和石家庄这3座城市O₃高浓度往往伴随着偏南风的影响.基于WRF-Chem模式模拟和过程分析技术对2019年京津冀区域O₃变化特征和成因进行了深入分析,典型城市化学过程、垂直混合和输送的日变化有着鲜明的季节变化差异.其中在夏季午后化学过程是各城市O₃浓度增加的主要来源;垂直混合导致天津和石家庄O₃浓度增加,但使得北京O₃浓度减少;天津和石家庄存在净输出,而北京则为净流入.通过对比分析O₃污染和清洁过程结果表明,化学过程主导北京和石家庄污染过程午后O₃浓度增加,天津则为垂直混合,此外,北京和石家庄存在O₃净输入,天津则为净输出;而清洁过程中,垂直混合主...     

A facial strategy to efficiently improve catalytic performance of CoFe2O4 to peroxymonosulfate

Cobalt iron spinel (CoFe₂O₄) has been considered as a good heterogeneous catalysis to peroxymonosulfate (PMS) in the degradation of persistent organic pollutants due to its magnetic properties and good chemical stability. However, its catalytic activity needs to be further improved. Here, a facial strategy, “in-situ substitution”, was adopted to modify CoFe₂O₄ to improve its catalytic performance just by suitably increasing the Co/Fe ratio in synthesis process. Compared with CoFe₂O₄, the newly synthesized Co_1.5Fe_1.5O₄, could not only significantly improve the degradation efficiency of phenol, from 50.69 to 93.6%, but also exhibited more effective mineralization ability and higher PMS utilization. The activation energy advantage for phenol degradation using Co_1.5Fe_1.5O₄ was only 44.2 kJ/mol, much lower than that with CoFe₂O₄ (127.3 kJ/mol). A series of related representations of CoFe₂O₄ and Co_1.5Fe_1.5O₄ were compared to explore the possible reasons for the outstanding catalytic activity of Co_1.5Fe_1.5O₄. Results showed that Co_1.5Fe_1.5O₄ as well represented spinel crystal as CoFe₂O₄ and the excess cobalt just partially replaced the position of iron without changing the original structure. Co_1.5Fe_1.5O₄ had smaller particle size (8.7 nm), larger specific surface area (126.3 m²/g), which was more favorable for exposure of active sites. Apart from the superior physical properties, more importantly, more reactive centers Co (Ⅱ) and surface hydroxyl compounds generated on Co_1.5Fe_1.5O₄, which might be the major reason. Furthermore, Co_1.5Fe_1.5O₄ behaved good paramagnetism, wide range of pH suitability and strong resistance to salt interference, making it a new prospect in environmental application.     

Natural Recovery of Technogenic Landscapes in Open Larch Forests in Northeastern Russia

Studies on the vegetation and soil complexes in areas of the Kolyma River basin disturbed by mining, in the northeast of the Chukchi Peninsula, have been performed to reveal trends in natural restorative processes in posttechnogenic landscapes. Data on the flora, phytomass stock, chemical composition of plants pioneering in the overgrowing of disturbed areas, and physicochemical properties of soils and technogenic eluvia have been obtained. The results have shown that plant cover restoration in disturbed areas depends primarily on the type (genesis) of technogenic substrates, the content of fine earth in the surface layer, and the distance from natural plant complexes that serve as a source of seeds coming to the disturbed area.     

高级氧化技术在水处理中的应用

介绍了高级氧化技术的发展及其特点,并综述了化学氧化、光催化氧化、水热氧化以及高压脉冲放电等离子体、超声等高级氧化技术及其在水处理中的应用。随着对高级氧化技术不断深入的研究,其在水处理领域的应用将更加成熟并且越来越广泛。