基于WASP 7模型的水质模拟应用——以淮沭新河东海段为例

应用WASP 7模型的EUTRO子模块对淮沭新河东海段的溶解氧(DO)和化学需氧量(COD)指标进行模拟研究,采用2014年与2015年的水文、水质数据进行模型参数率定,并以2016年1月—2017年9月的水质数据进行验证,验证结果为DO和COD的模拟值与实际值的相对误差分别能控制在15%和10%以内,线性回归分析结论显示相关系数R2均在0.9以上,表明两者的吻合度较高。     

Sodium borohydride reduction of individual polybrominated diphenyl ethers

Many chemicals in use today lack appropriate documentation on their environmental properties, fate, and effects. To counteract this lack of documentation it is vital to thoroughly investigate a compound’s fate in the environment before it comes into use. The present study is describing a novel method for assessing the reduction potential of polybrominated diphenyl ethers (PBDEs), as a part of a project aimed to create an experimental model for determination of chemical persistence. The reductive transformation of 15 PBDE congeners using sodium borohydride was determined. Pseudo-first-order reaction rate constants of the transformations were determined by monitoring the disappearance of the investigated congeners. The reductions lead primarily to formation of lower brominated PBDEs. Each PBDE congener was tested in a total of ten replicates which showed a relative standard deviation of 31% or less. The decaBDE, BDE-209 was approximately 3 times as prone to reductive transformation as BDE-207. The three nonaBDEs, BDE-206, BDE-207, and BDE-208, showed similar reductive potential. The reactivity of the tested octaBDEs was quite variable, from 5% to 24% of the reactivity of BDE-209 for BDE-196 and BDE-198, respectively. The heptaBDEs studied were in the range of the less reactive octaBDEs, except for BDE-181 which was as high as 13% of the reactivity of BDE-209. The results presented give a method for measuring the propensity of PBDEs, and possibly similar compounds, to undergo reductions. They indicate a potential route to a vital piece of information in the assessment of environmental persistence of chemicals.     

化工安全生产与生态环境保护管理措施探究

现代社会进入一个科技化、现代化发展阶段,人们的生活条件不断提升,其中诸多民生相关的产业都发挥着关键作用。化工产业作为社会产业基础构成部门与民生息息相关。但从其基本属性来看,实践工作难免会遇到一些安全性的问题,以及相应的环境污染。需要探索生态环境保护管理与化工安全生产协调配合的有效措施,由此才能达成可持续化发展目标,提升其积极影响作用。     

A^2/O-MBR组合工艺运行优化与氮磷深度控制的分析

为了遏制水环境不断恶化的趋势,应加强对氮、磷超标的治理工作,促进水生态环境平衡发展。本文采用A^2/O-MBR作为主体工艺,后续辅以化学除磷和以深床滤池为反硝化单元的组合工艺,确保最终出水满足天津市《城镇污水处理厂污染物排放标准》(DB12/599-2015)A标准排放要求。     

化工园区污水深度处理工艺的选择及可行性分析

现阶段,我国经济仍保持着良好的发展势头,而在此发展过程中,也出现了更多的化工企业,化工园区数量也有所增加。因此,也相应增加了化工污水排放量,加剧了对环境的污染,加大了污水处理的难度。所以,当前做好污水处理工艺的选择及可行性分析显得愈加重要。本文从笔者工作经验出发,对污水深度处理工艺的选择及可行性分析展开了着重探讨。     

Preparation of calcium oxalate—bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters

Background, aim, and scope  Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods  On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ^2––BPR–Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results  The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 × 10⁵ M^–1. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30–50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion  The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ^2– captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions  By characterizing the C₂O₄ ^2––BPR–Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] _n ^2n–, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives  The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Modification of cloud condensation nucleus activity of organic aerosols by hydroxyl radical heterogeneous oxidation

The modification of cloud condensation nucleus (CCN) activity of saturated organic particles resulting from heterogeneous oxidation by OH radicals was studied. Submicron Bis-2-ethylhexyl sebacate (BES) and stearic acid particles were exposed to OH radicals in a reactor flow tube and CCN activity was monitored. The hygroscopicity parameter, κ, for monodisperse stearic acid and BES particles of 145–150 nm in size increased from <0.008 up to 0.08 as a result of OH exposures equivalent to atmospheric exposure timescales of several days to a week. The oxidation of stearic acid particles led to a 50% reduction in particle volume at high OH exposures, indicating an enhanced degree of volatilization of oxidation products compared to oxidized BES particles, along with possible shape/phase change. Surface tension measurements of water extracts of oxidized BES films showed a significant reduction in surface tension due to oxidation. Köhler calculations modeling the CCN measurements suggest that the surface active oxidation products play an important role.     

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

Chemical composition and seasonal variation of acid deposition in Guangzhou, South China: comparison with precipitation in other major Chinese cities

With the aim of understanding the origin of acid rains in South China, we analyzed rainwaters collected from Guangzhou, China, between March 2005 and February 2006. The pH of rainwater collected during the monitoring period varied from 4.22 to 5.87; acid rain represented about 94% of total precipitation during this period. The rainwater was characterized by high concentrations of SO₄²⁻, NO₃⁻, Ca²⁺, and NH₄⁺. SO₄²⁻ and NO₃⁻, the main precursors of acid rain, were related to the combustion of coal and fertilizer use/traffic emissions, respectively. Ca²⁺ and NH₄⁺ act as neutralizers of acid, accounting for the decoupling between high SO₄²⁻ concentrations and relatively high pH in the Guangzhou precipitation. The acid rain in Guangzhou is most pronounced during spring and summer. A comparison with acid precipitation in other Chinese cities reveals a decreasing neutralization capacity from north to south, probably related to the role and origin of alkaline bases in precipitation.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.