Chemical segregation by heterogeneous emissions

Ozone pollution in the boundary layer results from photoactivated chemistry of primary pollutants released at the ground. As emissions are highly inhomogeneous in space and time and some chemical time-scales are of the order or larger than dynamical time-scales, it is admitted that turbulent transport and mixing is a key factor in ozone production. We study the interaction between chemistry and convective boundary layer turbulent with a large eddy simulation model coupled to CHIMERE, a detailed chemical model, over a $10\times 10\mathrm{km}$ domain. Our results show that when emissions are concentrated over a limited area, strong values of segregation between chemical species are obtained over the first two active hours during the morning, leading to significant impact in terms of pollutants concentration. After 3 h, for each heterogeneous emission case considered, segregation drops to a few percents for most compounds pairs, due to the strong convective mixing of the boundary layer.     

Short communication

Abstract

The presence of the insecticide carbaryl (Sevin) and its decomposition product l‐napthol was confirmed in irrigation and drainage canal water. However, their residues disappeared from the water 6 days after application.     

光催化氧化-混凝工艺处理化工废水

探索了光催化氧化－混凝工艺处理废水的工艺条件,最佳光催化氧化处理条件为ＰＨ＝３,催化剂为铁盐,氧化剂Ｈ２Ｏ２,低压汞灯,光照时间１．５ｈ,废水温度４５℃,温凝剂选用ＰＡＣ和ＰＡＭ（混凝剂的投加量为原水ＣＯＤｃｒ：ＰＡＣ：ＰＡＭ＝７：１．５：０．０１）,混凝ＰＨ６,沉降时间０．５ｈ,在该工艺条件对ＣＯＤｃｒ为１７３－７０１４４ｍｇ／Ｌ的十二烷基苯磺酸钠废水、苯酐废水、富马酸废水、邻苯二甲酸二辛酯废水     

锆化工废渣无害化处理与利用研究

研究了锆化工废渣用在水泥生产中替代部分混合材料，经正常水泥生产各道工序后，生产水泥的无害化处理与利用技术。所采用的工艺既解决了锆化工废渣的出路，又减少了水泥混合材料的使用量，节省了其它原料，具有较好的环境效益和经济效益。     

强电离放电脱除NO的化学反应动力学模拟

强电离放电脱除NO是集化学、物理学和环境工程学为一体的交叉学科,其脱除过程本质上是等离子体中进行的一系列微观过程,难以通过实验进行直接研究。故通过建立强电离放电脱除模拟烟气中NO的化学模型并运用MATLAB对其进行数值模拟以探讨NO的去除机理。数值模拟结果表明,在800 μs内产生大量·O和·OH,而仅产生少量·N,由此可知NO的去除主要是通过与·O和·OH的氧化反应生成HNO3实现的,在脱除过程中NO先被氧化成NO2,再进一步被转化成HNO3。同时,通过实验验证了所建立模型的合理性。实验结果表明：随着NO初始浓度的增加,NO脱除效率逐渐下降;随着含氧量的增加,NO脱除效率显著增大。     

Chemical modifications of groundwater contaminated by recharge of treated sewage effluent

Long-term monitoring of the chemical composition of recharge sewage effluent and associated contaminated groundwater from the Dan Region Sewage Reclamation Project shows, after 16 years of recharge operation, the presence of a distinct saline plume (up to 400 mg/l Cl), extending 1600 m downgradient in the Coastal Plain aquifer of Israel. The recorded electrolyte composition of groundwater in the vicinity of the recharge area reflects the variations in the compositions of the sewage effluents, as well as water-rock interactions induced by the recharge of treated sewage effluents. The original sewage composition was modified, particularly during early stages of effluent migration in the unsaturated zone, by cation-exchange and adsorption reactions. Since the soil sorption capacity is finite these reactions caused only limited modifications, and once the system reached a steady state the inorganic composition of the contaminated groundwater became similar to that of the recharge water. Decomposition of organic matter in the unsaturated zone resulted in CO₂ generation and dissolution of CaCO₃ minerals in the aquifer. It was shown that chemical and/or bio-degradation of organic matter takes place mainly in the unsaturated (vadose) zone. Hence, monitoring the efficiency of the vadose zone to retain contaminants is essential for evaluating the quality of groundwater since it was shown that organic compounds behave almost conservatively once the effluents enter and flow within the saturated zone.     

生活垃圾焚烧飞灰重金属药剂稳定化研究

采用几种不同厂家提供的有机重金属飞灰螯合剂和一种无机飞灰稳定剂对湖北某垃圾焚烧厂及四川某垃圾焚烧厂所产飞灰分别进行了稳定化处理的研究。结果表明,就2种飞灰而言,有机螯合剂在处理效果上较无机药剂具有一定的优势,为使飞灰处理后的浸出毒性低于《生活垃圾填埋场污染控制标准》(GB16889-2008)所规定的限值,满足进入垃圾填埋场分区填埋的要求,不同种类的有机螯合剂添加量在1%~5%之间,各有机螯合剂的稳定效果与其分子结构和分子大小的关系密切。而某无机药剂在添加剂量为15%时仅能使四川某厂所产生的飞灰勉强达标。从经济上考虑,使用有机螯合剂的药剂成本费用也低于某无机药剂,同时对比实验发现,飞灰初始浸出毒性的大小,飞灰粒径大小,飞灰的物理性状对螯合过程具有一定的影响。     

Chemical composition of burnt smell caused by accidental fires: environmental contaminants

The chemical composition of the odors typical of fires has recently been deciphered. Basically the constituents are mixtures of acetophenone, benzyl alcohol, hydroxylated derivatives of benzaldehyde, methoxylated and/or alkylated phenols and naphthalene. This finding makes it possible to develop objective, practical analytic measurement methods for the burnt smell as a contribution to improving fire damage assessment and remediation monitoring. With the aid of an artificially produced burnt smell and a panel of testers the odor detection threshold of a test mixture was determined olfactometrically to 2 μg m⁻³. Using a defined burnt-smell atmosphere in a test chamber, analytical methods with active sampling, the adsorbents XAD 7 and TENAX TA, and GC/MS measurement were then optimized and tested with a view to being able to carry out sensitive quantitative measurement of burnt smells. A further practical method with particular application to the qualitative characterization of this odor is based on the use of a new SPME (solid-phase microextraction) field sampler with DVB/CAR/PDMS (divinylbenzene/Carboxen™/polydimethylsiloxane) fibers.     

酸雨对污染环境中重金属化学行为的影响

综述了酸雨对污染环境中重金属化学行为的影响。在酸雨作用下 ,不同环境介质中重金属活性明显增强 ,化学形态转化明显 ,迁移能力和生态危害能力亦明显加强。探讨了控制酸雨发生、重金属污染环境修复技术以及开展复合污染环境化学风险评价的必要性     

Modifications of the sex pheromonal communication of trichogramma brassicae by a sublethal dose of deltamethrin

Pyrethroid insecticides, by their intensive use and their persistence that can exceed 3 months, largely contribute to the environmental pollution. In this work, we determined the effects of a very low dose of deltamethrin on the sex pheromonal communication of Trichogramma brassicae. The dose used was a dose that would theoretically kill one insect over 1000 (an LD 0.1). We found that this dose slightly but very significantly increased the arrestment behavior of treated males responding to the female pheromone. On the other hand when females were exposed to the same dose of insecticide, the response of males to their pheromone was very significantly decreased. In Trichogramma, like in other insects, sex pheromonal communication probably involves nervous transmissions both for the reception and the emission of the pheromone. Then, the sublethal effects of deltamethrin, observed in this work, are certainly due to multiple actions of this insecticide on nervous transmissions. Trichogramma is a beneficial insect that contributes to the control of pest populations of moths. Actions of this insecticide at a dose that can correspond to environmental pollution could be a real threat to the equilibrium of these populations.     

Chemical transport models

Background, aim, and scope  Improving the parameterization of processes in the atmospheric boundary layer (ABL) and surface layer, in air quality and chemical transport models. To do so, an asymmetrical, convective, non-local scheme, with varying upward mixing rates is combined with the non-local, turbulent, kinetic energy scheme for vertical diffusion (COM). For designing it, a function depending on the dimensionless height to the power four in the ABL is suggested, which is empirically derived. Also, we suggested a new method for calculating the in-canopy resistance for dry deposition over a vegetated surface. Materials and methods  The upward mixing rate forming the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. The vertical eddy diffusivity is parameterized using the mean turbulent velocity scale that is obtained by the vertical integration within the ABL. In-canopy resistance is calculated by integration of inverse turbulent transfer coefficient inside the canopy from the effective ground roughness length to the canopy source height and, further, from its the canopy height. Results  This combination of schemes provides a less rapid mass transport out of surface layer into other layers, during convective and non-convective periods, than other local and non-local schemes parameterizing mixing processes in the ABL. The suggested method for calculating the in-canopy resistance for calculating the dry deposition over a vegetated surface differs remarkably from the commonly used one, particularly over forest vegetation. Discussion  In this paper, we studied the performance of a non-local, turbulent, kinetic energy scheme for vertical diffusion combined with a non-local, convective mixing scheme with varying upward mixing in the atmospheric boundary layer (COM) and its impact on the concentration of pollutants calculated with chemical and air-quality models. In addition, this scheme was also compared with a commonly used, local, eddy-diffusivity scheme. Simulated concentrations of NO₂ by the COM scheme and new parameterization of the in-canopy resistance are closer to the observations when compared to those obtained from using the local eddy-diffusivity scheme. Conclusions  Concentrations calculated with the COM scheme and new parameterization of in-canopy resistance, are in general higher and closer to the observations than those obtained by the local, eddy-diffusivity scheme (on the order of 15–22%). Recommendations and perspectives  To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO₂) were compared for the years 1999 and 2002. The comparison was made for the entire domain used in simulations performed by the chemical European Monitoring and Evaluation Program Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

Chemical oxidative degradation of methyl tert-butyl ether in aqueous solution by Fenton's reagent

Degradation of methyl tert-butyl ether (MTBE) in aqueous solution by Fenton's reagent (Fe2+ and H2O2) was investigated. Effects of reaction conditions on the oxidation efficiency of MTBE by Fenton's reagent were examined in batch experiments. Under optimum conditions, 15 mM H2O2, 2 mM Fe2+, pH 2.8 and room temperature, the initial 1 mM MTBE solution was reduced by 99% within 120 min. Results showed that MTBE was decomposed in a two-stage reaction. MTBE was first decomposed swiftly based on a Fe2+/H2O2 reaction and then decomposed somewhat less rapidly based on a Fe3+/H2O2 reaction. The detection of Fe2+ also supported the theory of the two-stage reaction for the oxidation of MTBE by Fenton's reagent. The dissolved oxygen in the solution decreased rapidly in the first stage reaction, but it showed a slow increase in the second stage with a zero-order kinetics. A reaction mechanism involving two different pathways for the decomposition of MTBE by Fenton's reagent was also proposed. Chemicals including tert-butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified to be the primary intermediates and by-products of the degradation processes.     

Chemical transformation of S-benzyl O-ethyl phenylphosphonothiolate (Inezin) by ultraviolet light.

The photodecomposition of Inezin (S-benzyl O-ethyl phenylphosphonothiolate) in n-hexane under the ultraviiolet irradiation was investigated by gas liquid chromatography, thin layer chromatography, mass spectrometry, and infrared spectroscopy. Two main steps of photodecomposition were observed at the initial stage of irradiation. One was the cleavage of P-S bond to produce O-ethyl phenylphosphinate and dibenzyl disulfide, the latter of which was degraded rather rapidly to produce sulfuric acid and benzoic acid through toluene-alpha-sulfonic acid by oxidation. The other step was the isomerization to the thionate, O-benzyl O-ethyl phenylphosphonothionate, which was gradually oxidized to itx oxygen analogue, O-benzyl O-ethyl phenylphosphate. O-ethyl phenylphosphinate, O-benzyl O-ethyl phenylphosphonate and O-benzyl O-ethyl phenylphosphonthionate were fairly stable under the ultraviolet light, as compared with Inezin. As hydrolysis products of the parent compound, phenylphosphonic acid, O-ethyl hydrogen phenylphosphonate, O-ethyl hydrogen phenylphosphonothioate and benzyl alcohol were detected.     

Chemical kinetic modelling of PCDD formation from chlorophenol catalysed by incinerator fly ash

A kinetic model is developed for PCDD formation from chlorophenol catalysed by incinerator fly ash. The key step in the model is a Langmuir-Hinshelwood type elementary step for the coupling of two adsorbed chlorophenol species to PCDD. Kinetic expression is derived which can relate PCDD formation rates with process variables including temperature, precursor concentration, fly ash loading and number of active sites in fly ash. Calculated PCDD formation rates based on this kinetic model are in good agreement with laboratory measurements reported in the literature. When the model is applied to industrial incinerator conditions, at maximum a PCDD yield of 10(-3) microg/N m3 is calculated.     

两级混凝-化学氧化处理生活污水的研究

采用两级混凝-化学氧化组合工艺处理城市生活污水，在混凝试验中确定了两级不同混凝剂的适宜投加量，并对自制混凝剂Inx进行了氧化再生重复利用实验。结果表明：经两级混凝-化学氧化组合工艺处理后的城市污水达到国家污水综合排放标准，并且自制混凝剂Inx可以重复利用。     

Radon risk communication research: practical lessons

Those responsible for state and local radon programs often express frustration about the small share of homes that have been tested for radon, and the small share of those with high readings that have been mitigated. There are now a number of completed studies that have examined how well alternative ways of communicating about radon risk have accomplished the goals of motivating appropriate testing and mitigation. This paper summarizes the research results that are most crucial for planning and implementing effective radon risk communication programs. We identify six reasons why people do not respond to radon as a serious threat and provide some remedies suggested by radon studies.     

Chemical recycling of poly(ethylene terephthalate) (pet) by hydrolysis and glycolysis

In this paper we review an interesting method of PET recycling, i.e. chemical recycling; it is based on the concept of depolymerizing the condensation polymer through solvolytic chain cleavage into low molecular products which can be purified and reused as raw materials for the production of high-quality chemical products. In this work our attention is confined to the hydrolysis (neutral, acid and alkaline) and glycolysis processes of PET chemical recycling; operating conditions and mechanism of each method are reported and described. The neutral hydrolysis has an auto accelerating character; two kinetic models have been proposed: an half-order and a second order kinetic model. The acid hydrolysis could be explained by a modified shrinking core model under chemical reaction control and the alkaline hydrolysis by a first-order model with respect to hydroxide ion concentration. To describe glycolysis, two different kinetic models have been proposed where EG can act or not as internal catalyst. Further experimental and theoretical investigations are required to shed light on the promising processes of PET chemical recycling reviewed in this work.     

Chemical modification of montan resin by peracetic acid and agricultural application of its modified products

ABSTRACT

Montan resin (MR) is a by-product produced during the refinement process of montan wax extracted from lignite and has no usage yet. Chemical modification is an effective method to change the material property for expanding or converting the application area of the material itself. Our previous study found that the high hydrophobicity of MR is the primary limiting factor for its utilization in agriculture. Based on this point, this study attempted to chemically modify MR using the oxidation of peracetic acid, resulting that the MR hydrophilicity was significantly improved, and a water-soluble product (WSP) was obtained. The optimized oxidation conditions of MR, including the reaction temperature (X₁), reaction time (X₂), weight ratio of oxidant and montan resin (X₃), and oxidant concentration (X₄), were determined using single-factor experiments and response surface analysis. The modification degree was evaluated using elemental and oil-water partition coefficient analyses, infrared (IR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS), revealing that the oil-water partition coefficient of the modified product decreased and that the number of chemical constituents with oxygen-containing functional groups clearly increased after modification. Furthermore, the WSP was tested its effects on germination and seedling growth of the wheat seed. Compared with the control group, the WSP showed a promoting effect on the growth and germination of wheat. The WSP concentrations of 600 mg·L^?1 and 300 mg·L^?1 had the most substantial effect on the root and seedling growth of wheat, respectively.

Implications: Montan resin, a useless by-product produced from crude montan wax, was chemically modified via oxidation of peracetic acid. Its hydrophilicity was significantly improved, and a water-soluble product was obtained after the chemical modification. The optimized oxidation conditions of montan resin were determined using single-factor experiments and response surface analysis. The amount of chemical constituents with oxygen-containing functional groups increased in the modified products after modification, as determined by IR and GC-MS analysis, among other methods. The water-soluble modified product showed an obvious effect in promoting growth and germination of wheat at 600 mg·L-1 and 300 mg·L-1, respectively.