Photochemical transformation of terbutaline (pharmaceutical) in simulated natural waters: Degradation kinetics and mechanisms

In this study, varied nature organic matter isolates were employed to investigate the indirect photo transformation of terbutaline, which is a major feed additive medicine to increase the proportion of lean meat in the livestock. In the indirect photolysis of terbutaline under solar simulated irradiation, ¹O₂ plays an important role among the •OH and ³DOM^∗. The reaction rate constant of ¹O₂ was determined as (7.1 ± 0.3) × 10⁶ M⁻¹ s⁻¹ at pH 7.0, while the reaction rate constant of •OH was (6.87 ± 0.43) × 10⁹ M⁻¹ s⁻¹. The contribution of singlet oxygen to the indirect photolysis of terbutaline (19–44%) was higher than that of the hydroxyl radical (1–7%). The pseudo first order rate constants for the photodegradation of terbutaline increase with increasing pH, which indicates that pH mainly affects the reaction rate of the singlet oxygen with the phenolic part of the terbutaline. The Quinone was identified as the main photosensitized product through LC–MS/MS analysis. It is also proposed that the degradation pathway of terbutaline involves reaction between the phenolic part of terbutaline and singlet oxygen. This finding strongly suggests that singlet oxygen was important factor for the photodegradation of terbutaline in natural waters.     

Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes

The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone ( [Formula: see text] =3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.     

Kinetics of the transformation of phenyl-urea herbicides during ozonation of natural waters: rate constants and model predictions

Oxidation of four phenyl-urea herbicides (isoproturon, chlortoluron, diuron, and linuron) was studied by ozone at pH=2, and by a combination of O3/H2O2 at pH=9. These experiments allowed the determination of the rate constants for their reactions with ozone and OH radicals. For reactions with ozone, the following rate constants were obtained: 1.9 +/- 0.2, 16.5 +/- 0.6, 393.5 +/- 8.4, and 2191 +/- 259 M(-1) s(-1) for linuron, diuron, chlortoluron, and isoproturon, respectively. The rate constants for the reaction with OH radicals were (7.9 +/- 0.1) x 10(9) M(-1) s(-1) for isoproturon, (6.9 +/- 0.2) x 10(9) M(-1) s(-1) for chlortoluron, (6.6 +/- 0.1) x 10(5) M(-1) s(-1) for diuron, and (5.9 +/- 0.1) x 10(9) M(-1) s(-1) for linuron. Furthermore, the simultaneous ozonation of these selected herbicides in some natural water systems (a commercial mineral water, a groundwater, and surface water from a reservoir) was studied. The influence of operating conditions (initial ozone dose, nature of herbicides, and type of water systems) on herbicide removal efficiency was established, and the parameter Rct (proposed by Elovitz, M.S., von Gunten, U., 1999. Hydroxyl radical/ozone ratios during ozonation processes. I. The Rct concept. Ozone Sci. Eng. 21, 239-260) was evaluated from simultaneous measurement of ozone and OH radicals. A kinetic model was proposed for the prediction of the elimination rate of herbicides in these natural waters, and application of this model revealed that experimental results and predicted values agreed fairly well. Finally, the partial contributions of direct ozone and radical pathways were evaluated, and the results showed that reaction with OH radicals was the major pathway for the oxidative transformation of diuron and linuron, even when conventional ozonation was applied, while for chlortoluron and isoproturon, direct ozonation was the major pathway.     

Oxidative transformation of micropollutants during municipal wastewater treatment: Comparison of kinetic aspects of selective (chlorine, chlorine dioxide, ferrate, and ozone) and non-selective oxidants (hydroxyl radical)

Chemical oxidation processes have been widely applied to water treatment and may serve as a tool to minimize the release of micropollutants (e.g. pharmaceuticals and endocrine disruptors) from municipal wastewater effluents into the aquatic environment. The potential of several oxidants for the transformation of selected micropollutants such as atenolol, carbamazepine, 17α-ethinylestradiol (EE2), ibuprofen, and sulfamethoxazole was assessed and compared. The oxidants include chlorine, chlorine dioxide, ferrate^VI, and ozone as selective oxidants versus hydroxyl radicals as non-selective oxidant. Second-order rate constants (k) for the reaction of each oxidant show that the selective oxidants react only with some electron-rich organic moieties (ERMs), such as phenols, anilines, olefins, and deprotonated-amines. In contrast, hydroxyl radicals show a nearly diffusion-controlled reactivity with almost all organic moieties (k ≥ 10⁹ M⁻¹ s⁻¹). Due to a competition for oxidants between a target micropollutant and wastewater matrix (i.e. effluent organic matter, EfOM), a higher reaction rate with a target micropollutant does not necessarily translate into more efficient transformation. For example, transformation efficiencies of EE2, a phenolic micropollutant, in a selected wastewater effluent at pH 8 varied only within a factor of 7 among the selective oxidants, even though the corresponding k for the reaction of each selective oxidant with EE2 varied over four orders of magnitude. In addition, for the selective oxidants, the competition disappears rapidly after the ERMs present in EfOM are consumed. In contrast, for hydroxyl radicals, the competition remains practically the same during the entire oxidation. Therefore, for a given oxidant dose, the selective oxidants were more efficient than hydroxyl radicals for transforming ERMs-containing micropollutants, while hydroxyl radicals are capable of transforming micropollutants even without ERMs. Besides EfOM, ammonia, nitrite, and bromide were found to affect the micropollutant transformation efficiency during chlorine or ozone treatment.     

The transformation of hexabromocyclododecane in aerobic and anaerobic soils and aquatic sediments

The biological transformation of hexabromocyclododecane (HBCD), a brominated fire retardant commonly used in a variety of consumer goods, was investigated in aerobic and anaerobic soils and freshwater sediments. Soil, river water, and aquatic sediments were collected from several locations in the United States and transformation of HBCD was evaluated in the correspondingly composed microcosms based on the Organisation for Economic Co-Operation and Development (OECD) Test Guidelines 307 (Aerobic and Anaerobic Transformation in Soil) or 308 (Aerobic and Anaerobic Transformation in Aquatic Sediment Systems). Soil and sediment reaction mixtures, prepared under either aerobic or anoxic conditions, were dosed with HBCD at a concentration ranging from approximately 10 to 80 ng/g dry weight. The soils and sediments were then placed at 20 degrees C for approximately 4 months and the concentration of HBCD in the microcosms was determined at selected time intervals utilizing high-performance liquid chromatography-mass spectrometry (LC-MS). HBCD loss was observed in both the aerobic and anaerobic soils and sediments although the rates were appreciable faster under anoxic conditions. Biologically mediated transformation processes (i.e., biotransformation) accelerated the rate of loss of HBCD when compared to the biologically inhibited (i.e., autoclaved) soils and sediments. Biotransformation half-lives for HBCD were determined to be 63 and 6.9 days in the aerobic and anaerobic soils, respectively, while biotransformation half-lives for HBCD in the two river systems ranged from 11 to 32 days and 1.1 to 1.5 days under aerobic and anaerobic conditions, respectively. Brominated degradation products were not detected in any of the soils or sediments during the course of the study.     

Degradation of plasmid and plant DNA in water microcosms monitored by natural transformation and real-time polymerase chain reaction (PCR)

Extracellular DNA exists in the environment and can be taken up by competent bacterial cells, leading to horizontal gene transfer. The persistence of extracellular plasmid and plant DNA in water microcosms was monitored in this study. Water samples were two groundwater (GW1 and GW2) and one river water (RW) samples. Three treatments included: (1) intact, (2) 0.22 microm filter-sterilized, and (3) autoclaved water. DNA from a plasmid (pNS1) and a transgenic Bt (Bacillus thuringiensis) corn line, both carrying a neomycin phosphotransferase gene (nptII gene) conferring kanamycin and neomycin resistance, was inoculated into the microcosms at 0.4 and 0.8 microg/ml, respectively. By monitoring its ability to transform a competent Pseudomonas stutzeri strain harboring plasmid pMR7 (P. stutzeri pMR7), plasmid DNA was degraded to undetectable levels in the intact and/or filter-sterilized water treatments within 48-96 h in GW1, GW2, and RW. Meanwhile, plasmid DNA persisted in the autoclaved treatment throughout the entire incubation period. For plant DNA, a highly sensitive real-time PCR method using SYBR Green I was developed to monitor the degradation dynamics of the nptII gene carried by the transgenic corn line in the microcosms. The results showed that the concentration of plant DNA was reduced by two orders of magnitude (from 0.8-0.008 microg/ml) within 96 h in the intact and filter-sterilized treatments of GW1, GW2, and RW, in contrast to its persistence in the autoclaved treatment. In addition, no kanamycin resistant (Km R) transformants were detected from in situ transformation of P. stutzeri pMR7 with plasmid pNS1 DNA.     

The effect of electrode material on the generation of oxidants and microbial inactivation in the electrochemical disinfection processes

Electrochemical disinfection has gained increasing attention as an alternative for conventional drinking water treatment due to its high effectiveness and environmental compatibility. The most common method of electrochemical disinfection is the use of electro-generated oxidants, such as active chlorine and reactive oxygen species, as disinfectants. This study examined the role of electrode material on the generation of oxidants, and elucidated the different reaction pathways for generating individual oxidants by employing boron-doped diamond (BDD), Ti/RuO₂, Ti/IrO₂, Ti/Pt-IrO₂, and Pt as anode materials. The efficiency of OH production, as determined by para-chlorobenzoic acid (pCBA) degradation, was in the order of BDD ? Ti/RuO₂ ≈ Pt. No significant production of OH was observed at Ti/IrO₂ and Ti/Pt-IrO₂. The OH was found to play a key role in O₃ generation at BDD, but not at the other electrodes. The production of active chlorine was in the order of Ti/IrO₂ > Ti/RuO₂ > Ti/Pt-IrO₂ > BDD > Pt. The large difference in this order from that of ROS was attributed to the difference in the electrocatalytic activity of each electrode material toward the production of active chlorine, as evidenced by linear sweep voltammetry (LSV) measurements. In addition, the characteristics of microbial inactivation as a function of electrode material were examined under the presence of an inert electrolyte, using Escherichia coli as an indicator microorganism.     

Incorporation of initiation, promotion and inhibition in the Rct concept and its application in determining the initiation and inhibition capacities of natural water in ozonation

Ozonation is widely employed in water treatment to purify water. The R_ct concept, which is defined as the ratio of OH exposure to ozone exposure, has been commonly used to quantify the OH concentration generating from ozone decomposition and model the removal of organic pollutant. Due to its empirical nature, however, the R_ct concept is limited in quantitatively elucidating how initiator, promoter and inhibitor involved in the OH chain reactions affect its value. A new R_ct model was developed by integrating the R_ct concept and the transient steady-state OH concentration to evaluate the influences of these modes of reactions on the R_ct value. It was found that the R_ct value is not only the ratio of OH exposure to ozone exposure but also the ratio of the total initiation capacity to the total inhibition capacity in a system. The presence of promoter, however, does not affect the R_ct value although it does accelerate ozone decomposition leading to lower ozone and OH exposures and result in hindered removal of target pollutant. The hindered removal of ibuprofen by ozonation in the presence of methanol (promoter) can be quantitatively described by the new R_ct model. The model can also be used to quantify the initiation and inhibition capacities of an ozonation system via the addition of an external inhibitor. Its application in determining the initiation and inhibition capacities of natural water was demonstrated.     

Effects of natural and synthetic surface active substances on the electrochemical reduction of cadmium in natural waters

Effects of surface active substances, natural and synthetic, in selected samples of seawater, river water and industrial effluents on the oxidation-reduction processes of cadmium have been studied by electrochemical methods and compared with the behaviour of different model compounds.Kinetic parameters, transfer coefficient α and apparent standard rate constant of the cadmium electrode reaction have been estimated from the shape and the height of the corresponding differential pulse voltammograms using theoretical curves obtained by digital simulation of the electrode process. The measure of the inhibition effect of surface active substances on the electrode reaction of cadmium was expressed in terms of the ratio of the rate constants determined in the presence and in the absence of surface active substances.It was found that the degree of inhibition depends on the concentration and type of surface active substances and on the pH of solution.     

厦门市旧城商业改造与人文保护

保护性更新是任何一个拥有历史的城市在自身发展的道路上都会遇到的课题。如何处理好商业的利益最大化与商业所在地的人文资源保护之间的矛盾成为厦门旧城商业改造必须要面对的问题。     

输变电施工企业安全管理的文化思考

结合电网建设的特点和现状,针对如何深入有效地进行安全生产管理展开思考,从提升安全管理实践水平入手,提出应强化安全意识,强化安全防护体系,强化事先控制及过程控制等措施并进行了具体阐述,以期构建输变电施工安全管理长效机制。     

转型期我国城市规划教育的问题与改革

从上世纪50年代初期在高校开设城市规划专业算起,我国城市规划教育已走过半个世纪的历程,这期间我国城市规划教育取得了巨大进展,也出现了不少问题。本文分析了我国城市规划教育出现的问题及其产生的原因并就我国城市规划教育的改革方向谈了一些看法,认为我国城市规划教育问题的产生和改革的内在动力,应是种种表象背后的深刻的政治和经济因素。我国经济社会全面转型期城市规划教育改革的出发点和归宿应该也必须是去适应我国政治和经济的变革。     

Chlorination of bromide-containing waters: Enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems

Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu₂O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pK_a of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu₂O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate >> sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO.     

Impact of the spectral and spatial properties of natural light on indoor gas‐phase chemistry: Experimental and modeling study

The characteristics of indoor light (intensity, spectral, spatial distribution) originating from outdoors have been studied using experimental and modeling tools. They are influenced by many parameters such as building location, meteorological conditions, and the type of window. They have a direct impact on indoor air quality through a change in chemical processes by varying the photolysis rates of indoor pollutants. Transmittances of different windows have been measured and exhibit different wavelength cutoffs, thus influencing the potential of different species to be photolysed. The spectral distribution of light entering indoors through the windows was measured under different conditions and was found to be weakly dependent on the time of day for indirect cloudy, direct sunshine, partly cloudy conditions contrary to the light intensity, in agreement with calculations of the transmittance as a function of the zenithal angle and the calculated outdoor spectral distribution. The same conclusion can be drawn concerning the position within the room. The impact of these light characteristics on the indoor chemistry has been studied using the INCA‐Indoor model by considering the variation in the photolysis rates of key indoor species. Depending on the conditions, photolysis processes can lead to a significant production of radicals and secondary species.     

Environmental performance evaluation of thermal insulation materials and its impact on the building

The purpose of this paper is to examine the building's environmental performance through the insulation's material selection. Contemporary insulation materials achieve thermal conductivity values of less than 0.04 W/mK, whilst a plethora of materials, which fulfil specific requirements like mechanical and physical features according to the object specific specifications, can be found in the market. Still, the latter is dominated by inorganic fibrous materials and organic foamy ones, which were the subject of this study. The two materials’ production process was registered and evaluated based on environmental criteria with Life Cycle Analysis’ implementation, which was supported by the GEMIS model. The results obtained were used to set operating performance indicators and environmental condition indicators based on the ISO 14031 standard and accomplish the Environmental Performance Evaluation for the two materials. Moreover, insulation materials’ life cycle correlation to building's life cycle examined and expressed with energy consumption indicators.     

杭州市地名数据采集及转换入库技术方案研究

针对杭州市地名数据库建设，提出了地名数据库建设的技术流程，研究了地名数据采集及转换入库的技术方案，并在杭州市地名数据库建设项目中进行了实践，取得了良好的效果。     

The effect of surface active substances on the electrochemical behaviour of copper ions in chloride solutions and in natural waters

Electrochemical methods have been used in the study of the adsorption behaviour of different surface active substances, biogenic and non-biogenic, as well as in the study of their complexation properties for copper ions in chloride solutions and in natural waters. The influence on the anodic oxidation wave of copper has been examined.

For surface active substances (humic substances and proteins), which at the same time exhibit complexation properties towards copper ions, the main interaction will be complexation, especially in the lower concentration range of both copper and the organic substance. At higher concentrations of the surface active substances and copper ions adsorption effects may play a role in oxido-reduction processes of copper at the electrode surface covered with organic coating.

Contrary to cadmium, the electrode reaction of copper is not greatly influenced by synthetic surface active substances like Triton X-100 and sodium dodecylsulphate, since in the potential range of the anodic wave of copper most synthetic surface actice substances are desorbed from the mercury electrode surface.

In natural samples the main interaction will be complexation of copper ions with the organic matter. Investigations of the interfacial interactions between copper and organic coatings have to be continued on the other surfaces, natural and/or model ones, which have different surface properties and will be of greater environmental significance. Mercury electrode/solution interface is not a very convenient model for the study or interfacial interactions of copper ions because of the nature of the electrode process of copper.     

The impact of auxiliary energy on the efficiency of the heating and cooling system: Monitoring of low-energy buildings

This paper presents a detailed meta-analysis of end and primary energy use for heating, cooling and ventilation of 11 low-energy non-residential buildings and one residential building in Germany that belong to the EnOB research program launched by the German Federal Ministry for Economy. In particular, the analysis emphasizes the substantial impact of auxiliary energy use on the efficiency of heating and cooling performance. The investigated buildings employ environmental energy sources and sinks - such as the ground, ground water, rainwater and the ambient air - in combination with thermo-active building systems. These concepts are promising approaches for slashing the primary energy use of buildings without violating occupant thermal comfort. A limited primary energy use of about 100 kWh_prim/(m²_neta) as a target for the complete building service technology (HVAC and lighting) was postulated for all buildings presented. With respect to this premise, a comprehensive long-term monitoring in high time resolution was carried out over the course of two to five years, with an accompanying commissioning of the building performance. Measurements include the energy use for heating, cooling, and ventilation, as well as the auxiliary equipment, the performance of the environmental heat source and sink, and local climatic site conditions.     

Stormwater impact on water quality of rivers subjected to point sources and urbanization – the case of Addis Ababa,Ethiopia

Urbanization of a catchment often causes degeneration of rivers. We studied the water quality of three rivers in Addis Ababa based on the impact of stormwater and non‐point sources, and urbanization. Along these rivers several point sources were registered, with direct discharge of industrial and domestic wastes into them. To distinguish the impact of these year‐round point‐sources from stormwater, we analysed physicochemical parameters, nutrients and heavy metals sampled from upstream to downstream sections of each river in the dry and wet season. Dissolved oxygen (DO), NO₂–N, NH₄–N, PO₄–P, (Cr(VI) and Cu) exceeded international standards, pointing to a generally poor water quality of the rivers in both seasons. NO₃–N, Mn and Zn were problematic in dry season only. Although stormwater improved DO, conductivity, PO₄–P, Cr(VI) and Zn, the levels were still critical, pointing to construction sites, agriculture and pit latrines, somewhat offsetting the effect of stormwater dilution. No clear impact of urbanization pressure was found.