Hydroxyl radical-mediated degradation of diclofenac revisited: a computational approach to assessment of reaction mechanisms and by-products

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) are based on the in situ production of hydroxyl radicals (•OH) and reactive oxygen species (ROS) in water...     

A critical review of the water quality classification system in Turkey: A case study on Meric Basin

An 11-year period of water quality data, collected by the Directorate of Sate Water Works of Turkey are thoroughly analyzed for the purpose of implementing water quality classes to water resources in the Meric Basin, located on the European land mass of Turkey. Water quality parameters are divided into four groups as physical, organic, inorganic, and bacteriological. The quality class of each group is evaluated by taking into account the poorest quality of any parameter in the group, after which a quality rank is assigned to the sampling station and the waterbody in question. This method of water quality classification imposed by the Turkish Water Quality Act, is then criticized with respect to a statistical approach.     

Impact of dilution on the transport of poly(acrylic acid) supported magnetite nanoparticles in porous media

This paper investigates the impact of dilution on the mobility of magnetite nanoparticles surface coated with poly(acrylic acid) (PAA). Transport experiments were conducted in a water-saturated sand-packed column for input nanoparticle solutions with total Fe concentrations ranging from 100 to 600mg/L. Particle size analysis of the synthesized nanoparticle solutions showed that PAA provides good size stability for Fe concentrations as low as about 1mg/L. Time-moment analysis of the nanoparticle breakthrough curves, on the other hand, revealed that nanoparticle mass recovery from the column decreased consistently with dilution, with greater attenuation, sharper fronts and longer tails compared to that of the tracer. Particle size analysis of the eluted solutions shows that the nanoparticle size is negatively correlated with nanoparticle concentration. Modeling results suggest that the decrease in nanoparticle mobility with input concentration can be represented using a kinetic time-dependent deposition term with finite deposition capacity and a kinetic detachment term. For field applications, the increase in particle size and detachment resulting from dilution means reduced transport efficiency of nanoparticles and reaction potential with travel distance.     

Sequential extraction of cadmium in different soil phases and plant parts from a former industrialized area

Cd concentrations in mobile phases of soil are more representative than total Cd concentration for estimating Cd bioavailability, physicochemical reactivity and mobility. In this study, selective sequential extraction procedures were used to determine Cd in different soil phases. Soil samples and plants grown in these soils were collected from a serpentine and copper-mining area in Maden-Elazig-Turkey. The extracted fractions were exchangeable/carbonate, reducible-iron/manganese oxides, oxidizable-organic matter and sulfides, and residual phases except silicates. Concentrations of Cd in soils and plant samples were determined by flame atomic absorption spectrometry and inductively coupled plasma-mass spectrometry. We found that Cd concentrations in the EDTA and NH₂OH·HCl extracts are higher in most soil samples compared to the other extracts. We conclude that Cd levels in mobile phases are unexpectedly high. The observed Cd concentrations are in ranges of 0.03–3.4 mg kg⁻¹ for soil and 0.02–2.5 mg kg⁻¹ for plant parts. The percentages of cadmium up to 56% in exchangeable and carbonates fractions were observed to be significantly higher than in those values less than 2% reported in literature. This study has shown that the modified extraction method can be usefully applied to determine Cd concentrations in potentially mobile phase of soil. Furthermore, it was concluded that Brassicasea and Rumex leaves can be used as hyperaccumulator plants because their translocation factor and/or enrichment coefficient values were found to be higher than 1.0.     

Bioenergy production from diluted poultry manure and microbial consortium inside Anaerobic Sludge Bed Reactor at sub-mesophilic conditions

In this study, anaerobic treatability of diluted chicken manure (with an influent feed ratio of 1 kg of fresh chicken manure to 6 L of tap water) was investigated in a lab-scale anaerobic sludge bed (ASB) reactor inoculated with granular seed sludge. The ASB reactor was operated at ambient temperature (17–25°C) in order to avoid the need of external heating up to higher operating temperatures (e.g., up to 35°C for mesophilic digestion). Since heat requirement for raising the temperature of incoming feed for digestion is eliminated, energy recovery from anaerobic treatment of chicken manure could be realized with less operating costs. Average biogas production rates were calculated ca. 210 and 242 L per kg of organic matter removed from the ASB reactor at average hydraulic retention times (HRTs) of 13 and 8.6 days, respectively. Moreover, average chemical oxygen demand (COD) removal of ca. 89% was observed with suspended solids removal more than 97% from the effluent of the ASB reactor. Influent ammonia, on the other hand, did not indicate any free ammonia inhibition due to dilution of the raw manure while pH and alkalinity results showed stability during the study. Microbial quantification results indicated that as the number of bacterial community decreased, the amount of Archaea increased through the effective digestion volume of the ASB reactor. Moreover, the number of methanogens displayed an uptrend like archaeal community and a strong correlation (?0.645) was found between methanogenic community and volatile fatty acid (VFA) concentration especially acetate.     

Potential of ultrafiltration for organic matter removal in the polymer industry effluent based on particle size distribution analysis

The purpose of the study was the experimental evaluation of ultrafiltration as a potential innovative technology for the removal of organic matter of around 15,000 mg chemical oxygen demand (COD) per liter in the polymer industry wastewater. Particle size distribution (PSD) analysis served as the major experimental instrument along with conventional chemical settling. Biodegradation characteristics of the remaining COD after ultrafiltration were determined by model interpretation of the corresponding oxygen uptake rate (OUR) profile. The study first involved a detailed characterization of the polymer wastewater including PSD analysis of the COD content. Chemical treatability was investigated using lime alone and with ferric chloride as coagulants followed with a PSD assessment of the chemically settled effluent. Modeling of the OUR profile generated by the ultrafiltration effluent defined related biodegradation kinetics and provided information on the overall COD removal potential. PSD analysis indicated that more than 70 % of the total COD accumulated in the 220- to 450-nm size range. It indicated that ultrafiltration was potentially capable of removing more than 90 % of the COD with an effluent lower than 1,500 mg COD/L. Chemical settling with 750 mg/L of FeCl₃ dosing at a pH of 7.0 provided a similar performance. The ultrafiltration effluent included mainly hydrolysable COD and proved to be biodegradable, with the process kinetics compatible with domestic sewage. PSD evaluation proved to be a valuable scientific instrument for underlining the merit of ultrafiltration as the appropriate innovative technology for polymer wastewater, removing the major portion of the COD in a way that is suitable for recovery and reuse and producing a totally biodegradable effluent.     

Constructing domestic retrofit as a new urban infrastructure: experimentation,equitability and contested priorities

ABSTRACT

British cities and residential suburbs were originally developed under a modernist growth logic: separating home from work, with little concern for energy use. But recent political and social priorities such as climate change and energy security have created an imperative to reduce domestic energy use, with many existing dwellings rendered “obsolete” on account of their poor energy efficiency. This precipitated a need to develop domestic retrofit – the modification of building fabrics and systems to improve their energy efficiency – as an urban infrastructure. The UK Government responded in 2011 with policies such as the “Green Deal”, through which coalitions of actors in cities including local authorities, voluntary sector organisations and private businesses were encouraged to experiment with place-based retrofit. This paper examines the challenges and effects of developing a domestic retrofit infrastructure in a North London borough under particularly challenging policy conditions. We develop a hybrid framework for understanding the process and product of this place-based experimentation and through this we ask two questions: 1. How did both local and national conditions enable and limit the development of this infrastructure? 2. Was the emerging urban infrastructure functional and equitable? In Haringey’s case, a strong local political agenda positioned retrofit as a development opportunity and vehicle for reducing inequality, but national priorities around market-making and technological fixes dominated emerging responses. Whilst Haringey’s efforts in a difficult policy context did result in retrofits and improvements to around a thousand properties, the emerging infrastructure of retrofit services was incomplete, inequitable and temporary.     

Modelling cadmium bioaccumulation in Gammarus pulex by using experimental design approach

Recently, although dynamic approaches have been used increasingly to describe metal bioaccumulation in aquatic organisms, the validation of such laboratory-derived modelling is rarely assessed under environmental conditions. The present study aims to evaluate and verify statistical and mathematical models for the bioaccumulation of cadmium (Cd) and to evaluate the suitability of Gammarus pulex as a biomonitor for Cd. To optimise Cd²⁺ ion bioaccumulation conditions a Box–Behnken design was used and whether G. pulex can be used as an estimated tool to assess aquatic quality was investigated. A Box–Behnken experimental design combined with response surface modelling (RSM) was employed for Cd²⁺ bioaccumulation in G. pulex. Independent variables including temperature, contact time and Cd²⁺ ion concentration significance and their interactions were tested using analysis of variance. The selected variables’ optimum values were obtained by solving the quadratic regression model along with by analysing the response surface contour plots. Based on Box–Behnken design, the applied model is significant because model F-value and R² were obtained as 5121.49, 0.9998, respectively. Bioaccumulation of Cd amount was analysed using electrothermal atomic absorption spectrophotometer. The obtained data suggest that G. pulex can be evaluated as Cd biomonitor.     

Synthetic endocrine disruptors in the environment and water remediation by advanced oxidation processes

The present study is an overview of the literature on classes and types of compounds described as "endocrine disruptors" and their treatability in water by advanced oxidation processes, which generate hydroxyl radicals in water. The review is limited to details of the destruction of three classes of endocrine disruptors, namely bisphenols, alkylphenols and phthalates, which are among the most highly suspected endocrine disrupting compounds that interfere with the hormonal system of wildlife. It was found that photocatalysis with titanium dioxide was the most frequently tested advanced oxidation method most likely due its potential to render complete mineralization. There is sufficient research also with direct and indirect photolysis and ozonation, which were less effective for the overall mineralization but more representative of the conditions existing in real water treatment plants.     

Sonochemical degradation of diclofenac: byproduct assessment,reaction mechanisms and environmental considerations

The study covers a thorough assessment of the overall degradation of diclofenac-Na (DCF) by high-frequency ultrasound, focusing particularly on identification, interpretation, and characterization of the oxidation byproducts and their reaction mechanisms. It was found that sonication of 5 mg L^?1 DCF at near neutral pH rendered complete conversion of the compound, 45 % carbon, 30 % chlorine, and 25 % nitrogen mineralization. Density functional theory (DFT) calculations confirmed the experimentally detected major byproduct 2,6-dichloroaniline, the formation of which was explained by OH? addition to the ipso-position of the amino group. The stability of UV absorption at around 276–280 nm throughout reaction was in agreement with the detected byproduct structures, i.e., the presence of amino/amine groups and phenolic, aniline, benzene, and quinine-type derivatives, which all absorbed at around the same band. Microtox toxicity of the reactor aliquots at early reaction showed that initially the reaction products, specifically 1-(2,6-dichlorophenyl)-2-indoline-one, were very toxic; subsequently toxicity exhibited a fluctuating pattern, and a steady declination towards the “non-toxic” level was observed only after 90 min. Oxygen uptake analysis also revealed the formation of harmful products at early reaction, but the reactor was totally biodegradable upon 1-h sonication.