Monitoring of the booster biocide dichlofluanid in water and marine sediment of Greek marinas

Dichlofluanid (N-dichlorofluoromethylthio-N'-dimethyl-N-phenylsulphamide) is used as booster biocide in antifouling paints. The occurrence of dichlofluanid and its metabolite DMSA (N'-dimethyl-N-phenyl-sulphamide) was monitored in seawater and marine sediment from three Greek marinas. Seawater and sediment samples were collected at three representative positions and one suspected hotspot in each marina and shipped to the laboratory for chemical analysis. As part of the project, an analytical method had been developed and validated. Furthermore, some additional experiments were carried out to investigate the potential contribution of paint particle bound dichlofluanid on the total concentration in the sediment. As expected, given its known high hydrolytic degradation rate, no detectable concentrations of dichlofluanid were measured in any of the seawater samples. DMSA was detected in seawater samples at very low concentrations varying from <3 ng l(-1) (LOD) to 36 ng l(-1). During method validation, it had already been demonstrated that dichlofluanid is unstable in sediment and can therefore only be determined as its metabolite DMSA. In a separate experiment, in which marine sediment was spiked with artificial paint particles containing dichlofluanid and then analysed according to the validated method, it was demonstrated that if there is any dichlofluanid originating from paint particles, this would be determined as DMSA. No DMSA was detected in any of the sediment samples. It could therefore be concluded that there were no significant concentrations of dichlofluanid in the sediment samples.     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

湿式烟气脱硫喷淋塔内部流场数值模拟研究

以300MW机组湿法烟气脱硫喷淋塔为研究对象,利用计算流体力学通用软件对其内部两相流场进行模拟。气相湍流由标准k 模型描述,喷淋液滴由拉格朗日颗粒轨道模型描述。预测了无喷淋和有喷淋2种条件下的气相湍流流场分布、沿塔高方向不同截面上的气速分布以及喷淋液滴的轨迹。模拟结果表明,引入喷淋液后,出口截面气速分布明显均匀化,其最大值由无喷淋时的12m/s降至6m/s。该最大值出现在靠近塔壁处,是由塔壁附近喷淋密度较低造成的,可通过改进周边喷嘴的布置方式及喷嘴型式进行优化。     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

Pencycuron application to soils: degradation and effect on microbiological parameters

Clay loam soil from agricultural fields of alluvial (AL) soil (typic udifluvent) and coastal saline (CS) soil (typic endoaquept) were investigated for the degradation and effect of pencycuron application at field rate (FR), 2-times FR (2FR) and 10-times FR (10FR) with and without decomposed cow manure (DCM) on soil microbial variables under laboratory conditions. Pencycuron degraded faster in CS soil and in soil amended with DCM. Pencycuron spiking at FR and 2FR resulted in a short-lived (in case of 10FR slightly longer) and transitory toxic effect on soil microbial biomass-C (MBC), ergosterol content and fluorescein diacetate hydrolyzing activity (FDHA). Amendment of DCM did not seem to have any counteractive effect of the toxicity of pencycuron on the microbial variables. The ecophysiological status of the soil microbial communities as expressed by microbial metabolic quotient (qCO2) and microbial respiration quotient (Q(R)) changed, but for a short period, indicating pencycuron induced disturbance. The duration of this disturbance was slightly longer at 10FR. Pencycuron was more toxic to the metabolically activated soil microbial populations, specifically the fungi. It is concluded that side effects of pencycuron at 10FR on the microbial variables studied were only short-lived and probably of little ecological significance.     

A lysimeter experiment to investigate the leaching of veterinary antibiotics through a clay soil and comparison with field data

Pharmaceuticals used in livestock production may be present in manure and slurry as the parent compound and/or metabolites. The environment may therefore be exposed to these substances due to the application of organic fertilisers to agricultural land or deposition by grazing livestock. For other groups of substances that are applied to land (e.g. pesticides), preferential flow in clay soils has been identified as an extremely important mechanism by which surface water pollution can occur. This lysimeter study was therefore performed to investigate the fate of three antibiotics from the sulphonamide, tetracycline and macrolide groups in a clay soil. Only sulphachloropyridazine was detected in leachate and soil analysis at the end of the experiment showed that almost no antibiotic residues remained. These data were analysed alongside field data for the same compounds to show that soil tillage which breaks the connectivity of macropores formed over the summer months, prior to slurry application, significantly reduces chemical mobility.     

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Interpretation of heavy metal data from mussel by use of multivariate classification techniques

Different strategies of multivariate analysis of metals concentrations (Mn, Fe, Ni, V, Co, Cu, Cd, Hg, Pb, Na, K) in mussel samples from different spanish markets are used to interpret a data base and identify differences between species and origin of the samples. Principal Component Analysis and Potential curves are applied to properly classify unknown samples from representative mussels samples (Mytilus edulis and Perna canaliculus). Also, Principal Components Analysis is used as display method to visualize the relation between the variables and objects of interest.     

Laboratory simulation of biodegradation of chemicals in surface waters: closed bottle and respirometric test

Microbial degradation is the most dominant elimination mechanism of organics from the environment. For evaluation of biodegradability of pure chemicals many standardized tests are available, but no standardized procedure for assessment of biodegradability of chemicals in surface water is agreed upon. Rates of in-situ biodegradation are usually estimated in laboratory simulation where environmental factors are reproduced to some extent. The aim of our study was to compare standardised ready biodegradability assessment, test (Closed bottle test) and its modifications employing the basic agreements on test conditions to simulate biodegradation in surface water. Standard test was modified using various natural river waters to simulate the natural environment in a simplified way. The impact of different types and amounts of nutrients and microorganisms on biodegradation was confirmed. The conditions in the recipient should be examined to extrapolate the results from ready biodegradability tests to real surface water.     

Methane emission from lakes

A physico-chemical model to describe methane and carbon dioxide emission from lakes was developed. The model describes the emission by diffusion, bubbles and plants. The intensity of the fluxes can be calculated either for total or particular emission in dependence on gas bubbles composition. It was found, that diffusional (Q) and bubble (J) fluxes depend on the methane molar ratio (X) in bubbles as follows: [formula: see text]. The model allows to estimate the role of the methane oxidation by atmospheric oxygen in the total methane flux. It was shown, that the methane oxidation does not influence much methane fluxes to the atmosphere for most of the experimentally observed situations.