低频率干湿交替环境中有机涂层失效过程

目的 研究低频率干湿循环条件下的有机涂层失效过程。方法 应用电化学阻抗谱技术,结合浸泡过程中涂层表面以及基底金属的形貌变化,对比研究全浸环境和低频率干湿交替环境下,浸泡初期、浸泡中期、浸泡末期有机涂层的失效过程及特征。结果 低频率干湿交替环境下,涂层在浸泡初期、中期、末期所经历的时长分别为18、4、46天,较全浸环境来讲,显著缩短了浸泡中期的时长,同时也显著延长了浸泡末期的时长。两种环境下的涂层均发生明显的局部剥离,且基底金属也均有明显的局部腐蚀。结论 低频率干湿交替环境明显延长了涂层的失效过程,且此环境下基底金属出现了明显的局部腐蚀。     

FPSO工艺水舱阳极快速消耗原因分析

目的 研究FPSO工艺水舱中铝牺牲阳极消耗过快的原因。方法 参照GB 17848—1999牺牲阳极电化学性能试验方法,对比水舱环境与普通环境下,在役阳极的电化学性能数据,并模拟水舱环境,监测阳极工作时实际的发生电流与工作电位等情况,据此分析牺牲阳极在工艺水舱中消耗过快的原因。结果 在常温（25 ℃）、常温充空气、高温（65 ℃）充空气等条件下,阳极的电化学容量分别是2522.07、2464.29、1943.74 Ah/kg,且高温（65 ℃）充空气环境下阳极的晶间腐蚀较其他两组试验严重许多,说明温度是影响阳极电化学容量的关键因素。在模拟工艺水舱环境下,实测的阳极发生电流最高可达100 mA。将工艺水与海水1:5稀释后,实测的保护电流密度最高达45 mA,说明工艺水中存在大量的去极化剂,是造成阳极快速消耗的又一重要因素。结论 工艺水舱环境下,阳极发生严重的晶间腐蚀,严重影响了阳极的电化学容量,使阳极寿命缩短。工艺水成分中含大量去极化剂,使船舱所需的保护电流密度大大增加,促使阳极发生电流加大,亦缩短了阳极的实际服役寿命。     

Solid wastes integrated management in Rio de Janeiro: input-output analysis

This paper analyzes the socioeconomic aspects of solid waste management in Rio de Janeiro. An "input-output" methodology was used to examine how the secondary product resulting from recycling is re-introduced into the productive process. A comparative profile was developed from the state of recycling and the various other aspects of solid waste management, both from the perspective of its economic feasibility and from the social aspects involved. This was done analyzing the greenhouse gas emissions and the decreased energy consumption. The effects of re-introducing recycled raw materials into the matrix and the ensuing reduction of the demand for virgin raw materials was based on the input-output matrix for the State of Rio de Janeiro. This paper also analyzes the energy savings obtained from recycling and measures the avoided emissions of greenhouse gases.     

Anaerobic digestion of linear alkyl benzene sulfonates: biodegradation kinetics and metabolite analysis

In the present work the effect of the alkyl chain length and the position of the sulfophenyl substituent of the linear alkylbenzene sulfonates (LAS) on their anaerobic biodegradability have been investigated. Degradation kinetics of the linear alkyl benzene sulfonates homologues, 2C₁₀LAS, 2C₁₂LAS and 2C₁₄LAS, have been studied. It has been also investigated the effect of the isomer type on the degradation rate of the LAS molecule through the comparative study of the 2C₁₀LAS and 5C₁₀LAS isomers. Batch anaerobic biodegradation tests were performed using sludge from the anaerobic digester of a wastewater treatment plant as microorganisms source. Ultimate biodegradation was evaluated from the biogas production whereas primary biodegradation was determined by specific analysis of the surfactant. LAS homologues and isomers showed a negligible primary biodegradation under anaerobic conditions. Furthermore, analysis of sulfophenyl carboxilates (SPC) by LC–MS indicated a low and constant level of these LAS degradation metabolites over the test period. These data are consistent with a minimal transformation of the LAS parent molecule in the anaerobic digesters. On the other hand, the addition of the shortest alkyl chain length homologues, decyl and dodecylbenzene sulfonates, reduces the biogas production whereas the most hydrophobic homologue, the tetradecylbenzene sulfonate, enhances the biogas production. This LAS homologue seems to increase the availability of organic compounds sorbed on the anaerobic sludge promoting their biodegradation.     

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.     

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems

Gamma-hexachlorocyclohexane (gamma-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of alpha-, beta-, gamma-, delta-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While alpha- and gamma-HCH disappeared after 20-40d, the most recalcitrant isomers: beta- and delta-HCH were only degraded after 102d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.     

Enantiomeric separation of metolachlor and its metabolites using LC-MS and CZE

The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography-mass spectrometry (LC-MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC-MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (gamma-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background CZE electrolyte was found to consist of borate buffer (pH=9) containing 20% methanol (v/v) and 2.5% gamma-CD (w/v). Maximum resolution of ESA and OXA enantiomers was achieved using a capillary temperature of 15 degrees C and applied voltage of 30 kV. The applicability of the LC-MS and CZE methods was demonstrated successfully on the enantiomeric analysis of metolachlor and its metabolites in samples from a soil and water degradation study that was set up to probe the stereoselectivity of metolachlor biodegradation. These techniques allow the enantiomeric ratios of the target analytes to be followed over time during the degradation process and thus will prove useful in determining the role of chirality in pesticide degradation and metabolite formation.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Influences of macroalga-derived dissolved organic carbon on the aquatic toxicity of copper and cadmium

In this study, the effect of dissolved organic carbon (DOC) derived from macroalga (Sargassum) on the acute toxicity of copper (Cu) and cadmium (Cd) to a freshwater cladoceran (Daphnia magna) was investigated. Potassium-loaded macroalga was incubated with ultrapure water to extract macroalgal DOC, which was then spiked with the constituents of the Elendt M7 hard water media. The 48 h median lethal concentration of Cu increased linearly with DOC levels but that of Cd was relatively independent of DOC levels (0-44 mg l(-1)). The independence of Cd toxicity on DOC level might be due to the competitive effect of high calcium concentrations in the media with Cd for the binding sites of DOC. The decreased Cu toxicity was a result of reduced Cu uptake as evidenced in a separate accumulation test. Also, the capability of the macroalgal DOC on reducing Cu toxicity was found to be comparable to DOC tested in other studies. Therefore, the present study suggested that the biosorption treatment process using macroalgae should consider the effect of DOC release from the biomass as a step of modifying the metal toxicity as well as influencing metal biosorption capacity.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.