碳素纤维在近岸海洋污染物磷酸盐、硅酸盐处理中的应用

对碳素纤维进行氧化改性,利用改性后的碳素纤维处理近岸污染海水,重点研究了改性碳素纤维对海水中活性磷酸盐和活性硅酸盐的吸附作用。考察了碳素纤维液相改性时间、碳素纤维投加量、活性磷酸盐初始浓度、活性硅酸盐初始浓度、吸附时间、海况、pH值等单因素对近岸海洋污染物磷酸盐、硅酸盐吸附效果的影响。研究结果表明:改性碳素纤维对硅酸盐的吸附效果较好,去除率可达70%,对活性磷酸盐的去除率为31%左右。通过正交实验确定改性碳素纤维材料修复模拟近岸海水的优化条件为:碳素纤维改性时间为1.5 h,投加量为0.01 g,硅酸盐初始浓度为3mg/L,磷酸盐初始浓度为20 mg/L,海况为3级,pH值为8,吸附时间为3 h。在此条件下,碳素纤维对磷酸盐的去除率可达31.06%,硅酸盐去除率可达70.88%。     

Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.     

Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.     

二氧化氯消毒前后污水毒性的变化及消毒条件的影响

采用发光细菌试验和umu试验,分别考察了二氧化氯投加量和反应时间对污水二氧化氯消毒后急性毒性和遗传毒性变化的影响.结果表明,随着二氧化氯消毒剂投加量的增加,消毒后水样的急性毒性不断增大,但遗传毒性逐渐减小后趋于稳定.随着反应时间的延长,二氧化氯的消耗量不断增大,消毒后水样的急性毒性先增大后减小,遗传毒性逐渐减小后趋于稳定.由于消毒条件对污水急性毒性和遗传毒性有着不同的影响,说明污水中产生急性毒性和产生遗传毒性的物质不同,对于某一种污水,通过控制消毒条件可以使消毒后污水的急性毒性和遗传毒性都较低.     

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

Polycyclic aromatic hydrocarbons in the bulk precipitation and surface waters of Northern Greece

Bulk (wet and dry) precipitation and surface water sampling was undertaken in the main plain of central Macedonia in Northern Greece. Fourteen polycyclic aromatic hydrocarbons (PAHs) included in the US EPA's priority pollutant list were analysed. The concentrations determined in bulk precipitation were in general within the range of values worldwide reported. Concentrations were highest in the cold months. Deposition fluxes of PAHs were of the same order of magnitude as reported data. The greatest values were found when high concentrations of PAHs in precipitation coincided with large precipitation amounts. The concentrations of PAHs in surface waters (main rivers, tributaries, ditches, etc) were in general lower than those in bulk precipitation, and among the lowest reported for European rivers, excepting Np and Ph. Bulk deposition and domestic effluents are suggested as being the main PAH sources into surface waters.     

Levels, sources and spatiotemporal variation of nutrients and micropollutants in small streams of a Mediterranean River basin

In this study, nutrients, trace metals and priority pesticide compounds were investigated for the first time in water and sediment samples in streams of the Evrotas River basin (S.E. Greece) from 2006 to 2008. The most important sources of contamination were from the entry of pesticides and nutrients into surface waters and sediments as a result of the intensive agricultural activity as well as from the uncontrolled disposal of olive mill and citrus processing wastewaters. Aquatic risk assessment revealed that all insecticides detected showed high risk, suggesting adverse effects on the stream biota. Among the metals analyzed, Cr, Ni and Ba presented the highest concentrations in sediments, however, due to natural geological processes. Multivariate statistical techniques applied for data compression, exploration and interpretation proved to be useful tools for identifying the most critical pollutants affecting the surface water quality. The findings of this study suggest that the inclusion of streams with small catchment areas into WFD monitoring and assessment programs is essential, especially those of the Mediterranean region.     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

中国地区多溴联苯醚在不同环境介质中的监测进展

多溴联苯醚(Polybrominated diphenyl ethers, PBDEs)为一类新型的溴代阻燃剂,广泛应用于塑料制品、纺织品、电路板和建筑材料等领域。随着生产量和使用量的增加,PBDEs已造成全球环境污染,其带来的环境问题已引起各国关注。同时PBDEs的长距离迁移性和难降解性,使其在环境介质中进行富集,从而加重污染。归纳了中国地区PBDEs的监测进展,分别从大气、水体、沉积物和土壤中PBDEs的污染水平以及原因进行了分析和探讨。在此基础上,对于我国PBDEs的研究方向提出了展望。     

Organochlorine contaminants in eggs of the yellow-legged gull (Larus cachinnans michahellis) in the North Eastern Mediterranean: is this gull a suitable biomonitor for the region?

Levels of eight PCB congeners and thirteen organochlorine pesticides were measured in eggs sampled at four yellow-legged gull colonies from the Aegean Sea (NorthEastern Mediterranean) in 1997. There were no significant differences among colony areas in the median concentrations in any of the pollutants whereas cluster analyses did not generally reveal reasonable pollution patterns. The maximum concentrations of four congeners were found at Kinaros colony and of nine compounds were found at Lipsos colony. Fingerprints in both groups were similar in all areas. Of PCBs, congener 28, 118, 138, 180 and of pesticides beta-BHC and 2,4'-DDD were prominently dominant suggesting a particular pollution pattern in this region. Statistically significant correlations were found between most of the higher PCBs in all areas studied. The DDT metabolites correlated mostly with other OCs. We suggest that regional pollution by both groups is not adequately reflected in the eggs of this gull probably due to its extensive scavenging habits and, though information is needed from more colonies, it seems to be a poor biomonitor for organochlorines in this region.