Removal and pre-concentration of phenolic species onto beta-cyclodextrin modified poly(hydroxyethylmethacrylate-ethyleneglycoldimethacrylate) microbeads

Poly(Hydroxyethylmethacrylate-Ethyleneglycoldimethacrylate), poly(HEMA-EGDMA), microbeads with 150-200 microm in size, was prepared by suspension polymerization. Beta-cyclodextrin was modified onto the polymeric microbeads using glutaraldahyde activation in an acidic medium at pH=2.5. FT-IR and TGA were used for the characterization of modified polymers and the determination of the nature of the interaction between phenolic compounds and the modified polymeric microbeads. Plain and beta-cyclodextrin modified microbeads were used in adsorption-desorption studies of phenolic species in single solution. Adsorption capacities of the phenolic species onto the plain microbeads were found to be 28.2, 17.0, 14.3, 9.8, and 1.92 mg/g polymer for o-chloro phenol, p-nitro phenol, p-chloro phenol, o-nitro phenol, and phenol, respectively. However, for beta-cyclodextrin modified microbeads, adsorption capacity of phenolic species was determined as 274, 365, 128, 182, and 87 mg/g for phenol, o-nitro phenol, p-nitro phenol, o-chloro phenol, and p-chloro phenol, respectively. Desorption ratio for the phenolic species was more than 90%, except for o-nitro phenol. Detection limits of the phenolic species were improved at least 500-fold for UV-Vis spectrophotometric detection, after the pre-concentration of all phenolic species used in this study. Adsorption time for the phenolic species onto beta-cyclodextrin-modified poly(HEMA-EGDMA) microbeads was found to be reasonable short (10-60 min) and suitable for the applications. Also, synthesized microbeads were useful for the repeated use for the removal and pre-concentration of phenolic species.     

Investigation of acute toxicity of chlorpyrifos-methyl on guppy Poecilia reticulata

Static bioassays were made to determine acute toxicity of chlorpyrifos-methyl, a wide spectrum organophosphorus insecticide and potential toxic pollutant of aquatic ecosystem, Guppy fish (Poecilia reticulata). Bioassays were made at a regulated temperature of 22+/-1 degrees C and were repeated three times. Lethal doses of the insecticides were determined using LC50 software programme of U.S. EPA based on Finney's Probit Analysis statistical method. The 96 h LC50 value and 95% confidence limit of chlorpyrifos-methyl for Guppy was estimated as 1.79 (1.47-2.10) mg/l. The fish exposed to chlorpyrifos-methyl exhibited behavioral changes in the form of neurotoxin toxicity: less general activity than control group, loss of equilibrium, erratic swimming and staying motionless at a certain location generally at mid-water level for prolonged periods. The 1 mg/l (lowest) concentration had similar behavior (NOEC) with the control group.     

Effects of two herbicidal wastewaters on Chlorella sp. and Phaeodactylum tricornutum

The effects on Chlorella sp. and Phaeodactylum tricornutum of two industrial wastewaters known to contain the herbicide residues of Trifluralin and Propanil have been determined by monitoring the number of cells, the chlorophyll fluorescence and the carbon dioxide assimilation simultaneously for a period of 14 days. The growth of the diatom, Phaeodactylum tricornutum, was inhibited by concentrations of herbicidal waste of the order of 0.1-0.5%, apparently because the rate of reproduction was reduced. Chlorella sp. cells, on the other hand, whilst dramatically inhibited by 1% concentrations of herbicidal waste, were able to recover over a period of 14 days. If discharged at concentrations below 0.01%, the industrial wastes appeared not to affect phytoplankton.     

4-Methylsterols in recent lacustrine sediments: Terrestrial,planktonic or some other origin?

Sediment cores from oxygen depleted zones of lake Léman (lake of Geneva) and from anoxic surface sediment from Voua de la Motte (France) were analyzed for their sterol compositions. 4-methylstanols were found to be major sterols in Motte lake sediment, which is rich in organic matter. In lake Léman, the relative abundances of the same 4-methylstanols increase with the depth in the core, but they remain always minor compounds. An extensive search for a possible external source for these compounds included the analysis of water, of the plankton and of the surrounding soil material. All these results, along with those of an in situ incubation experiment, give strong evidence in favor of their in situ bacterial biosynthesis.     

Use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution: accumulation and cellular distribution tests

Laboratory experiments were conducted to investigate the potential use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution. Lichen thalli were exposed to 0.00, 0.25, 0.50, 0.75 and 1.00 mM copper in synthetic freshwater to solve the problems of metal bioavailability. The mineral composition of this media was prepared so that it corresponded to the ion composition of natural waters in D. luridum ecosystems. Sequential elution procedures using NiCl2 or Na2-EDTA (20 mM) were used to determine the distribution of metals at different cellular sites. The copper concentration extracted from thalli was correlated with pollution intensity, the greater correlation being with the Na2-EDTA extractant. The malondialdehyde concentration in thalli can be used as indicator of copper pollution; however, similar membrane degradation was observed for 0.25 and 0.50 mM copper and for 0.75 and 1.00 mM copper.     

On the sedimentary occurrence of chlorophyllone a

The 13(2),17(3)-cyclopheophorbide a enol (CPP) is shown to convert mainly to a approximately 1:1 mixture of (13(2)R/S) chlorophyllones a (Chlone), when chromatographed over silica gel or alumina supports. 15(1)-hydroxychlorophyllonelactone a and some other chlorophyll a related compounds are also tentatively identified as minor transformation products of CPP. This raises the possibility that the chlorophyllones reported in recent sediments may be analytical artifacts from CPP. However, data for the surface sediments from Lake Motte as well as literature data for other contemporary sediments show that, (i) they are not artifacts, (ii) considering that CPP is the intermediate compound in the formation of chlorophyllones from chlorophyll a, the hydroxylation of CPP in the sedimentary environment involves an enzymatic process leading preferentially to 13(2)S chlorophyllone a.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO2) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography-electron capture detector (GC-ECD) indicated that the herbicide trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid-phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low-cost home-made system that did not require the use of organic solvents.     

Solventless sample preparation for pesticides analysis in environmental water samples using solid-phase microextraction-high resolution gas chromatography/mass spectrometry (SPME-HRGC/MS)

Solid-phase micro-extraction (SPME) coupled on line with high resolution gas chromatography and mass spectrometric detection is described for the analysis of pesticides in environmental water samples. Experiments were performed in order to optimize the SPME extraction conditions for selected pesticides including tiomethon, trichorfon, dimethoate, diazinon, malathion, dicofol, methidathion, ethion, bromopropylate and pyrazophos from spiked water solutions. To enhance the SPME efficiency, experimental conditions including the fiber composition, stirring rate, temperature, adsorption time, desorption time and salt concentration were optimized. After validation, the SPME-GC/MS methodology was applied to real-world environmental water samples.     

Limited scope for reproductive senescence in wild populations of a short-lived fish

Senescence in wild populations was long considered negligible but current evidence suggests that it is widespread in natural populations of mammals and birds, affecting the survival and reproductive output of older individuals. In contrast, little is known about reproductive senescence in species with asymptotic growth that can keep increasing their reproductive output as they grow older and larger. Using a cross-sectional study, we tested age-related decline in fecundity and relative allocation to reproduction in five wild populations of an annual killifish, Nothobranchius furzeri (Cyprinodontiformes). We did not detect any decline in absolute female egg production over their short lifespan in the wild. Relative fecundity (egg production controlled for female body mass) tended to decrease with age. This effect was driven primarily by a single population that survived 17 weeks, almost twice as long as the median persistence of the other four study populations. There was no decrease in relative ovary mass while in males, relative testes mass actually increased with age. Intra-population variation in relative ovary mass increased in older females suggesting heterogeneity in individual trajectories of female reproductive allocation. Overall, we demonstrate that annual killifish do not experience significant age-related decline in reproductive functions during their very short lifespan in the wild despite the marked deterioration of gonad tissue detected in captivity.     

Living within fallen palm leaves: the discovery of an unknown Blommersia (Mantellidae: Anura) reveals a new reproductive strategy in the amphibians of Madagascar

We describe a new mantelline frog of the genus Blommersia found in rainforest in North East Madagascar, from the protected areas of Ambatovaky, Betampona, Masoala, and Zahamena. Blommersia angolafa n.sp. is a small frog, with a body size of 17–21 mm, expanded finger and toe tips, and colouration ranging from yellow to dark brown, with pale-bluish spots on the flanks and light tips of fingers and toes. A peculiar aspect characterising this new species is its novel life history and reproductive mode. Both sexes live and breed in a phytotelmic habitat of water accumulated within fallen prophylls and fallen leaf sheaths of at least three species of Dypsis palms. Within these phytotelmata, egg laying and complete larval development occur. Thus, B. angolafa n.sp. represents a new evolutionary lineage of Malagasy frogs in which phytotelmy is known. Up to now, reproduction in phytotelmata in Malagasy frogs has been reported for many cophyline microhylids, most species of Guibemantis, Mantella laevigata, and possibly in a still-undescribed species belonging to the genus Spinomantis. We consider the reproductive mode of B. angolafa as a derived character, having evolved from the more typical reproduction in lentic water bodies. The general scarcity of lentic habitats in Malagasy rainforests may have provided the conditions that favoured the evolution of this phytotelmic breeding strategy. The new species, being specialised to a habitat represented by a few selected Dypsis species, potentially suffers the selective exploitation of these palms.