Occurrence of alkylphenolic substances in a Great Lakes coastal marsh, Cootes Paradise, ON, Canada

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 microg g(-1). To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions.     

Anaerobic degradation of nonylphenol in soil

This study investigated the effects of various factors on the anaerobic degradation of nonylphenol (NP) in soil. The results show that the optimal pH for NP degradation was 7.0 and that the degradation rate was enhanced when the temperature was increased. The addition of compost enhanced NP degradation. The individual addition of the electron donors lactate, acetate, and pyruvate inhibited NP degradation. The high-to-low order of NP degradation rates under three anaerobic conditions was sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the anaerobic degradation of NP, with sulfate-reducing bacteria being a major component of the soil. Of the anaerobic strains isolated from the soil samples, strain AT3 expressed the best ability to biodegrade NP.     

Numerical simulation of hydrogen–air detonation for damage assessment in realistic accident scenarios

An accidental hydrogen release within an equipment enclosure may result in the presence of detonable mixture in a confined environment. From a safety standpoint, it is then useful to assess the potential for damage. In that context, numerical simulation of the sequence of events subsequent to detonative ignition provides a useful tool, although with obvious limitations. This article describes the procedure, summarizes two case studies, and reviews the limitations. First, a hydrogen dispersion pattern is obtained from numerical simulation of dispersion, using a commercial package designed primarily for incompressible flow. This dispersion cloud is then used as the initial condition in an inviscid, compressible, reactive flow simulation. To force detonative ignition, a sufficiently large amount of energy is deposited in a small region that corresponds to the ignition location. Chemistry is modeled using a single step Arrhenius model. Because the wave thickness is small compared with the computational domain, a fine mesh is needed, limiting the practicality of the process to two-dimensional geometries. This is the most significant limitation; it is conservative. The two cases described in the paper include an electrolyzer, in which a small release occurs, leading potentially to some damage to the enclosure, and a reformer, in which the consequences are potentially more serious.     

On the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education

This paper describes the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education. The curriculum is being developed as part of the educational and training activities of the European Network of Excellence Safety of Hydrogen as an Energy Carrier (HySafe) and has been implemented into a 1-year Postgraduate Certificate Course in Hydrogen Safety Engineering by the University of Ulster. The course is taught in the distance learning mode and comprises of two 30 CATS-point modules, namely, ‘Principles of Hydrogen Safety’ and ‘Applied Hydrogen Safety’. The first delivery of this course began in January 2007 and the second delivery will commence in September 2007.     

Variability of soil-water quality due to Tsunami-2004 in the coastal belt of Nagapattinam district, Tamilnadu

In this study, the Tsunami-caused deterioration of soil and groundwater quality in the agricultural fields of coastal Nagapattinam district of Tamilnadu state in India is presented by analyzing their salinity and sodicity parameters. To accomplish this, three sets of soil samples up to a depth of 30cm from the land surface were collected for the first six months of the year 2005 from 28 locations and the ground water samples were monitored from seven existing dug wells and hand pumps covering the study region at intervals of 3 months. The EC and pH values of both the soil and ground water samples were estimated and the spatial and temporal variability mappings of these parameters were performed using the geostatistical analysis module of ArcGIS((R)). It was observed that the spherical semivariogram fitted well with the data set of both EC and pH and the generated kriged maps explained the spatial and temporal variability under different ranges of EC and pH values. Further, the recorded EC and pH data of soil and ground water during pre-Tsunami periods were compared with the collected data and generated variability soil maps of EC and pH of the post-Tsunami period. It was revealed from this analysis that the soil quality six months after the Tsunami was nearing the pre-Tsunami scenario (EC< 1.5dSm(-1); pH<8), whereas the quality of ground water remained highly saline and unfit for irrigation and drinking. These observations were compared with the ground scenarios of the study region and possible causes for such changes and the remedial measures for taking up regular agricultural practices are also discussed.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Estimating naphthenic acids concentrations in laboratory-exposed fish and in fish from the wild

Naphthenic acids (NAs) are the most water-soluble organic components found in the Athabasca oil sands in Alberta, Canada, and these acids are released into aqueous tailing waters as a result of bitumen extraction. Although the toxicity of NAs to fish is well known, there has been no method available to estimate NAs concentrations in fish. This paper describes a newly developed analytical method using single ion monitoring gas chromatography-mass spectrometry (GC-MS) to measure NAs in fish, down to concentrations of approximately 0.1mgkg(-1) of fish flesh. This method was used to measure the uptake and depuration of commercial NAs in laboratory experiments. Exposure of rainbow trout (Oncorhynchus mykiss) to 3mg NAsl(-1) for 9d gave a bioconcentration factor of approximately 2 at pH 8.2. Within 1d after the fish were transferred to NAs-free water, about 95% of the NAs were depurated. In addition, the analytical method was used to determine if NAs were present in four species of wild fish - northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis), white sucker (Catostomus commersoni), walleye (Sander vitreus) - collected from near the oil sands. Flesh samples from 23 wild fish were analyzed, and 18 of these had no detectable NAs. Four fish (one of each species) contained NAs at concentrations from 0.2 to 2.8mgkg(-1). The GC-MS results from one wild fish presented a unique problem. However, with additional work it was concluded that the NAs concentration in this fish was <0.1mgkg(-1).     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.