Toxicity characterization of urban stormwater with bioanalytical tools

Stormwater harvesting has become an attractive alternative strategy to address the rising demand for urban water supply due to limited water sources and population growth. Nevertheless, urban stormwater is also a major source of surface water pollution. Runoff from different urban catchments with source contributions from anthropogenic activities and various land uses causes variable contaminant profiles, thus posing a challenging task for environmental monitoring and risk assessment. A thorough understanding of raw stormwater quality is essential to develop appropriate treatment facilities for potential indirect potable reuse of stormwater. While some of the key chemical components have previously been characterized, only scarce data are available on stormwater toxicity. We benchmarked stormwater samples from urban, residential and industrial sites across various Australian capital cities against samples from the entire water cycle, from sewage to drinking water. Six biological endpoints, targeting groups of chemicals with modes of toxic action of particular relevance for human and environmental health, were investigated: non-specific toxicity (Microtox and combined algae test), the specific modes of action of phytotoxicity (combined algae test), dioxin-like activity (AhR-CAFLUX), and estrogenicity (E-SCREEN), as well as reactive toxicity encompassing genotoxicity (umuC) and oxidative stress (AREc32). Non-specific toxicity was highly variable across sites. The baseline toxicity equivalent concentrations of the most polluted samples were similar to secondary treated effluent from wastewater treatment plants. Phytotoxicity results correlated well with the measured herbicide concentrations at all sites. High estrogenicity was found in two sampling events and could be related to sewage overflow. Genotoxicity, dioxin-like activity, and oxidative stress response were evident in only three of the samples where the stormwater drain was beside a heavy traffic road, confirming that road runoff is the potential source of contaminants, while the bioanalytical equivalent concentrations (BEQ) of these samples were similar to those of raw sewage. This study demonstrates the benefit of bioanalytical tools for screening-level stormwater quality assessment, forming the basis for the evaluation of future stormwater treatment and reuse schemes.     

Aroma-active compounds of butter: a review

This review article shows that more than 230 volatile compounds have been identified in butter, however, only a small number of them can be considered as key odorants of butter aroma. Gas chromatography olfactometry was used to determine the character impact odorants of different kinds of butter. Sweet cream butter is characterised by lactones with fruity and creamy notes and by sulphur compounds, having corn-like and garlic odours. The key odour compounds of sour cream butter are diacetyl (buttery-like), butanoic acid (cheesy) and δ-decalactone (peach), mainly due to lactic acid bacteria fermentation. The aroma of butter oil is characterised by aldehydes, such as (E)- and (Z)-2-nonenal and (E,E)-2,4-decadienal, conferring green and oily notes. Olfactometric studies of heated butter showed the formation of new aroma compounds during heating, such as 3-methylbutanoic acid (cheesy), methional (potato-like) and 2,5-dimethyl-4-hydroxy-3-(2H)-furanone (caramel-like). High temperature treatment of butter can also induce off-flavour development. Off-odours in butter originate from autooxidative and as well as from lipolytic reactions, microbial contamination and animal feeding. The views expressed in this publication are the sole responsibility of the authors and do not necessarily reflect the views of the European Commission. Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use, which might be made of the information contained herein.     

Reduced 11beta-hydroxysteroid dehydrogenase activity in the remaining kidney following nephrectomy

Intracellular access of steroids to gluco- and mineralocorticoid receptors is regulated by reduced 11beta-hydroxysteroid dehydrogenase (OHSD) 1 and 2. These enzymes convert active 11beta-OH-steroids into inactive 11-keto-steroids. The purpose of the present study was to establish whether the 11beta-OHSD1 and 11beta-OHSD2 are modulated in the remnant kidney 24 h or 14 days after uninephrectomy (UNX) in rats. Overall, 11beta-OHSD activity was analyzed by measuring the ratio of the exogenous 11beta-OH-steroid prednisolone to its 11-keto metabolite prednisone in vivo in kidney tissue using high performance liquid chromatography. To determine which isoenzyme accounts for the changed activity 24 h after UNX, the oxidation and reduction attributable to 11beta-OHSD1 and oxidation to 11beta-OHSD2 were analyzed in total renal extracts and in isolated glomeruli, proximal convoluted tubules (PCT), cortical ascending limbs, and cortical convoluted tubules (CCT). The messenger RNA content of 11beta-OHSD1 and 11beta-OHSD2 was measured by RT-PCR in renal tissues and single segments, using glyceraldehyde-3-phosphate-dehydrogenase as an internal standard. Protein amounts of 11beta-OHSD1 and 11beta-OHSD2 were assessed by Western blot. The prednisolone/prednisone ratio increased 24 h after UNX in 9 out of 10 animals (P < or = 0.0011), and was unchanged 14 days after UNX. 11Beta-OHSD1 oxidation (P < or = 0.032) and reduction activity (P < or = 0.002) declined 24 h after UNX in total extracts. 11Beta-OHSD1 oxidase activity was more than 3 times higher in PCT than in glomeruli, cortical ascending limbs, and CCT, and declined by 50% after UNX (P < or = 0.001). The reductase activity did not change following UNX in PCT. 11Beta-OHSD2 activity was 5-15 times higher in CCT than in the other segments, and decreased significantly after UNX (P < or = 0.008). UNX did not affect messenger RNA and protein levels of both enzymes in total renal extracts. In conclusion, 11beta-OHSD1 and 11beta-OHSD2 are predominantly expressed in PCT and CCT, respectively, and their corresponding oxidative activities decline after UNX. Thus, the access of 11beta-glucocorticosteroids to gluco- and mineralocorticoid receptors in the remaining kidney is facilitated after UNX.     

A key intermediate in the platinum-mediated hydrodesulfurization of dibenzothiophene

The thiaplatinacycles, [PtL2(C,S–C₁₂ H₈S)] and [PtL₂(C,S–C₁₃H10S)] (L = PEt₃, PMe₃; L₂=Ph₂PCH₂ CH2PPh₂), obtained from oxidative insertion of [Pt⁰Ln] into dibenzothiophene and 4-methyldibenzothiophene are hydrodesulfurized by reaction with hydrogen (toluene, 20 atm, 100°C) to biphenyl and 3-methylbiphenyl, respectively; addition of acidic alumina improves the reaction. These observations link the model systems and the latest generation of commercial second-stage HDS catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparative Characterisation of Aqueous Starch Dispersions by Light Microscopy,Rheometry and Iodine Binding Behaviour

Aqueous potato, wheat and pea starch dispersions (2 g dry Starch/100 g dispersion) were prepared at different time-temperature conditions and characterised by light microscopy of stained cryo-sections, amperometric iodine titration and rheometry. Depending on the gelatinisation conditions and the type of starch, a broad range of microstructures was obtained ranging from limited swelling to complete disintegration of starch granules. The swelling was accompanied by leaching of amylose from the granules and accumulation of amylose in the centre of the granules. The iodine binding capacity of the starch systems was related to the extent of swelling and solubilisation of starch and is therefore an appropriate indicator to follow the gelatinisation process. The flow behaviour was also sensitive to differences in the microstructure. The combination of light microscopy, iodometry and rheology successfully allowed the extensive characterisation of the supramolecular structure of low concentration starch systems.     

Evaluating dissolved organic carbon-water partitioning using polyparameter linear free energy relationships: Implications for the fate of disinfection by-products

The partitioning of micropollutants to dissolved organic carbon (DOC) can influence their toxicity, degradation, and transport in aquatic systems. In this study carbon-normalized DOC-water partition coefficients (K_DOC-w) were measured for a range of non-polar and polar compounds with Suwannee River fulvic acid (FA) using headspace and solid-phase microextraction (SPME) methods. The studied chemicals were selected to represent a range of properties including van der Waal forces, cavity formation and hydrogen bonding interactions. The K_DOC-w values were used to calibrate a polyparameter linear free energy relationship (pp-LFER). The difference between experimental and pp-LFER calculated K_DOC-w values was generally less than 0.3 log units, indicating that the calibrated pp-LFER could provide a good indication of micropollutant interaction with FA, though statistical analysis suggested that more data would improve the predictive capacity of the model. A pp-LFER was also calibrated for Aldrich humic acid (HA) using K_DOC-w values collected from the literature. Both experimental and pp-LFER calculated K_DOC-w values for Aldrich HA were around one order of magnitude greater than Suwannee River FA. This difference can be explained by the higher cavity formation energy in Suwannee River FA. Experimental and pp-LFER calculated K_DOC-w values were compared for halogenated alkanes and alkenes, including trihalomethane disinfection by-products, with good agreement between the two approaches. Experimental and calculated values show that DOC-water partitioning is generally low; indicating that sorption to DOC is not an important fate process for these chemicals in the environment.     

Solar/hydrogen systems for the 1985–2000 time frame: a review and assessment

A comprehensive state-of-the-art review of solar/hydrogen technologies has been conducted. From this, solar/hydrogen production systems which could be commercialized by the year 2000 have been characterized technically and economically. Incentives and disincentives for the early commercialization of four solar/hydrogen systems have been explored, conclusions drawn and recommendations made.This paper is an extreme condensation of the full (617 pp.) study report.