Evaluation of a detailed model of secondary organic aerosol formation from α-pinene against dark ozonolysis experiments

BOREAM, a detailed model for the gas-phase oxidation of α-pinene and its subsequent formation of Secondary Organic Aerosol (SOA), is tested against a large set of SOA yield measurements obtained in dark ozonolysis experiments. For the majority of experiments, modelled SOA yields are found to agree with measured yields to within a factor 2. However, the comparisons point to a general underestimation of modelled SOA yields at high temperatures (above 30 °C), reaching an order of magnitude or more in the worst cases, whereas modelled SOA yields are often overestimated at lower temperature (by a factor of about 2). Comparisons of results obtained using four different vapour pressure prediction methods indicate a strong sensitivity to the choice of the method, although the overestimated temperature dependence of the yields is found in all cases. Accounting for non-ideality of the aerosol mixture (based on an adapted UNIFAC method) has significant effects, especially at low yields. Our simulations show that the formation of oligomers through the gas-phase reactions of Stabilised Criegee Intermediates (SCI) with other molecular organic products could increase the SOA yield significantly only at very low relative humidity (below 1%). Further tests show that the agreement between model and measurements is improved when the ozonolysis mechanism includes additional production of non-volatile compounds.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Petroleum refinery stripped sour water treatment using the activated sludge process

A pilot study was performed over 91 days to determine if the activated sludge process could treat a segregated stripped sour water (SSW) stream from a petroleum refinery. The study was performed in two periods. The first period was terminated after 19 days, as a result of excessive sludge bulking. The elimination of sludge bulking during the 70-day second period is attributed to operational changes, which included aerating the influent to oxidize reduced sulfur, adjusting the influent pH, and adding micronutrients to satisfy biological requirements. The pilot plant provided a chemical oxygen demand (COD) removal of up to 93%. Nitrification was achieved, with effluent ammonia values < 1 mg-N/L. These results indicate that direct treatment of SSW with the activated sludge process is possible and has direct application to full-scale petroleum refinery wastewater plant upgrades.     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

Metal bioaccumulation and metallothionein concentrations in larvae of Crassostrea gigas

Larval stages of bivalve molluscs are highly sensitive to pollutants. Oysters from a hatchery from Normandy (English Channel) were induced to spawn, and fertilized eggs were exposed to copper or cadmium for 24 h. Metal accumulation (from 0.125 to 5 microg Cu L(-1) and from 25 to 200 microg Cd L(-1)) and MT concentrations were measured in larvae. Compared to controls, larvae accumulated copper and cadmium with an increase in MT concentrations particularly with cadmium (i.e. 130.96 ng Cu (mg protein)(-1) and 12.69 microg MT (mg protein)(-1) at 1 microg Cu L(-1) versus 23.19 ng Cu (mg protein)(-1) and 8.92 microg MT (mg protein)(-1) in control larvae; 334.3 ng Cd (mg protein)(-1) and 11.70 microg MT (mg protein)(-1) at 200 microg Cd L(-1) versus 0.87 ng Cd (mg protein)(-1) and 4.60 microg MT (mg protein)(-1) in control larvae). Larvae were also obtained from oysters of a clean area (Arcachon Bay) and a polluted zone (Bidassoa estuary) and exposed to copper in the laboratory, their MT concentration was measured as well as biomarkers of oxidative stress. Biomarker responses and sensitivity to copper for the larvae from Arcachon oysters were higher than for those from Bidassoa.     

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.     

Associated skeletons of a new middle Triassic "Rauisuchia" from Brazil

For more than 30 million years, in early Mesozoic Pangea, ??rauisuchian?? archosaurs were the apex predators in most terrestrial ecosystems, but their biology and evolutionary history remain poorly understood. We describe a new ??rauisuchian?? based on ten individuals found in a single locality from the Middle Triassic (Ladinian) Santa Maria Formation of southern Brazil. Nine articulated and associated skeletons were discovered, three of which have nearly complete skulls. Along with sedimentological and taphonomic data, this suggests that those highly successful predators exhibited some kind of intraspecific interaction. Other monotaxic assemblages of Triassic archosaurs are Late Triassic (Norian-Rhaetian) in age, approximately 10 million years younger than the material described here. Indeed, the studied assemblage may represent the earliest evidence of gregariousness among archosaurs, adding to our knowledge on the origin of a behavior pattern typical of extant taxa.     

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.