Stable carbon kinetic isotope effects for the production of methacrolein and methyl vinyl ketone from the gas-phase reactions of isoprene with ozone and hydroxyl radicals

The stable-carbon kinetic isotope effects (KIEs) associated with the production of methacrolein (MACR) and methyl vinyl ketone (MVK) from the reactions of isoprene with ozone and OH radicals were studied in a 25 L reaction chamber at (298±2) K and ambient pressure. The time dependence of both the stable-carbon isotope ratios and the concentrations was determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The average yields of ¹³C-containing MACR and MVK generated from the ozone reaction of ¹³C-containing isoprene differed by ?3.6‰ and ?4.5‰, respectively, from the yields for MACR and MVK containing only ¹²C. For MACR and MVK generated from the OH-radical oxidation of isoprene the corresponding values were ?3.8‰ and ?2.2‰, respectively. These values indicate a significant depletion in the ¹³C abundance of MACR and MVK upon their formation relative to isoprene’s pre-reaction ¹³C/¹²C ratio, which is supported by theoretical interpretations of the oxidation mechanism of isoprene and its ¹³C-substituted isotopomers. Numerical model calculations of the isoprene + O₃ reaction predicted a similar depletion in ¹³C for both reaction products upon production. Furthermore, the model predicts mixing ratios and stable carbon delta values for isoprene, MACR, and MVK that were in agreement with the experimental results. The combined knowledge of isotope enrichment values with KIEs will reduce uncertainties in determinations of the photochemical histories of isoprene, MACR, and MVK in the troposphere. The studies presented here were conducted with using isoprene without any artificial isotope enrichment or depletion and it is therefore very likely that these results are directly applicable to the interpretation of studies of isoprene oxidation using stable carbon isotope ratio measurements.     

Low field-relevant tebufenozide concentrations affect reproduction in Chironomus riparius (Diptera: Chironomidae) in a long-term toxicity test

A few studies reporting the effects of tebufenozide, a non-steroidal ecdysone agonist that mimics natural moulting hormones in chironomids exist in the literature. However, nothing is known about its chronic or multigenerational effects on the reproduction of aquatic insects, although tebufenozide is present in aquatic ecosystems. Here, we investigated the chronic toxicity of tebufenozide in two successive generations of Chironomus riparius using nominal concentrations that ranged from 4 to 26.2 μg/L. We started the test from the first instar larvae in the parental (P) generation, quantifying life cycle parameters (emergence, sex ratio, development rate, fecundity and fertility) until the emergence in the subsequent F1 generation. Results showed a reduction in reproduction and a significant decrease in male developmental rate of midges for all treatments, in the F1 generation compared with the P generation (paired t?test; p?<?0.001). Two-way analysis of variance revealed a significant exposure?×?generation effect on male fraction with male fraction increasing (P generation) or decreasing (F1 generation) with increasing exposure. These effects on C. riparius underline the importance of conducting long-term studies with environmentally relevant concentrations to investigate population-level endpoints for endocrine disrupting chemicals.     

Atmospheric concentrations and air-sea exchanges of nonylphenol, tertiary octylphenol and nonylphenol monoethoxylate in the North Sea

Concentrations of nonylphenol isomers (NP), tertiary octylphenol (t-OP) and nonylphenol monoethoxylate isomers (NP1EO) have been simultaneously determined in the sea water and atmosphere of the North Sea. A decreasing concentration profile appeared following the distance increasing from the coast to the central part of the North Sea. Air-sea exchanges of t-OP and NP were estimated using the two-film resistance model based upon relative air-water concentrations and experimentally derived Henry's law constant. The average of air-sea exchange fluxes was -12+/-6 ng m(-2)day(-1) for t-OP and -39+/-19 ng m(-2)day(-1) for NP, which indicates a net deposition is occurring. These results suggest that the air-sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols in the North Sea.     

Think globally, act locally'? Climate change and public participation in Manchester and Frankfurt

'Think Globally, Act Locally' was one of the most famous slogans of the 1970s environmental movement. Discourses about global climate change are now a vivid illustration of this new 'global thinking'. Although there is a substantial amount of research about global environmental issues and policy initiatives, there is still a gap in understanding of how lay publics actually comprehend global climate change. Using qualitative research method, this study is a comparison of how lay publics in Frankfurt (Germany) and Manchester (UK) perceive these issues and the possible solutions. The study found strong similarities in lay public perceptions in both cities including that (1) awareness of global environmental issues is always contextualised in broader perspectives not exclusively 'environmental', (2) there is a shared and strong sense of global equity based on recognition of differences and (3) there is an ambivalence about the role of environmental 'information'. Differences between lay public perceptions in Manchester and Frankfurt can be explained by specific features of national cultures.     

Formation of secondary inorganic aerosols by power plant emissions exhausted through cooling towers in Saxony

Background, aim, and scope  The fraction of ambient PM₁₀ that is due to the formation of secondary inorganic particulate sulfate and nitrate from the emissions of two large, brown-coal-fired power stations in Saxony (East Germany) is examined. The power stations are equipped with natural-draft cooling towers. The flue gases are directly piped into the cooling towers, thereby receiving an additionally intensified uplift. The exhausted gas-steam mixture contains the gases CO, CO₂, NO, NO₂, and SO₂, the directly emitted primary particles, and additionally, an excess of ‘free’ sulfate ions in water solution, which, after the desulfurization steps, remain non-neutralized by cations. The precursor gases NO₂ and SO₂ are capable of forming nitric and sulfuric acid by several pathways. The acids can be neutralized by ammonia and generate secondary particulate matter by heterogeneous condensation on preexisting particles. Materials and methods  The simulations are performed by a nested and multi-scale application of the online-coupled model system LM-MUSCAT. The Local Model (LM; recently renamed as COSMO) of the German Weather Service performs the meteorological processes, while the Multi-scale Atmospheric Transport Model (MUSCAT) includes the transport, the gas phase chemistry, as well as the aerosol chemistry (thermodynamic ammonium–sulfate–nitrate–water system). The highest horizontal resolution in the inner region of Saxony is 0.7 km. One summer and one winter episode, each realizing 5 weeks of the year 2002, are simulated twice, with the cooling tower emissions switched on and off, respectively. This procedure serves to identify the direct and indirect influences of the single plumes on the formation and distribution of the secondary inorganic aerosols. Results and conclusions  Surface traces of the individual tower plumes can be located and distinguished, especially in the well-mixed boundary layer in daytime. At night, the plumes are decoupled from the surface. In no case does the resulting contribution of the cooling tower emissions to PM₁₀ significantly exceed 15 μgm⁻³ at the surface. These extreme values are obtained in narrow plumes on intensive summer conditions, whereas different situations with lower turbulence (night, winter) remain below this value. About 90% of the PM₁₀ concentrations in the plumes are secondarily formed sulfate, mainly ammonium sulfate, and about 10% originate from the primarily emitted particles. Under the assumptions made, ammonium nitrate plays a rather marginal role. Recommendations and perspectives  The analyzed results depend on the specific emission data of power plants with flue gas emissions piped through the cooling towers. The emitted fraction of ‘free’ sulfate ions remaining in excess after the desulfurization steps plays an important role at the formation of secondary aerosols and therefore has to be measured carefully.     

Simultaneous measurements of formaldehyde and nitrous acid in dews and gas phase in the atmosphere of Santiago,Chile

The amounts of formaldehyde and nitrous acid (HONO) in gas phase and dews of Santiago de Chile were simultaneously measured. Formaldehyde concentrations values in the liquid phase (dews) correlate fairly well with those in the gaseous phase and are even higher than those expected from gas–dew equilibrium. On the other hand, nitrite concentrations in dews were considerably smaller (ca. 15 times) than those expected from the gas-phase concentrations. This under-saturation is attributed to diffusion limitations due to the relatively large HONO solubility. In agreement with this, under-saturation increases with the rate of dew formation and the pH of the collected waters, factors that should increase the rate of gas to liquid HONO transfer required to reach equilibrium.     

Influence of pH on the sonolysis of ciprofloxacin: Biodegradability, ecotoxicity and antibiotic activity of its degradation products

The presence of antibiotics in the aquatic environment has raised concerns due to the potential risk for the emergence or persistence of antibiotic resistance. Antibiotics are often poorly degraded in conventional wastewater treatment plants. In this study, sonolysis at 520 kHz and 92 W L⁻¹ was used for the degradation of the fluoroquinolone antibiotic ciprofloxacin. In a first experiment at pH 7, 57% of the ciprofloxacin (15 mg L⁻¹) was degraded after 120 min of ultrasonic irradiation at 25 °C. pH proved to be an important parameter determining the degradation rate, since the pseudo first order degradation constant increased almost fourfold when comparing treatment at pH 7 (0.0058 min⁻¹) and pH 10 (0.0069 min⁻¹) with that at pH 3 (0.021 min⁻¹). This effect can be attributed to the degree of protonation of the ciprofloxacin molecule. The BOD/COD ratio of the solutions, which is a measure for their biodegradability, increased from 0.06 to 0.60, 0.17, and 0.18 after 120 min of irradiation depending on the pH (3, 7, and 10, respectively). The solution treated at pH 3 can even be considered readily biodegradable (BOD/COD > 0.4). The antibiotic activity against Escherichia coli (G−) and Bacillus coagulans (G+) of the treated solutions also reduced after sonolysis. The highest decrease was again found when irradiated at pH 3. In contrast, ecotoxicity of the solutions to the alga Pseudokirchneriella subcapitata increased 3- to 10-fold after 20 min of treatment, suggesting the formation of toxic degradation products. The toxicity slowly diminished during further treatment.