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.     

Spatial surrogates for the disaggregation of CORINAIR emission inventories

CORINAIR atmospheric emission inventories are frequently used input data for air quality models with a domain situated in Europe. In CORINAIR emission inventories, sources are broken down over 11 major source categories. This paper presents spatial surrogates for the disaggregation of CORINAIR atmospheric emission inventories for input of air pollutants and particulate matter to grid or polygon based air quality model domains inside Europe. The basis for the disaggregation model was the CLC2000 land cover data to which statistical weights were added. Weights were population census data for residential emissions, employment statistics for agricultural and industrial area emissions, livestock statistics for ammonia emissions and annual aircraft movements for emissions realized by air transport. Additional road and off-road network information was used to disaggregate emissions realized by traffic. A comparison of top down produced emission estimates with spatially resolved national emission data for The Netherlands and the United Kingdom gave confidence in the present spatial surrogates as a tool for the top down production of atmospheric emission maps. Explained variance at a spatial resolution of 5 km was >70% for CO, NMVOC and NO_x, >60% for PM10 and almost 50% for SO₂.     

Climate Response by the Ski Industry: The Shortcomings of Snowmaking for Australian Resorts

Skier numbers, and revenues for the multi-billion-dollar ski industry, are highly sensitive to snow cover. Previous research projected that under climate change, natural snow cover will become inadequate at 65% of sites in the Australian ski resorts by 2020. Resorts plan to compensate for reduced snowfall through additional snowmaking. For the six main resorts, however, this would require over 700 additional snow guns by 2020, requiring approximately US $100 million in capital investment, and 2,500-3,300 ML of water per month, as well as increased energy consumption. This is not practically feasible, especially as less water will be available. Therefore, low altitude ski resorts such as these may not be able to rely on snowmaking even for short-term adaptation to climate change. Instead, they are likely to seek conversion to summer activities and increased property development.     

Hydrological regime and salinity alter the bioavailability of Cu and Zn in wetlands

In the context of the European Water Framework Directive, controlled flooding of lowlands is considered as a potential water management strategy to minimise the risk of flooding of inhabited areas. However, due to historical pollution and overbank sedimentation, metal levels are elevated in most wetlands, which can cause adverse effects on the ecosystem's dynamics. Additionally, salinity affects the bioavailability of metals present or imported into these systems. The effect of different flooding regimes and salinity exposure scenarios (fresh- and brackish water conditions) on Cu and Zn accumulation in the oligochaete Tubifex tubifex (Müller, 1774) was examined. Metal mobility was closely linked to redox potential, which is directly related to the prevalent hydrological regime. Flooded, and thus more reduced, conditions minimized the availability of metals, while oxidation of the substrates during a drier period was associated with a rapid increase of metal availability and accumulation in the oligochaetes.     

Polyfluorinated compounds in the atmosphere along a cruise pathway from the Japan Sea to the Arctic Ocean

Neutral polyfluorinated alkyl substances (PFASs) were measured in high-volume air samples collected on board the research vessel Snow Dragon during the 4th Chinese National Arctic Expedition from the Japan Sea to the Arctic Ocean in 2010. Four volatile and semi-volatile PFASs (fluorotelomer alcohols (FTOHs), fluorotelomer acids (FTAs), perfluoroalkyl sulfonamides (FASAs), and sulfonamidoethanols (FASEs)) were analyzed respectively in the gas and particle phases. FTOHs were the dominant PFASs in the gas phase (61-358 pg m⁻³), followed by FTAs (5.2-47.9 pg m⁻³), FASEs (1.9-15.0 pg m⁻³), and FASAs (0.5-2.1 pg m⁻³). In the particle phase, the dominant PFAS class was FTOHs (1.0-9.9 pg m⁻³). The particle-associated fraction followed the general trend of FASEs > FASAs > FTOHs. Compared with other atmospheric PFAS measurements, the ranges of concentrations of ∑FTOH in this study were similar to those reported from Toronto, north America (urban), the northeast Atlantic Ocean, and northern Germany. Significant correlations between FASEs in the gas phase and ambient air temperature indicate that cold surfaces such as sea-ice, snowpack, and surface seawater influence atmospheric FASEs.     

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity.