Kinetics of the tropospheric formaldehyde loss onto mineral dust and urban surfaces

The kinetics of the heterogeneous reaction between gaseous HCHO and TiO₂/SiO₂ mineral coatings were investigated using a coated-wall flow tube to mimic HCHO loss on mineral aerosol and TiO₂ coated depolluting urban surfaces. The measured uptake kinetics were strongly enhanced when the flow tube was irradiated with 340–420 nm UV light with an irradiance of 1.45 mW cm^?2. The associated BET uptake coefficients ranged from (3.00 ± 0.45) × 10^?9 to (2.26 ± 0.34) × 10^?6 and were strongly dependent on HCHO initial concentration, relative humidity, temperature, and TiO₂ content in the mineral coating, which ranged from 3.5 to 32.5 ppbv, 6–70%, 278–303 K, and 1–100 %wt, respectively. The measured kinetics were well described using a Langmuir–Hinshelwood type formalism. The estimated uptake coefficients were used to discuss the importance of heterogeneous HCHO surface loss, in terms of deposition lifetimes, as compared to major homogeneous gas-phase losses such as OH reaction and photolysis. It is found that deposition may compete with gas-phase removal of HCHO in a dense urban environment if more than 10% of the urban surface is covered with TiO₂ treated material.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

Impact of dry deposition of semi-volatile organic compounds on secondary organic aerosols

Dry deposition of semi-volatile organic compounds (SVOC) is not currently treated in most chemical transport models of air quality and this omission has been identified as a possible major source of uncertainty. The effect of dry deposition of SVOC on the concentration of secondary organic aerosols (SOA) is investigated in summertime with the chemical transport model CHIMERE that simulates SOA concentrations by means of molecular SOA surrogate species. Omitting dry deposition could overestimate SOA concentrations by as much as 50%. This overestimation is larger during nighttime due to higher relative humidity.     

Air pollution characteristics associated with mesoscale atmospheric patterns in northwest continental Europe

An impact related daily air quality index (DAQx), calculated for 15 air quality monitoring stations (traffic, background, and industry) in Belgium, France, Germany and Luxembourg, was compared to mesoscale atmospheric patterns between 2001 and 2007. Meteorological conditions were described by the Hess and Brezowsky synoptic weather classification system and gridded data of the EU FP6 ENSEMBLES project of total precipitation and mean surface temperature. DAQx values indicate sufficient to poor air quality in the urban area of Brussels and at urban traffic stations, as well as satisfactory air quality at the background stations. The air quality index refers to more than 90% to the presence of high PM₁₀, O₃ and NO₂ concentrations. SO₂ and CO play only a minor role. The investigation of weather regimes indicates that zonal and mixed cyclonic circulation regimes are associated with better air quality than meridional and anticyclonic weather regimes. In general, weather regimes with high daily precipitation lead to better air quality than dryer air masses because of lower contribution of PM₁₀ to the air quality index. A trend analysis of weather regimes from 1978 to 2007 shows significant (α = 0.05) positive trends for weather classes associated with lower PM₁₀ concentrations. The results of a case study at a German station examining the relationship between PM₁₀ concentrations and local meteorological quantities (wind speed and precipitation) confirm the results of the regional analysis.     

Forest plantations, water availability, and regional climate change: controversies surrounding Acacia mearnsii plantations in the upper Palnis Hills, southern India

Plantation forests not only impact carbon and water cycles, but also affect biodiversity, livelihoods, and shape regional economies. Each of these impacts differs across varying scales of analysis. This paper illustrates how forest, climate change and hydrology debates play out in the context of the forest plantations of Australian black wattle (Acacia mearnsii) in the upper Palni hills of southern India. We outline the contradictory perspectives of different local groups regarding the impact of plantations on catchment hydrology and water availability, and examine these in relation to changes in the regional economy and rainfall patterns. Our analysis indicates that changes in these two factors have played a more significant role than existing wattle plantations in affecting local and regional water availability. We suggest that ongoing debates regarding forest plantation–hydrology–climate change relationships need to broaden their scope to include changes in regional rainfall patterns and shifts in regional economic activity. This approach is likely to provide a more realistic assessment of plantation forests in a dynamic regional context, and offer more resilient strategies for regional landscape and catchment management under conditions of high variability in rainfall patterns.     

Integrated methodology for assessing the HCH groundwater pollution at the multi-source contaminated mega-site Bitterfeld/Wolfen

A large-scale groundwater contamination characterises the Pleistocene groundwater system of the former industrial and abandoned mining region Bitterfeld/Wolfen, Eastern Germany. For more than a century, local chemical production and extensive lignite mining caused a complex contaminant release from local production areas and related dump sites. Today, organic pollutants (mainly organochlorines) are present in all compartments of the environment at high concentration levels. An integrated methodology for characterising the current situation of pollution as well as the future fate development of hazardous substances is highly required to decide on further management and remediation strategies. Data analyses have been performed on regional groundwater monitoring data from about 10 years, containing approximately 3,500 samples, and up to 180 individual organic parameters from almost 250 observation wells. Run-off measurements as well as water samples were taken biweekly from local creeks during a period of 18 months. A kriging interpolation procedure was applied on groundwater analytics to generate continuous distribution patterns of the nodal contaminant samples. High-resolution geological 3-D modelling serves as a database for a regional 3-D groundwater flow model. Simulation results support the future fate assessment of contaminants. A first conceptual model of the contamination has been developed to characterise the contamination in regional surface waters and groundwater. A reliable explanation of the variant hexachlorocyclohexane (HCH) occurrence within the two local aquifer systems has been derived from the regionalised distribution patterns. Simulation results from groundwater flow modelling provide a better understanding of the future pollutant migration paths and support the overall site characterisation. The presented case study indicates that an integrated assessment of large-scale groundwater contaminations often needs more data than only from local groundwater monitoring. The developed methodology is appropriate to assess POP-contaminated mega-sites including, e.g. HCH deposits. Although HCH isomers are relevant groundwater pollutants at this site, further organochlorine pollutants are present at considerably higher levels. The study demonstrates that an effective evaluation of the current situation of contamination as well as of the related future fate development requires detailed information of the entire observed system.     

Toxicity of hydroquinone to different freshwater phototrophs is influenced by time of exposure and pH

The interaction of natural organic matter with phytoplankton communities in freshwater ecosystems is an intensively studied subject matter. Previous studies showed that apparently plant-derived phenols were able to inhibit algal and cyanobacterial growth. Furthermore, it was also assumed that humic substances (HS), which comprise the major part of dissolved organic carbon in freshwater ecosystems, directly interact with freshwater phototrophs. For example, quinoid building blocks of HS were thought to be algicidal. To identify key environmental variable for the toxic action of potential quinone algicides, we tested the toxicity of hydroquinone (HQ) to different eukaryotic and prokaryotic freshwater phototrophs in terms of growth performance and investigated also the effect of HQ oxidation at different pH values on its algicidal potential. It was shown that cyanobacterial species were much more susceptible to hydroquinone than coccal green algal species were, with Microcystis aeruginosa being the most sensitive species by far. In addition, it was obvious that the aging of hydroquinone-stock solution at pH 11 led to polymerization and, by this process, to a total loss of toxicity; whereas the algicidal potential sustained if the polyphenol was kept at pH 7. Since most lakes with heavy blooms of phototrophs possess pH values clearly above 7.0, it is questionable, if polyphenols in general and quinones in particular are the effective chemicals and if litter and straw leachates are applied as means to combat algal and cyanobacterial blooms.     

Trends of perfluorochemicals in Greenland ringed seals and polar bears: Indications of shifts to decreasing trends

Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.     

Distribution of antidepressants and their metabolites in brook trout exposed to municipal wastewaters before and after ozone treatment--evidence of biological effects

This study examined the tissues distribution of selected serotonin reuptake inhibitors (SSRIs) in brook trout exposed for 3 months to continuous flow-through primary-treated effluent before and after ozone treatment. A reliable analytical method was developed for the quantification of trace amounts of antidepressants in small tissue homogenate extracts. Levels of six antidepressants and four of their N-desmethyl metabolites were determined using liquid chromatography-tandem mass spectrometry. Significant amounts of the SSRIs were found in fish tissue-in decreasing order: liver>brain>muscle. Sertraline and its metabolite desmethylsertraline were the predominant substances observed in most tissues (0.04-10.3 ng g(-1)). However, less SSRIs (0.08-1.17 ng g(-1)) were bioaccumulated in the ozonated effluent. The early molecular effects of these SSRIs on the Na/K-dependent ATPase pump activity in brain synaptosomes where also investigated in vitro and in fish exposed to the municipal effluents. With respect to their potential biological effects, in vitro exposure to selected SSRIs induced a reduction of the brain Na/K-ATPase activity in synaptosomes in a dose-dependent manner. Results showed that Na/K-ATPase activity was readily inhibited by exposure to municipal effluent before and, to a lesser extent, after ozone treatment. Moreover, the Na/K-ATPase activity was significantly and negatively correlated with brain tissue concentrations of fluoxetine (r=-0.57; p<0.03), desmethylsertraline (r=-0.84; p<0.001), and sertraline (r=-0.82; p<0.001). The present study reveals that SSRIs are readily available in fish, biologically active and corroborates previous findings on the serotonergic properties of municipal effluents to aquatic organisms.     

Quantification of nitrate leaching from German forest ecosystems by use of a process oriented biogeochemical model

Simulations with the process oriented Forest-DNDC model showed reasonable to good agreement with observations of soil water contents of different soil layers, annual amounts of seepage water and approximated rates of nitrate leaching at 79 sites across Germany. Following site evaluation, Forest-DNDC was coupled to a GIS to assess nitrate leaching from German forest ecosystems for the year 2000. At national scale leaching rates varied in a range of 0–>80 kg NO₃–N ha⁻¹ yr⁻¹ (mean 5.5 kg NO₃–N ha⁻¹ yr⁻¹). A comparison of regional simulations with the results of a nitrate inventory study for Bavaria showed that measured and simulated percentages for different nitrate leaching classes (0–5 kg N ha⁻¹ yr⁻¹:66% vs. 74%, 5–15 kg N ha⁻¹ yr⁻¹:20% vs. 20%, >15 kg N ha⁻¹ yr⁻¹:14% vs. 6%) were in good agreement. Mean nitrate concentrations in seepage water ranged between 0 and 23 mg NO₃–N l⁻¹.