Impact of a NO₂-regenerated diesel particulate filter on PAH and NPAH emissions from an EURO IV heavy duty engine

In this study the emissions of polycyclic aromatic hydrocarbons (PAH) and their nitro-derivates (NPAH) from a modern heavy duty engine were analysed. Focus was on the effects of the aftertreatment system. It consisted of an oxidation catalyst coupled to a diesel particulate filter (DPF). In such systems the process of PAH and NPAH degradation may compete with the NPAH formation. Scope of the study was to explain to which extent modern DPF could support the formation of highly mutagenic NPAH by nitration of pre-existing PAH. It was found that the diesel trap reduced the total amount of PAH and NPAH emitted both at low load and high load. Nevertheless, at low load the lower temperatures and the higher NO(2) concentration furnished better conditions for PAH nitration while they were more adverse to NPAH degradation. These effects were NPAH-specific. For these reasons, some NPAH like 3-nitrophenanthrene were still efficiently degraded but others were newly formed. For instance emissions of the highly toxic 1-benzo(a)pyrene and 6-nitrobenzo(a)pyrene where increased by a factor 15 at low load and, even if in lower amount, were formed also at high load. The super-mutagen 1,6-dinitropyrene, which was not present in raw exhaust, could be found only after the DPF, indicating a new formation. In regard to emissions from the active regeneration mode, tremendous high emissions of 1-nitropyrene were reported. More accurate investigation of such a regeneration mode would be of great interest for the future.     

Nitro-PAH formation studied by interacting artificially PAH-coated soot aerosol with NO2 in the temperature range of 295–523 K

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO₂.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO₂ and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO₂ concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m^?1). Resulting 1-NPYR formation rate increased exponentially with [NO₂]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO₂] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat^®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.     

Bioavailability, ecotoxicity, and geological characteristics of trace lead in sediments from two sites on Negro River, Uruguay, South America

Bioassays of two sites along the Rio Negro in Uruguay indicate ecotoxicity, which could be attributable to trace concentrations of lead in river sediments. Monthly samples at two sites at Baygorria and Bonete locations were analyzed for both particle size and lead. Lead was determined by atomic spectrometry in river water and sediment and particle size by sieving and sedimentation. Data showed that Baygorria's sediments have greater percentage of clay than Bonete's (20.4 and 5.8%, respectively). Lead was measurable in Baygorria's sediments, meanwhile in Bonete's, it was always below the detection limit. In water samples, lead was below detection limit at both sites. Bioassays using sub-lethal growth and survival test with Hyalella curvispina amphipod, screening with bioluminescent bacteria Photobacterium leiognathi, and acute toxicity bioassay with Pimephales promelas fish indicated toxicity at Baygorria, with much less effect at Bonete. Even though no lethal effects could be demonstrated, higher sub-lethal toxicity was found in samples from Baygorria site, showing a possible concentration of the contaminant in the clay fraction.     

Comparing Landslide Maps: A Case Study in the Upper Tiber River Basin, Central Italy

/ The preparation of landslide maps is an important step in any landslide hazard assessment. Landslides maps are prepared around the world, but little effort is made to assess their reliability, outline their main characteristics, and pinpoint their limitations. In order to redress this imbalance, the results of a long-term research project in the Upper Tiber River basin in central Italy are used to compare reconnaissance and detailed landslide inventory maps, statistical and geomorphologically based density maps, and landslide hazard maps obtained by multivariate statistical modeling. An attempt is made to discuss advantages and limitations of the available maps, outlining possible applications for decision-makers, land developers, and environmental and civil defence agencies. The Tiber experiment has confirmed that landslides can be cost-effectively mapped by interpreting aerial photographs coupled with field surveys and that errors and uncertainties associated with the inventory can be quantified. The experiment has shown that GIS makes it easy to prepare landslide density maps and facilitates the production of statistically based landslide hazard models. The former supply an overview of the distribution of landslides that is easily comprehended but do not provide insight on the causes of instability. The latter, giving insight into the causes of instability, are diagnostically powerful, but are difficult to prepare and exploit.     

Fluxes of oxidised and reduced nitrogen above a mixed coniferous forest exposed to various nitrogen emission sources

Concentrations of nitrogen gases (NH(3), NO(2), NO, HONO and HNO(3)) and particles (pNH(4) and pNO(3)) were measured over a mixed coniferous forest impacted by high nitrogen loads. Nitrogen dioxide (NO(2)) represented the main nitrogen form, followed by nitric oxide (NO) and ammonia (NH(3)). A combination of gradient method (NH(3) and NO(x)) and resistance modelling techniques (HNO(3), HONO, pNH(4) and pNO(3)) was used to calculate dry deposition of nitrogen compounds. Net flux of NH(3) amounted to -64 ng N m(-2) s(-1) over the measuring period. Net fluxes of NO(x) were upward (8.5 ng N m(-2) s(-1)) with highest emission in the morning. Fluxes of other gases or aerosols substantially contributed to dry deposition. Total nitrogen deposition was estimated at -48 kg N ha(-1) yr(-1) and consisted for almost 80% of NH(x). Comparison of throughfall nitrogen with total deposition suggested substantial uptake of reduced N (+/-15 kg N ha(-1) yr(-1)) within the canopy.