Analysis and modelling of the pollutant emissions from European cars regarding the driving characteristics and test cycles

Within the European research project ARTEMIS, significant works have been conducted to analyse the hot emissions of pollutant from the passenger cars regarding the driving cycles and to propose modelling approaches taking into account large but heterogeneous datasets recorded in Europe. The review and analysis of a large range of test cycles enabled first the building-up of a set of contrasted cycles specifically designed for characterizing the influence of the driving conditions. These cycles were used for the measurement of the pollutants emission rates from nine passenger cars on a chassis dynamometer.Emissions measured on 30 vehicles tested on cycles adapted to their motorization (i.e., cycles for high- or low-powered cars, inducing thus a significant difference in the dynamic) were also considered for analysing the influence of the cycles and of the kinematic parameters on the hot emission rates of the regulated pollutants (CO, HC, NO_x, CO₂, PM). An analyses of variance demonstrated the preponderance of the driving type (urban, rural road, motorway), of the vehicle category (fuel, emission standard) and emitting status (high/normal emitter) and thus the pertinence of analysing and modelling separately the corresponding emissions. It also demonstrated that Urban driving led systematically to high diesel emission rates and to high CO₂, HC and NO_x emissions from petrol cars. Congested driving implied high CO₂ (diesel and petrol) and high diesel NO_x emission. On motorway, the very high speeds generated high CO₂, while unsteady speeds induced diesel NO_x and petrol CO over-emissions. A search for pertinent kinematic parameters showed that urban diesel emissions were mostly sensitive to stops and speed parameters, while petrol emissions were rather sensitive to acceleration parameters. On the motorway, diesel NO_x and CO₂ emissions rates increased with the speed variability and occurrence of high speeds, while CO₂ and CO over-emission from petrol cars were linked to the occurrence of strong acceleration at high speeds.A modelling approach based on partial least square regression was tested, which demonstrates its ability to discriminate satisfactorily the emissions according to dynamic related parameters and in particular when considering the two-dimensionnal distribution of instantaneous speed and acceleration.Finally, a strategy was proposed to analyse the large but heterogeneous set of hot emission data collected within the ARTEMIS project. The approach consisted in analysing the similarity of the numerous cycles as regards their kinematic, grouping them into reference test patterns through an automatic clustering, and then computing reference emissions for these patterns. These principles enabled the development of a method to compute the emissions at a low spatial scale, i.e. the so-called traffic situation approach, which was implemented in the European Artemis model for estimating the cars’ pollutant emissions.     

Expansion of Calamagrostis villosa in sub-alpine Nardus stricta grassland: Cessation of cutting management or high nitrogen deposition?

Calamagrostis villosa has recently expanded in Nardus stricta-dominated sub-alpine grassland of the Giant Mountains (Krkono?e/Karkonosze, the Czech Republic). To investigate whether this expansion has been promoted by high nitrogen deposition or by the cessation of agricultural management, grassland plots dominated by C. villosa were manipulated with four treatments: control (Con), fertilised (Fer), cut (Cut) and cut–fertilised (Cut–Fer). NH₄NO₃ was used at the rate of 30 kg N ha^?1 and fertilisation and cutting were performed once a year after data collection in late July between 2000 and 2006.Plant species composition (analysed by RDA) was significantly influenced by cutting but not by fertilisation. Cutting reduced the cover, biomass, sward height and tiller density of C. villosa. Seedlings of N. stricta and panicles of C. villosa were recorded only in plots with cutting management.To investigate the effect of treatments on the spread of C. villosa, grassland sods dominated by N. stricta were transplanted into the experimental plots. Six years later, the density and cover of C. villosa spreading into the N. stricta sods were highest in Fer treatment.C. villosa was recognised as a defoliation-sensitive species and this sensitivity cannot be overcome by an increase in N supply. Recent expansion of C. villosa in the sub-alpine grassland can by explained by a long-term succession after the cessation of agricultural management and an increase in the N availability in recent decades.     

Non-destructive quantification of water gradient in sludge composting with Magnetic Resonance Imaging

Sludge from a slaughter-house wastewater plant, and mixtures of bulking agent (crushed wood pallet) and sludge were studied by Nuclear Magnetic Resonance (NMR). The NMR spin–spin relaxation (T₂) and spin–lattice relaxation (T₁) signals for sludge, wet crushed wood pallet and mixtures of sludge and bulking agent were decomposed into three relaxation time components. Each relaxation time component was explained by a non-homogeneous water distribution on a microscopic length scale and by the porosity of the material. For all samples, the T₂ relaxation time value of each component was directly related to the dry matter content. The addition of wet crushed wood to sludge induced a decrease in the relaxation time, explained by water transfer between the sludge and the wood.Magnetic Resonance Imaging (MRI) and respirometric measurements were performed on sludge and wood mixtures. MR images of the mixtures were successfully obtained at different biodegradation states. Based on specific NMR measurements in an identified area located in the MRI cells, the results showed that grey levels of MR images reflected dry matter content. This preliminary study showed that MRI would be a powerful tool to measure water distribution in sludge and bulking agent mixtures and highlights the potential of this technique to increase the understanding of sludge composting.     

Degradation of toluene,xylene, and trimethylbenzene vapors by biofiltration: a comparison

This paper presents a comparative study of the biodegradation of three aromatic volatile compounds in a compost-based biofilter: toluene, xylene, and 1,2,4-trimethylbenzene, used in the course of this work for the first time in the field of biofiltration. Hence, three identical biofiltration units have been operated at the laboratory scale. During the experiments, nitrogen (as urea) was supplied at various concentrations to each reactor, via irrigated nutrient solutions. A comparative analysis of the results showed that the biodegradability scale followed the degree of substitution around the aromatic ring: toluene > xylene > trimethylbenzene, with 95, 80, and 70% maximum conversions, respectively. In addition, and despite the different removal levels achieved in the three bioreactors, it was established that from a reaction viewpoint, the degradation of the three compounds seemed to follow similar metabolic pathways involving methylcatechol isomers. Finally, by varying the nitrogen input concentrations in the three reactors, three degradation regimes have been highlighted: an N-limitation regime and an N-optimum regime, common to the three solvents, and an N-excess regime, favorable to the colonization of the filter beds by nitrifying species, which particularly affected the xylene and trimethylbenzene biodegradation.     

Modelling the influence of demographic parameters on group structure in social species with dispersal asymmetry and group fission

Female philopatry characterizes many mammal populations subdivided into social groups. Fission of these social groups is a relatively discrete event in the life of groups or of individuals, leading to the distribution of females among several newly formed groups. Fission is an important event because it can be a way for females to disperse. Group fissions have rarely been observed and their modalities generally remain poorly known, the best-documented species being primates. Most group fissions occur along lines of maternal relatedness, but the death of a matriarch may disrupt the cohesion within a matriline, inducing separation of sisters, accompanied by their descendants, when a group splits. Our model shows that the numbers and sizes of matrilines within groups depend on the precise demographic parameters and age structure of a population and not only on its rate of increase. For comparable population-growth periods, high survival rates of adult females induce an increase in the sizes of matrilines, whereas high survival rates of immature individuals induce an increase in the numbers of matrilines. Following fission, groups of a given size included, in the first case, only a few large matrilines, whereas in the second case, they consisted mainly of many small matrilines. The present study constitutes a preliminary stage, before modelling consequences of demographic structure of groups or populations on their genetic structure.     

Experimental study and modeling of the transfer of zinc in a low reactive sand column in the presence of acetate

Nowadays, it is necessary to understand and identify the reactions governing the fate of heavy metals introduced into the environment with low complexing organic compounds, particularly when they are transferred through soils in urban areas. In this work the concomitant influence of pH and acetate on the fate of zinc on siliceous sand was studied in batch and non-saturated column experiments. Total zinc concentrations varied between 2 and 20 mg/l, and total acetate concentrations were fixed at 22, 72, 132, and 223 mM to obtain solution pHs of 4, 5, 6 and 7, respectively. Natural sand (diameter, 0.3-2 mm), mainly constituted of silica, was used. In batch adsorption experiments, zinc adsorption is insignificant at pH 4, low and linear at pH 5, and increasingly nonlinear, of the Langmuir type, at pH 6 and 7 indicating near-saturation conditions of surface sites at these high pH values. In column experiments, Zn retardation increases and the maximum outlet concentration of Zn decreases with rising pH and acetate concentrations. Previous column tracer experiments revealed the occurrence of regionalized water transport in the column. Modeling these data was based on a non-electrostatic approach. Batch and column data modeling was based on the PHREEQC code that allows concomitant resolution of chemical speciation and regionalized water transport. The speciation calculation indicates that the ZnAcetate+ species is the dominant Zn species in the solutions used. Batch experimental curves are correctly modeled assuming the formation of the three surface species triple bond SiOZn+, triple bond SiOH-Zn Acetate+ and triple bond SiO-Zn(Acetate)2-. The column data could be adequately modeled assuming a two-region water transport and the formation of the same three species with the same thermodynamic constants determined in the batch experiments. The hypothesis of the modeling leads to a slight overestimation of the quantities of zinc eluted (10%) at pH 6 and 7, mostly in the desorption phase. These results show that the methodology used facilitates the correct modeling of both batch and transport experiments and formulation of the hypothesis on the interactions between the low reactive sand and a complex solution.     

Chemical egg defense in Photuris firefly “femmes fatales”

Summary. Female Photuris fireflies contain defensive chemicals of two types. They sequester steroidal pyrones (lucibufagins) from male fireflies of the genus Photinus that they eat, and themselves produce the defensive betaine N-methylquinolinium 2-carboxylate. Chemical analyses of Photuris eggs showed that females that fed on Photinus males endow their eggs with both lucibufagin and the betaine, while those that did not feed on Photinus lay eggs that contain betaine, but virtually no lucibufagin. Photuris females collected in the field during the Photinus flight season laid eggs that invariably contained betaine, but lucibufagin only at times. Predation experiments showed that Photuris eggs are essentially unacceptable to larvae of a coccinellid beetle (Harmonia axyridis) and an ant (Leptothorax longispinosus), but moderately acceptable to an earwig (Forficula auricularia). When applied experimentally to palatable insect eggs, lucibufagin proved deterrent to these three predators, while the betaine proved deterrent to the ant and coccinellid larva only. Both types of defensive compound decreased egg predation in the field. By endowing their eggs with both exogenous and endogenous chemicals, Photuris females are essentially “maximizing their options”– when feeding on Photinus, their eggs are doubly protected, but they are not entirely defenseless when the females are unable to procure lucibufagin. Received 12 August 1999; accepted 27 August 1999     

A case study of molinate application in a Portuguese rice field: herbicide dissipation and proposal of a clean-up methodology

This study was designed to monitor molinate losses in surface and underground waters during Ordram application in a rice field situated in central Portugal. Water samples were collected from different sites, before, during and about one month and a half after Ordram application. Molinate quantification was based on a solid-phase microextraction (SPME) method followed by gas chromatography with flame photometric detector (GC-FPD) analysis, and led to the conclusion that the herbicide was dissipated in the environment, reaching levels as high as 3.9 microgl(-1) in underground water and 15.8 microgl(-1) in the river receiving tail waters. The feasibility of the application of treatment methodologies based on adsorption or biodegradation as processes to remove molinate from real-world waters was assessed. These methods seem suitable to reduce molinate concentrations to values in the range of the legally recommended limits (<0.5 microgl(-1)).