Implementation of Portable Emissions Measurement Systems (PEMS) for the Real-driving Emissions (RDE) Regulation in Europe

Vehicles are tested in controlled and relatively narrow laboratory conditions to determine their official emission values and reference fuel consumption. ...

Joint Research Centre

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of uranium and other trace elements at selected Kosovo sites. The results suggested that the use of depleted uranium (DU) ammunitions in Kosovo did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic (235)U/(238)U measurements did not indicate the presence of DU particles in lichens. The present results also provided no indication of intense environmental contamination by the other trace elements analyzed, with the exception of Kosovska Mitrovica, where a diffuse environmental contamination by several heavy elements such as Pb, Zn, As and Cd was found.

Environmental distribution of uranium and other trace elements at selected Kosovo sites.

A depleted-uranium penetrator, shot in 1999 at Djakovica, Western Kosovo, and there collected in June 2001, shows evident alteration processes, perceivable as black and yellow coatings. XRD indicates that the black coating mostly consists of uraninite, UO2, with possible presence of other more oxidized uranium forms, such as U3O8. The yellow material is mostly amorphous, with variable weak diffraction lines, due to minor embedded uraninite grains, or possibly to schoepite, UO3 x 2H2O. SEM-EDS reveals only uranium. Whereas uraninite does not show any crystal shape, the yellow material recrystallizes to flattened pseudo-hexagonal prisms, approximately 2-10 microm wide and 1-4 microm long. Raman spectra of the yellow material have peaks at 3474 and 3222 cm(-1), indicative for OH groups, plus at 812 and 744 cm(-1), indicative for UO2(2+) uranyl ions. Based on the different data, the yellow material covering the depleted-uranium dart is an oxidized corrosion product, containing uranyl ions and hydroxyls and/or water molecules, akin to schoepite. Therefore, the Djakovica dart shows evident oxidation and leaching processes, progressively releasing mobile uranium forms. As uranium will be progressively dispersed far from the impact sites, at a rate controlled by the presence of effective fixing mechanisms, we feel necessary to maintain long term geochemical control of water pollution within the battlefield surroundings.

Chemical and mineralogical transformations caused by weathering in anti-tank DU penetrators ("the silver bullets") discharged during the Kosovo war.

The Colline Metallifere in SW Tuscany are characterized by strong anomalies in arsenic concentrations and distribution. The area is sparsely populated and largely wild, though it has been subject to human impact due to mining and metal processing since Etruscan and Roman times. In the Middle Ages it was exploited intensively for silver and copper. Until 1995, pyrite (FeS2) was mined and roasted to produce sulphuric acid and iron. Hypotheses based on geological and mineralogical factors formulated in the last 20 years have failed to explain the peculiar distribution of arsenic in the Colline Metallifere. Here we report preliminary results of widespread sampling and analysis of the fluvial sediments of rivers originating in this mining area. The data was analysed in relation to the archaeological features of the area, since the presence of ancient mining and ore processing sites can shed light on the peculiar distribution of arsenic. Comparison of data from two rivers and their respective contaminated and uncontaminated coastal lagoons also clarified the general mechanisms of arsenic mobility, pinpointing the source of arsenic contamination. The study methods also promise to be useful for discovering unknown archaeological sites.

Origin of arsenic pollution in Southwest Tuscany: comparison of fluvial sediments.

To assess the quality of the environment in southern Iraq after the Gulf War II, a geochemical survey was carried out. The survey provided data on the chemistry of Euphrates waters, as well as the trace element contents, U and Pb isotopic composition, and PAH levels in soil and tree bark samples. The trace element concentrations and the (235)U/(238)U ratio values in the Euphrates waters were within the usual natural range, except for the high contents of Sr due to a widespread presence of gypsum in soils of this area. The trace element contents in soils agreed with the common geochemistry of soils from floodplain sediments. Some exceptions were the high contents of Co, Cr and Ni, which had a natural origin related to ophiolitic outcrops in the upper sector of the Euphrates basin. The high concentrations of S and Sr were linked to the abundance of gypsum in soils. A marked geochemical homogeneity of soil samples was suggested by the similar distribution pattern of rare earth elements, while the (235)U/(238)U ratio was also fairly homogeneous and within the natural range. The chemistry of the tree bark samples closely reflected that of the soils, with some notable exceptions. Unlike the soils, some tree bark samples had anomalous values of the (235)U/(238)U ratio due to mixing of depleted uranium (DU) with the natural uranium pool. Moreover, the distribution of some trace elements (such as REEs, Th and Zr) and the isotopic composition of Pb in barks clearly differed from those of the nearby soils. The overall results suggested that significant external inputs occurred implying that once formed the DU-enriched particles could travel over long distances. The polycyclic aromatic hydrocarbon concentrations in tree bark samples showed that phenanthrene, fluoranthene and pyrene were the most abundant components, indicating an important role of automotive traffic.

Trace element distribution and 235U/238U ratios in Euphrates waters and in soils and tree barks of Dhi Qar province (southern Iraq).

Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100-1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H(2)SO(4)-H(2)O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation.

Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere. It is thought that amines may enhance nucleation, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid-amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid-dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere.

Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

Highly oxidised organic vapors can effectively stabilize sulphuric acid in heteronuclear clusters and drive new-particle formation. We present quantum chemical calculations of cluster stability, showing that multifunctional species can stabilize sulphuric acid and also present additional polar functional groups for subsequent cluster growth. We also model the multi-generation oxidation of vapors associated with secondary organic aerosol formation using a two-dimensional volatility basis set. The steady-state saturation ratios and absolute concentrations of extremely low volatility products are sufficient to drive new-particle formation with sulphuric acid at atmospherically relevant rates.

How do organic vapors contribute to new-particle formation?

Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.

Neutral molecular cluster formation of sulfuric acid-dimethylamine observed in real time under atmospheric conditions.

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.

The effect of acid-base clustering and ions on the growth of atmospheric nano-particles.

Fundamental questions remain about the origin of newly formed atmospheric aerosol particles because data from laboratory measurements have been insufficient to build global models. In contrast, gas-phase chemistry models have been based on laboratory kinetics measurements for decades. Here we build a global model of aerosol formation using extensive laboratory-measured nucleation rates involving sulfuric acid, ammonia, ions and organic compounds. The simulations and a comparison with atmospheric observations show that nearly all nucleation throughout the present-day atmosphere involves ammonia or biogenic organic compounds in addition to sulfuric acid. A significant fraction of nucleation involves ions, but the relatively weak dependence on ion concentrations indicates that for the processes studied variations in cosmic ray intensity do not significantly affect climate via nucleation in the present-day atmosphere.

Francesco Riccobono

Sustainable Transport Unit,
Institute for Energy,
Transport and Climate,
Sustainable Transport Unit, Institute for Energy, Transport and Climate

Joint Research Centre

Implementation of Portable Emissions Measurement Systems (PEMS) for the Real-driving Emissions (RDE) Regulation in Europe

Francesco Riccobono

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Sustainable Transport Unit,Institute for Energy,Transport and Climate,Sustainable Transport Unit, Institute for Energy, Transport and Climate

Joint Research Centre

Implementation of Portable Emissions Measurement Systems (PEMS) for the Real-driving Emissions (RDE) Regulation in Europe

Sustainable Transport Unit,
Institute for Energy,
Transport and Climate,
Sustainable Transport Unit, Institute for Energy, Transport and Climate