Evaluating urban PM10 pollution benefit induced by street cleaning activities

Despite their burden in urban particulate air pollution, road traffic non-exhaust emissions are often uncontrolled and information about the effectiveness of mitigation measures on paved roads is still scarce. The present study is aimed to evaluate the effectiveness of mechanical sweeping/water flushing treatments in mitigating urban road dust resuspension and to quantify the real benefit in terms of ambient PM₁₀ concentrations. To this aim a specific campaign was carried out in a heavily trafficked central road of Barcelona (Spain), a Mediterranean city suffering from a traffic-related pollution, both for a high car density and a frequent lack of precipitation. Several street washings were performed by means of mechanical sweepers and pressure water during night in all traffic lanes and sidewalks. PM₁₀ levels were simultaneously compared with four reference urban background air quality stations to interpret any meteorological variability. At the downwind measurement site, PM₁₀ concentrations registered a mean daily decrease of 8.8 μg m^?3 during the 24 h after street washing treatments. However 3.7–4.9 μg m^?3 of such decrease were due to the meteorological variability detected at the upwind site, as well as at two of the reference sites. This reveals that an effective decrease of 4–5 μg m^?3 (7–10%) can be related to street washing efficiency. Mitigation of road dust resuspension was confirmed by investigating the chemical composition of airborne-PM₁₀ filters. Concentrations of Cu, Sb, Fe and mineral matter decrease significantly with respect to concentrations of elemental carbon, used as tracer for exhaust diesel emissions. High efficiency of street washing in reducing road dust loads was found by performing periodic samplings both on the treated and the untreated areas.     

Physicochemical variations in atmospheric aerosols recorded at sea onboard the Atlantic–Mediterranean 2008 Scholar Ship cruise (Part I): Particle mass concentrations,size ratios,and main chemical components

We report on ambient atmospheric aerosols present at sea during the Atlantic–Mediterranean voyage of Oceanic II (The Scholar Ship) in spring 2008. A record was obtained of hourly PM₁₀, PM_2.5, and PM₁ particle size fraction concentrations and 24-h filter samples for chemical analysis which allowed for comparison between levels of crustal particles, sea spray, total carbon, and secondary inorganic aerosols. On-board monitoring was continuous from the equatorial Atlantic to the Straits of Gibraltar, across the Mediterranean to Istanbul, and back via Lisbon to the English Channel. Initially clean air in the open Atlantic registered PM₁₀ levels <10 μg m^?3 but became progressively polluted by increasingly coarse PM as the ship approached land. Away from major port cities, the main sources of atmospheric contamination identified were dust intrusions from North Africa (NAF), smoke plumes from biomass burning in sub-Saharan Africa and Russia, industrial sulphate clouds and other regional pollution sources transported from Europe, sea spray during rough seas, and plumes emanating from islands. Under dry NAF intrusions PM₁₀ daily mean levels averaged 40–60 μg m^?3 (30–40 μg m^?3 PM_2.5; c. 20 μg m^?3 PM₁), peaking briefly to >120 μg m^?3 (hourly mean) when the ship passed through curtains of higher dust concentrations amassed at the frontal edge of the dust cloud. PM₁/PM₁₀ ratios ranged from very low during desert dust intrusions (0.3–0.4) to very high during anthropogenic pollution plume events (0.8–1).     

Ecotoxicity and fungal deterioration of recycled polypropylene/wood composites: Effect of wood content and coupling

Recycled polypropylene (rPP) was recovered from an industrial shredder and composites were prepared with a relatively wide range of wood content and with two coupling agents, a maleated PP (MAPP) and a maleated ethylene-propylene-diene elastomer (MAEPDM). The mechanical properties of the composites showed that the coupling agents change structure only slightly, but interfacial adhesion quite drastically. The durability of the materials was determined by exposing them to a range of fungi and, ecotoxicity was studied on the aquatic organism Vibrio fischeri. The composites generally exhibit low acute toxicity, with values below the levels considered to have direct ecotoxic effect on aquatic ecosystems (<2 toxic units). Their toxicity to V. fischeri depended on the presence of the coupling agents with larger E₅₀ values in 24-h aqueous extracts from composites containing MAPP or MAEPDM in comparison to composites without any coupling agent. Evaluation of resistance against fungal colonization and deterioration proved that wood facilitates fungal colonization. Fungi caused slight mass loss (below 3%) but it was not correlated with substantial deterioration in material properties. MAPP seems to be beneficial in the retention of mechanical properties during fungal attack. rPP/wood composites can be considered non-ecotoxic and quite durable, but the influence of wood content on resistance to fungal attack must be taken into account for materials intended for applications requiring long-term outdoor exposure.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Effect of inoculation in composting processes: modifications in lignocellulosic fraction

Three microbial isolates, identified as Bacillus shackletonni, Streptomyces thermovulgaris and Ureibacillus thermosphaericus were tested as inoculants in composting processes in relation to their capacity to improve lignocellulose degradation. Different wastes from agricultural activities were used as raw material for the heaps: pepper plant waste (PPW) as the main component and olive-oil mill waste (OMW), almond shell (AS), pruning waste (PW) and rice straw (RS) as additives. Cellulose was more extensively degraded than hemicellulose and lignin, although the use of inoculants (B. shackletonni and S. thermovulgaris) improved the action of the autochthonous microbiota just in the AS heaps. A higher efficiency was observed for lignin, since lower concentrations of this polymer were detected in the inoculated heaps in relation to control heaps. U. thermosphaericus was the most efficient microorganism since inoculation with this strain decreased the final lignin content in a range between 17.23% and 24.34%. S. thermovulgaris and B. shackletonni led to a higher reduction of the lignin levels in the OMW and PW heaps (14.25% and 19.07% less lignin than control heaps) and OMW (13%), respectively. The composting process can therefore be improved by means of inoculation if the microorganisms used for this purpose are appropriate for the characteristics of the raw material.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Cadmium, zinc and copper accumulation in the squid Illex argentinus from the Southwest Atlantic Ocean

 The levels and burdens of Cd, Zn, Cu and Hg were measured in the dorsal mantle, digestive gland and gonads of the squid Illex argentinus, from the Southwest Atlantic Ocean. Mature and immature individuals of both sexes were analysed. Correlations of heavy metal concentrations and burdens with sex and food habits were studied. The highest metal levels were found, particularly for Cd, in the digestive gland, which attained a concentration of up to 270 μg g⁻¹ (wet weight). Dorsal mantle and gonads exhibited the same order of metal enrichment: Zn>Cu>Cd. Zinc and Cu levels were higher in ovaries than in testes and varied with the stage of maturation. The dorsal mantle exhibited the lowest heavy metal concentrations. Mercury levels were below the detection limit of the method in all the tissues analysed. Received: 7 September 1999 / Accepted: 9 March 2000     

Modification in the soil and traffic-related sources of particle matter between 1998 and 2007 in Santiago de Chile

Santiago de Chile is one of the most polluted South American cities, concentrating its pollution episodes during winter. Daily PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) concentrations over 80 microg/m3 have been reached frequently since 1998. Despite several regulations introduced over the past 20 yr to improve the air quality, PM concentration levels remain high. In this work, sampling in downtown Santiago was conducted from April 1998 to August 2007 for PM2.5 and from October 2003 to March 2006 for PM10-2.5 (PM between 2.5 and 10 microm in aerodynamic diameter) with dichotomous samplers. Elemental analysis was performed on the samples with X-ray fluorescence. The resuming series of 859 samples and 216 elements identified were divided into semiannual periods and analyzed with factor analysis. Five factors are clearly discerned: soil, motor vehicles, residual oil, marine aerosols, and secondary sulfates. The soil factor in the fine fraction shows a clear increase from 2002 to 2006, whereas the coarse fraction of this factor shows a stable trend. The most probable cause for this trend is the growth in the number of vehicles in Santiago (6.5%/yr), which increases the resuspension of particles from the ground. Another cause for the increase is the growth in the construction activity (4.2%/yr). The motor vehicle factor in the fine fraction shows a decrease between 1998 and 2006. The decrease in the apportionment of this factor can be explained by the improvement in the vehicle fleet. In Santiago, the number of noncatalytic vehicles has been reduced from 389,000 in 2001 to 275,000 in 2006. The residual oil factor also shows a decrease between 1998 and 2006. The decrease could be attributed to the adoption of cleaner technologies and norms regarding gasoline and diesels.     

Integration of techniques for early fault detection and diagnosis for improving process safety: Application to a Fluid Catalytic Cracking refinery process

In this paper we show the integration of techniques for early fault detection and diagnosis of operational faults in industrial processes, and we show an application example in a Fluid Catalytic Cracking refinery process. The early fault detection and diagnosis allow the operators in an industrial process to take the best actions during the real state of the process, avoiding incipient faults to scale to critical situations where there is risk of human lives and economical lost.