Chemical characterisation of particulate matter in urban transport modes

Traffic is a main source of air pollutants in urban areas and consequently daily peak exposures tend to occur during commuting. Personal exposure to particulate matter (PM) was monitored while cycling and travelling by bus, car and metro along an assigned route in Lisbon (Portugal), focusing on PM2.5 and PM10 (PM with aerodynamic diameter <2.5 and 10 µm, respectively) mass concentrations and their chemical composition. In vehicles, the indoor-outdoor interplay was also evaluated. The PM2.5 mean concentrations were 28?±?5, 31?±?9, 34?±?9 and 38?±?21?µg/m³ for bus, bicycle, car and metro modes, respectively. Black carbon concentrations when travelling by car were 1.4 to 2.0 times higher than in the other transport modes due to the closer proximity to exhaust emissions. There are marked differences in PM chemical composition depending on transport mode. In particular, Fe was the most abundant component of metro PM, derived from abrasion of rail-wheel-brake interfaces. Enhanced concentrations of Zn and Cu in cars and buses were related with brake and tyre wear particles, which can penetrate into the vehicles. In the motorised transport modes, Fe, Zn, Cu, Ni and K were correlated, evidencing their common traffic-related source. On average, the highest inhaled dose of PM2.5 was observed while cycling (55 µg), and the lowest in car travels (17 µg). Cyclists inhaled higher doses of PM2.5 due to both higher inhalation rates and longer journey times, with a clear enrichment in mineral elements. The presented results evidence the importance of considering the transport mode in exposure assessment studies.     

Ecotoxicological evaluation of the short term effects of fresh and stabilized textile sludges before application in forest soil restoration

The short term (eco)toxicity potential of fresh and stabilized textile sludges, as well as the short term (eco)toxicity of leachates obtained from both fresh and stabilized textile sludges, was evaluated by a battery of toxicity tests carried out with bacteria, algae, daphnids, fish, earthworms, and higher plants. The (eco)toxicological results showed that, after 120 d of stabilization, the experimental loading ratio of 25% sludge:75% soil (v/v) (equivalent to 64.4 ton/ha) did not significantly increase toxicity effects and increased significantly the biomass yield for earthworms and higher plants. The rank of biological sensitivity endpoints was: Algae approximately Plant biomass > Plant germination approximately Daphnids > Bacteria approximately Fish > Annelids. The lack of short term toxicity effects and the stimulant effect observed with higher plants and earthworms are good indications of the fertilizer/conditioner potential of this industrial waste, which after stabilization can be used in the restoration of a non-productive forest soil.     

Quantification of biotransformation of chlorinated hydrocarbons in a biostimulation study: added value via stable carbon isotope analysis

Stable carbon isotope analysis of chlorinated aliphatic compounds was performed at an in situ biostimulation pilot test area (PTA) at a site where 1,2-dichloroethane (1,2-DCA) and trichloroethene (TCE) were present in groundwater. Chlorinated products of TCE reductive dechlorination (cis-dichloroethene (cDCE) and vinyl chloride (VC)) were present at concentrations of 17.5 to 126.4 micromol/L. Ethene, a potential degradation product of both 1,2-DCA dihaloelimination and TCE reductive dechlorination was also present in the PTA. Emulsified soybean oil and lactate were added as electron donors to stimulate anaerobic dechlorination in the PTA. Stable carbon isotope analysis provided evidence that dechlorination was occurring in the PTA during biostimulation, and a means of monitoring changes in dechlorination efficiency over the 183 day monitoring period. Stable carbon isotope analysis was also used to determine if ethene production in the PTA was due to dechlorination of TCE, 1,2-DCA, or both. Fractionation factors (alpha) were determined in the laboratory during anaerobic biotransformation of 1,2-DCA via a dihaloelimination reaction in four separate enrichment cultures. These alpha values (as well as the previously published ranges of alpha for the dechlorination of TCE, cDCE and 1,2-DCA) were used, along with isotopic values measured during the pilot test, to derive quantitative estimates of biotransformation during the pilot test. Dechlorination was found to account for 10.7 to 35.9%, 21.9 to 74.9%, and 54.4 to 67.8% of 1,2-DCA, TCE and cDCE concentration loss respectively in the PTA. Stable carbon isotope analysis indicates that dechlorination of 1,2-DCA, TCE and cDCE were all significant processes during the pilot test, while ethene production during the pilot test was dominated by 1,2-DCA dihaloelimination. This study demonstrates how stable carbon isotope analysis can provide more conservative estimates of the extent of biotransformation than do conventional protocols. In addition, in a complex mixed plume such as this, compound specific isotope analysis is shown to be one of the few methods available for clarifying dominant biotransformation pathways where breakdown products are non-exclusive (i.e. ethene).     

Multi-residues analysis of pre-emergence herbicides in fluvial sediments: application to the mid-Garonne River

Contamination of man and ecosystems by pesticides has become a major environmental concern. Whereas many studies exist on contamination from agriculture, the effects of urban sources are usually omitted. Fluvial sediment is a complex matrix of pollutants but little is known of its recent herbicide content. This study proposes a method for a fast and reliable analysis of herbicides by employing the accelerated solvent extractor (ASE). The aim of the study is to show the impact of a major town (Toulouse) on the herbicide content in the river. In this study, three herbicide families (i.e.s-triazine, substituted ureas and anilides) were analysed in fluvial sediment fractions at 11 sampling sites along the mid-Garonne River and its tributaries. River water contamination by herbicides is minor, except for at three sites located in urban areas. Among the herbicidal families studied, urban and suburban areas are distinguished from rural areas and were found to be the most contaminated sites during the study period, a winter low-water event. The herbicide content of the coarse sediment fractions is about one third of that found in the fine fractions and usually ignored. The distribution of pesticide concentrations across the whole range of particle sizes was investigated to clarify the role of plant remains on the significant accumulation in the coarse fractions.     

Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro,Brazil

The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 μg m^?3 for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO₂ cartridges coated with C₁₈ and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 μg m^?3 for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 μg m^?3 for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.     

Response of Brazilian native trees to acute ozone dose

Ozone (O₃) is a toxic secondary pollutant able to cause an intense oxidative stress that induces visual symptoms on sensitive plant species. Controlled fumigation experiment was conducted with the aim to verify the O₃ sensibility of three tropical species: Piptadenia gonoachanta (Mart.) Macbr. (Fabaceae), Astronium graveolens Jacq. (Anacardiaceae), and Croton floribundus Spreng. (Euphorbiaceae). The microscopical features involved in the oxidative stress were recognized based on specific histochemical analysis. The three species showed visual symptoms, characterized as necrosis and stippling between the veins, mostly visible on the adaxial leaf surface. All the studied species presented hypersensitive-like response (HR-like), and peroxide hydrogen accumulation (H₂O₂) followed by cell death and proanthocyanidin oxidation in P. gonoachanta and A. graveolens. In P. gonoachanta, a decrease in chlorophyll autofluorescence occurred on symptomatic tissues, and in A. graveolens and C. floribundus, a polyphenol compound accumulation occurred. The responses of Brazilian native species were similar to those described for sensitive species from temperate climate, and microscopical markers may be useful for the detection of ozone symptoms in future studies in the field.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Elaboration and Characterization of Nano-Biocomposites Based on Plasticized Poly(Hydroxybutyrate-Co-Hydroxyvalerate) with Organo-Modified Montmorillonite

Nano-biocomposites based on a biodegradable bacterial copolyester, poly(hydroxybutyrate-co-hydroxyvalerate), have been elaborated with an organo-modified montmorillonite (OMMT) clay as nanofiller, and acetyl tributyl citrate as plasticizer. The corresponding (nano)structures, thermal and mechanical properties, permeability, and biodegradability have been determined. Polyhydroxyalkanoates are very thermal sensitive then to follow the degradation the corresponding matrices have been analyzed by size exclusion chromatography. The results indicate that the addition of the plasticizer decreases the thermo-mechanical degradation, during the extrusion. These nano-biocomposites show an intercalated/exfoliated structure with good mechanical and barrier properties, and an appropriated biodegradation kinetic. Intending to understand the changes in the thermal properties, the nano-biocomposites were characterized by thermal gravimetric analysis and differential scanning calorimetry. The presence of the OMMT clay did not influence significantly the transition temperatures. However, the filler not only acted as a nucleating agent which enhanced the crystallization, but also as a thermal barrier, improving the thermal stability of the biopolymer. The results indicated that the addition of the plasticizer reduces the glass transition temperature and the crystalline melting temperature. The plasticizer acts as a processing aid and increases the processing temperature range (lower melting temperature).     

Habitat use of a multispecific seagrass meadow by green turtles Chelonia mydas at Mayotte Island

We investigated the habitat use in green turtles exploiting a 13-ha multispecific seagrass meadow at Mayotte Island, south-western Indian Ocean. A phyto-ecological survey shows the occurrence of eight seagrass species, dominated by Halodule uninervis and Syringodium isoetifolium, distributed according to four distinct seagrass communities along the depth gradient. Direct underwater censuses show that green turtles occurred all over the meadow. Yet when community relative surface area was taken into account green turtles preferentially frequented the most seaward, biomass-richer S. isoetifolium-dominated community, suggesting that green turtles compensate for their intrinsically nutrient-poor herbivorous diet. Additionally, smaller (<80 cm standard curved carapace length, SCCL) individuals also preferentially occurred in the most shoreward H. univervis-dominated community where no larger (>80 cm SCCL) individuals were sighted, suggesting habitat use is indicative of diet selection and may reflect size-specific food requirements and physiology.