Methods,fluxes and sources of gas phase alkyl nitrates in the coastal air

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3–C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO₂ levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.     

Petroleum Hydrocarbons Rhizodegradation by Sebastiania commersoniana (Baill.) L. B. SM. & Downs

Petroliferous activities in Brazil have an accelerated development in the last years. As a consequence, the incidence of environmental accidents such as oil spills and contamination of soils has increased significantly. Therefore, it is extremely necessary to develop remediation techniques with lower costs, decontamination efficiency and impact minimisation. The aim of this work was to evaluate Sebastiania commersoniana phytoremediation potential in soil contaminated by petroleum. This species, which is a native tree, was selected due to its proven capacity for surviving in areas contaminated by petroleum. Experiments were carried out with soils that were vegetated but non-contaminated, soils that were freshly contaminated (25, 50 and 75 g kg^?1) but non-vegetated, and soils that were vegetated and contaminated, samples were collected 60 and 424 days after contamination with the purpose of evaluating the percentage of petroleum degradation in relation to the time. The results obtained in the present study allow us to state that S. commersoniana proves to be tolerant to petroleum contamination with respect to plant’s growth. The degradation of petroleum hydrocarbons was evaluated by gas chromatography with a flame ionisation detector (GC-FID) equipped with a capillary column HP-5 (5% phenyl-methylpolysiloxane, 30 m; 0.25 mm; 0.25 μm). According to chromatographic analysis, samples in contact with S. commersoniana showed a significant area reduction of the hydrocarbon peaks. Analysis of the 60-day samples showed a reduction of petroleum hydrocarbons area higher than 60% and the 424-day samples showed a reduction higher than 94%, which demonstrates that a petroleum degradation process is occurring.     

Rice straw ash extract, an efficient solvent for regioselective hydrothiolation of alkynes

Environmental Chemistry Letters - Herein, we describe a simple and inexpensive protocol for the hydrothiolation of alkynes. In this context, water extract of rice straw ash (WERSA) has been proven...     

Generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts: a review

Agro-waste extracts are considered green solvents since they are easy to handle, readily accessible from natural waste feedstock, biodegradable and recyclable. Therefore, the employment of these extracts in reaction media has emerged as the most useful and eco-friendly alternative in modern organic chemistry. Here, we review recent developments for the generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts. We show that these aqueous extracts have great applicability in several transformations, including condensations, oxidations, multicomponent and coupling reactions. The challenges and advantages on the use of water of agro-waste extracts in synthetic methodologies is also detail.

     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

Determination of BTEX by GC–MS in Air of Offset Printing Plants: Comparison between Conventional and Ecological Inks

The use of inks containing organic solvents by the offset printing process implies in the release of volatile organic compounds to the work environment. Many of these compounds such as benzene, toluene, ethylbenzene, and the xylene isomers (well known by the acronym BTEX) are extremely toxic. In this study, the BTEX concentrations were determined in two different printing plants that use distinct types of inks: the conventional and the so-called ecological, which is manufactured based on vegetal oil. Concentration ranges were 43–84, 15–3,480, 2–133, 5–459, and 2–236 μg m^?3 for benzene, toluene, ethylbenzene, m?+?p-xylene, and o-xylene, respectively, for the conventional printing plant. At the ecological printing plant, concentration ranges were below limit of detection (<LD)-31, <LD-618, <LD-1,690, <LD-10,500, <LD-3,360 μg m^?3 for benzene, toluene, ethylbenzene, m?+?p-xylene, and o-xylene, respectively. BTEX concentrations are lower at the ecological printing environment than in the conventional, where mineral oil-based inks are used. However, the worker who cleans the printing matrices is exposed to high concentrations of ethylbenzene and xylenes, due probably to the cleaning product’s composition (containing high amounts of BTEX). Although the BTEX concentrations found in both printing work environments were below the limits considered by the Brazilian Law for Activities and Unhealthy Operations (NR-15), the exposure to such vapors characterizes risk to the workers’ health for some of the evaluated samples, mainly the personal ones.     

Indoor Air Quality Assessment of Elementary Schools in Curitiba, Brazil

The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO₂; SO₂; O₃; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatography–ion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO₂ varied between 9.5 and 23?µg m^?3, whereas SO₂ showed an interval from 0.1 to 4.8?µg m^?3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5?µg m^?3 and 1.2?µg m^?3, respectively.     

Atmospheric BTEX-concentrations in an area with intensive street traffic

The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 μg/m³, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 μg/m³, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.     

Inferring episodic atmospheric iron fluxes in the Western South Atlantic

Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S–62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m^?2 day^?1 (October 29th–November 15th, 2003); 5.83–1586 nmolFe m^?2 day^?1 (February 15th–March 6th, 2004) and 4.73–586 nmolFe m^?2 day^?1(October 21st–November 5th, 2005).