Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products

The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m³ atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10^?16 cm³ molecule^?1 s^?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.     

Testing the capability of the chemistry transport model LOTOS-EUROS to forecast PM10 levels in the Netherlands

Since particulate matter has a direct and adverse impact on public health, a good air quality forecast is important. Several European countries presently use statistical forecasting models, which have their limitations, especially for PM10. An alternative approach is to use a chemistry transport model. Here, the ability of the chemical transport model LOTOS-EUROS to forecast PM10 concentrations in the Netherlands was investigated. LOTOS-EUROS models several PM10 components individually. For sulphate, nitrate and ammonium aerosol the evaluation against observations shows that the modelled annual mean concentrations are within 20% of the measured concentration and that the temporal correlation is reasonably good (R > 0.6). For sea salt the model tended to overestimate the measured concentrations. For elemental carbon the correspondence with black smoke observations was reasonable. However, total PM10 is seriously underestimated, due to unmodelled components (secondary organic aerosols, mineral dust) and missing sources. Therefore, a simple bias correction for four seasons was derived based on the years 2004–2006. The model was compared with the Dutch operational statistical model PROPART and ground-level observations. With bias correction, LOTOS-EUROS performed better than PROPART regarding the timing of events. The major flaw of LOTOS-EUROS was that high values (>50 μg m^?3) were still underestimated. Another advantage of LOTOS-EUROS over the statistical model was the more detailed information in space and time, which facilitates communication of the forecast to the general public.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

Nanofiltration of concentrated and salted tuna cooking juices

Tuna cooking juice from a Tunisian tuna-processing unit has a high level of polluting load: chemical oxygen demand (COD) is comprised between 4 and 20 g L⁻¹, nitrogen kjedahl (NK) between 0.6 and 3 g L⁻¹ and dry matter between 120 and 160 g L⁻¹. The juice has thus to be treated before being rejected into the environment. This paper considers the nanofiltration (NF) of these concentrated organic/inorganic mixtures using an AFC 30 (NF) membrane. The work focusses on the effect of organic and inorganic matters on the permeate flux and rejections of these matters. For this purpose, mixtures of salt and organic pollution (COD), used as model solutions, were prepared by the dilution of a typical industrial tuna cooking juice. The permeate flux was found to decrease when salt and organic matter concentrations increase. The recovery rate in organic matter decreases with increasing salt or organic matter content and the recovery rate of salt decreases when the COD concentration increases.     

Lorenz Curve and Gini Coefficient: Novel tools for analysing seasonal variation of environmental radon gas

Using a methodology derived from Economics, the Lorenz Curve and Gini Coefficient are introduced as tools for investigating and quantifying seasonal variability in environmental radon gas concentration. While the Lorenz Curve presents a graphical view of the cumulative exposure during the course of the time-frame of interest, typically one year, the Gini Coefficient distils this data still further, to provide a single-parameter measure of temporal clustering. Using the assumption that domestic indoor radon concentrations show annual cyclic behaviour, generally higher in the winter months than in summer, published data on seasonal variability of domestic radon concentration levels, in various areas of the UK, Europe, Asia and North America, are analysed. The results demonstrate significantly different annual variation profiles between domestic radon concentrations in different countries and between regions within a country, highlighting the need for caution in ascribing seasonal correction factors to extended geographical areas. The underlying geography, geology and meteorology of a region have defining influences on the seasonal variability of domestic radon concentration, and some examples of potential associations between the Gini Coefficient and regional geological and geographical characteristics are proposed. Similar differences in annual variation profiles are found for soil-gas radon measured as a function of depth at a common site, and among the activity levels of certain radon progeny species, specifically ²¹⁴Bi deposited preferentially in human body-fat by decay of inhaled radon gas. Conclusions on the association between these observed measures of variation and potential underlying defining parameters are presented.     

Effectiveness of Smokeless Ashtrays

Abstract

Most environmental tobacco smoke (ETS) issues from the tips of smoldering cigarettes between puffs. Smokeless ashtrays are designed to reduce ETS exposure by removing particulate and/or gas-phase contaminants from this plume. This paper describes an experimental investigation of the effectiveness of four smokeless ashtrays: two commercial devices and two prototypes constructed by the authors. In the basic experimental protocol, one or more cigarettes was permitted to smolder in a room. Particulate or gas-phase pollutant concentrations were measured in the room air over time. Device effectiveness was determined by comparing pollutant concentrations with the device in use to those obtained with no control device. A lung deposition model was applied to further interpret device effectiveness for particle removal. The commercial ashtrays were found to be substantially ineffective in removing ETS particles because of the use of low-quality filter media and/or the failure to draw the smoke through the filter. A prototype ashtray using HEPA filter material achieved better than 90% particle removal efficiency. Gasphase pollutant removal was tested for only one prototype smokeless ashtray, which employed filters containing activated carbon and activated alumina. Removal efficiencies for the 18 gas-phase compounds measured (above the detection limit) were in the range of 70 to 95%.     

Effect of Refractory on the Thermal Stability of SF6

The thermal decomposition of SF₆ is known to be oxygen-independent. Nevertheless, because of its high stability, the use of SF6 as a "conservative" surrogate in incinerator performance evaluation has been advocated and researched. This paper shows that refractory decreases markedly the stability of SF₆. The resulting increase in SF₆ decomposition was from 0 percent to 95 percent at 900°C, and the temperatures at which 90-99 percent decomposition occurred were lowered by 300-150°C. Refractory also decreased the stability of CCl₄ and C₂Cl₄, but to a lesser extent. The difference between the decompositions of C₂Cl₄ and SF₆ was reduced from several orders of magnitude to a factor of 2-4. Such a drastic and adverse change in relative stability could render SF₆ unsuitable as a "conservative" surrogate. The requirements for a "conservative" surrogate and the need for caution in its use are discussed, and further research areas are indicated.     

Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.