Influence of cosolvents on quinoline sorption by subsurface materials and clays

Quinoline sorption was measured on Na-saturated subsurface materials, a natural clay isolate, and montmorillonite, and was dominated by exchange of the quinolinium ion. In water/methanol and water/acetone mixtures, quinoline sorption on the subsoils and clays was lower than from water. In cosolvent, sorption followed the ionization fraction indicating the continued predominance of ion exchange. The reduction in quinoline sorption by cosolvent was similar for all the subsoils and clays indicating commonality in the surface-solute-solvent interaction. Conditional equilibrium constants (_cK_ex) for quinoline exchange on the subsoils in water/methanol mixtures decreased log-linearly with mole percent cosolvent up to 20% methanol. This decrease closely followed the increase in quinoline solubility in the cosolvent mixtures. Acetone caused greater reduction in sorption than methanol, at comparable mole percent, in accordance with its lower dielectric constant and enhanced solvating power. A generalized thermodynamic approach based on the concept of transfer activity coefficients was developed to account for the cosolvent effect on _cK_ex, and was successfully applied to the quinoline sorption data. The thermodynamic analysis suggested that enhanced solvation of the organic cation in the bulk solvent and desolvation of Na⁺ at the charged surface predominate the cosolvent effect.     

Airborne observations of vegetation and implications for biogenic emission characterization

Measuring hydrocarbons from aircraft represents one way to infer biogenic emissions at the surface. The focus of this paper is to show that complementary remote sensing information can be provided by optical measurements of a vegetation index, which is readily measured with high temporal coverage using reflectance data. We examine the similarities between the vegetation index and in situ measurements of the chemicals isoprene, methacrolein, and alpha-pinene to estimate whether the temporal behavior of the in situ measurements of these chemicals could be better understood by the addition of the vegetation index. Data were compared for flights conducted around Houston in August and September 2000. The three independent sets of chemical measurements examined correspond reasonably well with the vegetation index curves for the majority of flight days. While low values of the vegetation index always correspond to low values of the in situ chemical measurements, high values of the index correspond to both high and low values of the chemical measurements. In this sense it represents an upper limit when compared with in situ data (assuming the calibration constant is adequately chosen). This result suggests that while the vegetation index cannot represent a purely predictive quantity for the in situ measurements, it represents a complementary measurement that can be useful in understanding comparisons of various in situ observations, particularly when these observations occur with relatively low temporal frequency. In situ isoprene measurements and the vegetation index were also compared to an isoprene emission inventory to provide additional insight on broad issues relating to the use of vegetation indices in emission database development.     

Free phosphine from the anaerobic biosphere

The possible liberation of highly toxic and mutagenic phosphine from putrefying media raises the question of its significance as a problem of hygiene. Free phosphine was established by gas chromatography as a universal trace component in gas emitted from the anaerobic biosphere. Sources of phosphine include landfills, compost processing, sewage sludge, animal slurry and river sediments. We detected maximum concentrations in the order of 20 ppb(v/v).     

Sources of airborne CC14

Atmospheric mixing ratios of chlorinated C₁ and C₂ hydrocarbons (CHCs) were measured at the mountain Wank (Garmisch-Partenkirchen, Bavarian Alps) in autumn 1992. The data lead to the assumption that at least part of the observed CC1₄ originates from a source different to the other CHCs measured (C₂HCL₃, C₂C1₄, CHCl₃ and CH₃CCl₃). The nature of this source is discussed.     

CMAQ simulations of the benzo(a)pyrene distribution over Europe for 2000 and 2001

In order to investigate benzo(a)pyrene (B(a)P) concentrations in ambient air in Europe and the respective deposition fields an expanded version of the Community Multiscale Air Quality (CMAQ) Modelling system has been used to simulate these fields for the years 2000 and 2001. Significant differences exist between different regions in Europe and between winter and summer concentrations. Modelled B(a)P concentrations are highest in Central Europe, South Ukraine and around Moscow. Wet deposition shows mainly the same regional distribution as the concentrations. Simulated concentrations and depositions are compared to measurements at selected sites of the EMEP network and of the German Federal Environmental Agencies. The measurements are on average underestimated by 50%. The temporal evolution and the regional distribution of B(a)P are captured by the model. In the approach presented here, particle bound B(a)P undergoes degradation by reactions with ozone. In order to assess the importance of the degradation process the results are compared to a model run where no degradation of particle bound B(a)P is considered. It was found that the inclusion of heterogeneous reactions of B(a)P with ozone results in a reduction of the modelled air concentration by approx. a factor of 5.     

Intrageneric differences in the four stereoisomers of stenusine in the rove beetle genus, Stenus (Coleoptera, Staphylinidae)

Most species of the rove beetle genus Stenus employ the spreading alkaloid stenusine as an escape mechanism on water surfaces. In the case of danger, they emit stenusine from their pygidial glands, and it propels them over the water very quickly. Stenusine is a chiral molecule with four stereoisomers: (2′R,3R)-, (2′S,3R)-, (2′S,3S)-, and (2′R,3S)-stenusine. The percentile ratio of these four isomers is only known for the most common species of the genus: Stenus comma. With the intention of determining the stereoisomer ratios of five additional species from the two subgenera, Stenus and Hypostenus, we used GC/mass spectrometry measurements with a chiral phase. The results showed that the ratio differs among the genus. These findings can be a basis for chemotaxonomy. It is also possible that the biological function of stenusine, e.g., as antibiotic or fungicide, varies with changing stereoisomer composition.

Measuring eddy covariance fluxes of ozone with a slow-response analyser

Ozone (O₃) fluxes above a temperate mountain grassland were measured by means of the eddy covariance (EC) method using a slow-response O₃ analyser. The resultant flux loss was corrected for by a series of transfer functions which model the various sources of high- and, in particular, low-pass filtering. The resulting correction factors varied on average between 1.7 and 3.5 during night and daytime, respectively. A cospectral analysis confirmed the accuracy of this approach. O₃ fluxes were characterised by a comparatively large random uncertainty, which during daytime typically amounted to 60%. EC O₃ fluxes were compared against O₃ flux measurements made concurrently with the flux-gradient (FG) method. The two methods generally agreed well, except for a period between sunrise and early afternoon, when the FG method was suspected of being affected by the presence of photochemical sources/sinks. O₃ flux magnitudes and deposition velocities determined with the EC method compared nicely with the available literature from grassland studies. We conclude that our understanding of the causes and consequences of various sources of flux loss (associated with any EC system) has sufficiently matured so that also less-than-ideal instrumentation may be used in EC flux applications, albeit at the cost of relatively large empirical corrections.