Photochimie et environnement - V. Photohydrolyse du monochlorobenzene en solution aqueuse diluee

A primary photohydrolysis of monochlorobenzene into phenol in dilute aqueous solution is occuring quantitatively whatever the experimental conditions were: pH (1<pH<12), excitation wavelength (253.7 nm or 300 nm), presence or absence of oxygen, initial concentration (in the range 10^?4M – 4.10^?3 M). The initial quantum yield of appearance of phenol has been found to be 0.10 ± 0.02 at 253.7 nm, and 0.19 ± 0.06 at 300 nm. The excited state leading to phenol cannot be quenched by acetonitrile at concentration up to 1.9 M. An heterolytic scission of the C-Cl bond parallels the concerted scission of water; a photosubstitution mechanism cannot account for the observed phenomena, especially in acidic media.Monofluoro- and bromobenzene irradiated in degased solution undergo a similar photohydrolysis; the initial quantum yields of appearance of phenol are 0.003 ± 0.001 and 0.06 ± 0.01, respectively for fluoro- and bromobenzene.     

Ozone pollution and ozone biomonitoring in European cities. Part I: Ozone concentrations and cumulative exposure indices at urban and suburban sites

In the frame of a European research project on air quality in urban agglomerations, data on ozone concentrations from 23 automated urban and suburban monitoring stations in 11 cities from seven countries were analysed and evaluated. Daily and summer mean and maximum concentrations were computed based on hourly mean values, and cumulative ozone exposure indices (Accumulated exposure Over a Threshold of 40 ppb (AOT40), AOT20) were calculated. The diurnal profiles showed a characteristic pattern in most city centres, with minimum values in the early morning hours, a strong rise during the morning, peak concentrations in the afternoon, and a decline during the night. The widest amplitudes between minimum and maximum values were found in central and southern European cities such as Düsseldorf, Verona, Klagenfurt, Lyon or Barcelona. In the northern European cities of Edinburgh and Copenhagen, by contrast, maximum values were lower and diurnal variation was much smaller. Based on ozone concentrations as well as on cumulative exposure indices, a clear north–south gradient in ozone pollution, with increasing levels from northern and northwestern sites to central and southern European sites, was observed. Only the Spanish cities did not fit this pattern; there, ozone levels were again lower than in central European cities, probably due to the direct influence of strong car traffic emissions. In general, ozone concentrations and cumulative exposure were significantly higher at suburban sites than at urban and traffic-exposed sites. When applying the newly established European Union (EU) Directive on ozone pollution in ambient air, it was demonstrated that the target value for the protection of human health was regularly surpassed at urban as well as suburban sites, particularly in cities in Austria, France, northern Italy and southern Germany. European target values and long-term objectives for the protection of vegetation expressed as AOT40 were also exceeded at many monitoring sites.     

Removal of PCBs from wastewater using fly ash

Liquids and sludges containing polychlorinated biphenyls (PCBs) can be treated to concentrate the PCBs in a solid residue. The latter can then be handled to destroy the PCBs. A study on sorption kinetics of PCBs on fly ash was conducted in controlled batch systems. TCB and HeCB are removed at 25 degrees C by adsorption on fly ash up to 97% at pH 7, with an adsorbent dose of 5 g/l. An examination of the thermodynamic parameters shows that the adsorption of TCB and HeCB by fly ash is a process occurring spontaneously at ambient conditions. Activation energies for the sorption process ranged between 5.6 and 49.1 kJ/mol. It was observed that the rate at which TCB and HeCB are adsorbed onto fly ash showed a diffusion limitation. The uptake rate of TCB and HeCB increases with increasing initial concentration and gradually tends to a constant value. A decrease in the adsorption of TCB and HeCB was observed when interfering ions and other PCB congeners were present. Changing the pH in the aqueous solution from 2 to 10 had no effect on the adsorption process. Overall, fly ash can be used for an efficient removal of PCBs from several aqueous solutions.     

Variations of immune parameters in terrestrial isopods: a matter of gender, aging and Wolbachia

Ecological factors modulate animal immunocompetence and potentially shape the evolution of their immune systems. Not only environmental parameters impact on immunocompetence: Aging is one major cause of variability of immunocompetence between individuals, and sex-specific levels of immunocompetence have also been frequently described. Moreover, a growing core of data put in light that vertically transmitted symbionts can dramatically modulate the immunocompetence of their hosts. In this study, we addressed the influence of gender, age and the feminising endosymbiont Wolbachia (wVulC) on variations in haemocyte density, total PO activity and bacterial load in the haemolymph of the terrestrial isopod Armadillidium vulgare. This host–symbiont system is of particular interest to address this question since: (1) wVulC was previously shown as immunosuppressive in middle-aged females and (2) wVulC influences sex determination. We show that age, gender and Wolbachia modulate together immune parameters in A. vulgare. However, wVulC, which interacts with aging, appears to be the prominent factor interfering with both PO activity and haemocyte density. This interference with immune parameters is not the only aspect of wVulC virulence on its host, as reproduction and survival are also altered.     

Development and Evaluation of a Multiplexed Real-Time TaqMan RT-PCR Assay with a Sample Process Control for Detection of F-specific RNA Coliphage Genogroups I and IV

There are increasing concerns of zoonotic transmission of some animal enteric viruses, such as calicivirus, hepatitis E virus, and rotavirus, which are closely related to human pathogenic strains. Most enteric viruses are detected by molecular techniques because they cannot be cultured. Surrogates such as F-RNA coliphages are cultivable but few molecular methods exist. Individual real-time TaqMan RT-PCR assays for the replicase gene of F-RNA coliphage genogroups I and IV were developed and multiplexed with a real-time TaqMan RT-PCR assay for feline calicivirus as a sample process control for the simultaneous detection and enumeration of genogroup I and IV F-RNA coliphages. Genogroup IV were successfully detected with the multiplexed assay in 80% of fecal samples that contained F-RNA coliphage levels ≥3.2 log plaque forming units (pfu). F-RNA coliphage were at or below the limit of detection in most fecal samples when levels were ≤4 log pfu/g.     

Cars on crutches: How much abatement do smog check repairs actually provide?

Not as much abatement as has been presumed. Smog check programs aim to curb tailpipe emissions from in-use vehicles by requiring repairs whenever emissions, measured at regular time intervals, exceed a certain threshold. Using data from California, we estimate that on average 41% of the initial emissions abatement from repairs is lost by the time of the subsequent inspection, normally two years later. Our estimates imply that the cost per pound of pollution avoided is an order of magnitude greater for smog check repairs than alternative policies such as new-vehicle standards or emissions trading among industrial point sources.     

Kelvin–Helmholtz instability in the presence of variable viscosity for mudflow resuspension in estuaries

The temporal stability of a parallel shear flow of miscible fluid layers of different density and viscosity is investigated through a linear stability analysis and direct numerical simulations. The geometry and rheology of this Newtonian fluid mixing can be viewed as a simplified model of the behavior of mudflow at the bottom of estuaries for suspension studies. In this study, focus is on the stability and transition to turbulence of an initially laminar configuration. A parametric analysis is performed by varying the values of three control parameters, namely the viscosity ratio, the Richardson and Reynolds numbers, in the case of initially identical thickness of the velocity, density and viscosity profiles. The range of parameters has been chosen so as to mimic a wide variety of real configurations. This study shows that the Kelvin–Helmholtz instability is controlled by the local Reynolds and Richardson numbers of the inflection point. In addition, at moderate Reynolds number, viscosity stratification has a strong influence on the onset of instability, the latter being enhanced at high viscosity ratio, while at high Reynolds number, the influence is less pronounced. In all cases, we show that the thickness of the mixing layer (and thus resuspension) is increased by high viscosity stratification, in particular during the non-linear development of the instability and especially pairing processes. This study suggests that mud viscosity has to be taken into account for resuspension parameterizations because of its impact on the inflection point Reynolds number and the viscosity ratio, which are key parameters for shear instabilities.     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Genetic structure of wild European populations of the invasive Pacific oyster Crassostrea gigas due to aquaculture practices

As a result of aquaculture activities, Pacific oysters Crassostrea gigas (Thunberg, 1793) have invaded European coasts. Using seven microsatellites, we found virtually no genetic differentiation between natural populations throughout the European range (from the south of the Wadden Sea (the Netherlands) to the south of France) and French cultivated oysters. The genetic homogeneity of Pacific oyster samples appears to be the result of repeated transfers from same seed stocks made for aquaculture and, to a lesser extent, widespread dispersal due to specific biological traits of this species. The only genetic differentiation of Sylt population in the north of the Wadden Sea (Germany) suggests a stronger, persistent impact of ongoing supply of new genetic material from hatchery production, corresponding to seeds selection made by breeders. All of our genetic data highlighted the importance of aquaculture practices on the genetic structure of the keystone invader C. gigas in Europe.