Dissolution behavior of metals from particulate matter emissions

Exposure to air particulate matter (PM) is linked to numerous health effects. In order to improve the understanding of the role of its metallic components, their solubility was examined by using serial short-contact dissolutions totalling 1?h and additional sequential contact periods of 1, 4, and 8 days. The dissolution experiments were performed in solutions containing the main biological electrolytes. ICPMS determinations were used to quantify the dissolved metals. The total compositions were determined after closed vessel microwave digestion. Large variations in the rate and completeness of the dissolutions were observed. Fast and extensive dissolutions within the short-contact time (e.g., Zn, Cd) as well as slow dissolutions persisting during the last contact period (e.g., Ni, Cu, Sb, Pb) were found for smelting emissions. The multi-element determinations also made it possible to identify relationships between dissolution of different metals and define gradual composition changes of residual PM. When comparing with dissolutions performed in de-ionized water, similar major fractions were observed at short-contact time for minor components of smelting or combustion emissions (e.g., V, Ni, Cd), suggesting a preponderance of easily available forms at the surface of the relatively inert particle cores. The use of these time sequential methods may help in (1) modeling metal partitioning in biological media and (2) investigating the causes of adverse effects attributed to air PM.     

Levels of plasma B-esterases and glutathione-S-transferase activities in three South American toad species

We determined the normal levels of butyrylcholinesterase (BChE), carboxylesterase (CbE), and glutathione S-transferases (GST) activities in three South American toad species in order to establish reference values for field pesticide monitoring purposes. Interspecies variations in B-esterase and GST activities were examined according to body mass. In addition, comparative inhibition of BChE and CbE activities using malaoxon, and chemical reactivation of malaoxon-inhibited BChE activity using pyridine-2-aldoxime methochloride (2-PAM) were investigated. Bufo fernandezae had average activity values for BChE: 17.31 mmol min^?1 ml^?1; CbE: 621.49 nmol min^?1 ml^?1 and GST: 1.94 mmol min^?1 ml^?1 while B. arenarum enzymatic average activities were BChE: 9.51 mmol min^?1 ml^?1; CbE: 270.07 nmol min^?1 ml^?1, and GST: 1.59 mmol min^?1 ml^?1; finally Bufo schneideri had enzymatic mean values of BChE: 2.08 mmol min^?1 ml^?1; CbE: 301.95 nmol min^?1 ml^?1, and GST: 1.60 mmol min^?1 ml^?1. Moreover, we found an allometric relationship between plasma BChE and CbE activities and body size for the three toad species. We suggest that B. fernandezae would be the species with a higher tolerance capacity to organophosphorous insecticides compared to the other toad species, while B. schneideri may be the most vulnerable toad species to field pesticide exposure, although some other factors (e.g., brain AChE sensitivity or pesticide metabolism by phosphotriesterases) should be also taken into account. The malaoxon-inhibited BChE activity of the three toad species was reactivated in the presence of 2-PAM, and it is recommended as a specific and sensitive methodology in the assessment of field exposure to OP insecticides together to compare BChE activity levels between OP-exposed and nonexposed individuals.     

Potential correlation between perfluorinated acids and liver morphology in East Greenland polar bears (Ursus maritimus)

In this study, residual concentrations of chlorpyrifos (CPF) were determined in feed (40) and fodder (25) samples collected from various locations of Tarai region of Uttarakhand. For extracting residues, liquid–liquid partition followed by alumina column clean up was used and the detection and quantification of residues was undertaken with the help of high-performance liquid chromatography using C18 column and diode array detector at 220?nm. Of the total 40 feed samples analyzed, 7 (17.5%) samples were found positive for CPF with the mean residual concentration of 0.058?µg?g^?1; while out of 25 fodder samples, CPF residues were detected in a single (4%) sample with residual concentration of 0.39?µg?g^?1. However, none of the feed or fodder samples contained CPF residues above the prescribed limit.     

Mutagenicity of diesel engine exhaust in the Ames / Salmonella assay using a direct exposure method

The aim of this study was to investigate the potential mutagenic activity of diesel engine exhaust in the Ames/Salmonella assay using a direct aerosol exposure system. So, TA 98 and TA 100 strains, with or without added S9 mix, were exposed to diesel emissions after varying degrees of filtration. Variants of these two strains, deficient in nitroreductase (TA 98NR and TA 100NR) or over-expressing O-Acetyl Transferase (YG 1024 and YG 1029), were also exposed to total (unfiltered) diesel exhaust to highlight the putative mutagenicity of any nitro-PAHs present in these emissions. Mutagenic activity of the diesel exhaust was demonstrated on Salmonella typhimurium, strains TA 100 and variants TA 100 NR and YG1029. The use of a particle filter did not modify the genotoxicity of the diesel emissions, indicating a major contribution of the gas phase to the mutagenicity of these diesel emissions. The prominent role of the particulate-associated nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) claimed by some authors working on diesel exhaust organic extracts was not confirmed by our results with native diesel exhaust exposure. Our results show that the gas phase is potentially more mutagenic than the particles alone.     

Voltammetric studies of damages in DNA by mutagenic and carcinogenic alkylating chemicals

Voltammetry provides new insights into the effects exerted in vitro by methylation of native DNA. Applying single sweep voltammetry at a stationary mercury electrode the successive steps of the destabilization of alkylated DNA are investigated. The methylation of the nucleic acids is manifested by a specific electrochemical response, due to the 7‐methylguanine, a major product of the methylation of DNA. Short time effects of the methylation include the labilization of 4 to 5 base pairs per methylated guanine base. Furthermore, uncommon protonation properties of the base 7‐methylguanine‐cytosine have been detected. Long term effects of the methylation are ultimately spontaneous hydrolytic strand breaks induced by the prior depurination connected with the release of the 7‐methylguanine from the methylated DNA. A half time t_1/2 of 102 h for the depurination at 37°C has been determined. The depurination and the subsequent strand breaks alter the hydrodynamic properties of the damaged DNA, an effect which can be sensitively followed with voltammetry via the resulting changes in the diffusion coefficient of the damaged biopolymer.     

Polarographic investigations on the complexation of cadmium and zinc by thiol peptides

Complex formation of Cd²⁺ and Zn²⁺ with thiol derivatives has been investigated by differential pulse polarography. The binding of Cd²⁺ and Zn²⁺ with cysteine (CySH), glutathione (GSH) and the model peptide N‐acetyl‐cysteine‐methylamide (ASH) reveals different stoichiometry. Thus, Cd²⁺ forms 1:1 and 1:2 complexes with CySH while 1:2 and 1:4 complexes have been observed with GSH and ASH, respectively. Overall formation constants of Cd²⁺ with CySH (Iogβ ₂ 15.3) and with GSH (Iogβ5₂ 14.4) have been estimated using competitive complexation with nitrilotriacetic acid (NTA). Investigation of competition between Zn²⁺ and Cd²⁺ for the thiol complexation has underlined the role played by the amino group in CySH for the stabilization of Zn complexes in contrary to Cd complexes.     

Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

Dealing with urban noise: vermilion flycatchers sing longer songs in noisier territories

In noisy conditions, several avian species modulate their songs in amplitude and in the temporal or frequency domains, presumably to improve communication. Most studies on how passerine birds perform such adjustments have been carried out in oscines, a group well known for the importance of learning in the development of their songs. On the other hand, suboscines, in which learning appears to have little influence on the development of their songs, have been largely neglected. We evaluated song adjustment to noise in the vermilion flycatcher (Pyrocephalus rubinus), a suboscine bird. We conducted song recordings and noise measurements at several territories within Mexico City during the length of the dawn chorus. Males living in noisier places sang long songs, while those males inhabiting quieter places sang both short and long songs. We also found evidence of individual song plasticity, as males sang less versatile songs (i.e., songs with more introductory elements) later in the morning when noise levels were higher. This individual shift in song seems to be more associated to time of the day rather than to the observed rise in noise. However, we cannot discard an effect of noise, which should be evaluated with an experiment. We discuss our results in the context of other studies with oscine passerines and other taxa and consider implications for signaling in intra- and intersexual contexts.     

New aspect in seagrass acclimation: leaf mechanical properties vary spatially and seasonally in the temperate species Cymodocea nodosa Ucria (Ascherson)

Seagrasses may acclimate to environmental heterogeneity through phenotypic plasticity. In contrast to leaf morphology, which has been a central point in seagrass acclimation studies, plasticity in leaf biomechanics and fibre content is poorly understood, despite being crucial in plant ecological performance, especially regarding physical forces. We hypothesised that mechanical traits (e.g. breaking force, strength, toughness, and stiffness) and fibre content of seagrass leaves vary as morphology does under differential environments. Cymodocea nodosa was seasonally monitored at three locations around Cádiz Bay (southern Spain) with hydrodynamic regime as the most noticeable difference between them. Leaves showed plasticity in both morphology and mechanical traits, with wave-exposed individuals presenting short but extensible and tough leaves. Leaf fibre content was invariant along the year and with little spatial variability. Cross-sectional area rather than material properties or fibre content differentiates leaf mechanical resistance. Seagrass capacity to thrive under a range of mechanical forces may be dictated by their plasticity in morpho-biomechanical traits, a key element for the hydrodynamical performance and, hence, for species colonisation and distribution.