Sampling of airborne polycyclic aromatic hydrocarbons with semipermeable membrane devices

Semipermeable membrane devices (SPMDs) are nowadays used as passive samplers of organic pollutants. The knowledge of the sampling rate values (R_S) of each substance trapped on membranes is necessary to calculate their average concentration. Here we calculate R_S values for 16 polycyclic aromatic hydrocarbons using the comparison of active sampling method results and the amounts sequestered by SPMDs at varying exposure times.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organized by Dr. Branimir Jovancicevic.     

Pressurised liquid-liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils

Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.     

Photodegradation of the herbicide Norflurazon sensitised by Riboflavin. A kinetic and mechanistic study

The kinetics and mechanism of the Riboflavin (Rf)-promoted photochemical degradation with visible light of the herbicide Norflurazon (NF) has been studied by time-resolved and stationary techniques. Using light of wavelength higher than 400 nm--a region where NF is totally transparent--and with concentrations of Rf and NF of ca. 0.02 and 1 mM, respectively, only the excited triplet state of Rf ((3)Rf*) is quenched by NF, in competition with dissolved ground state triplet oxygen, O(2)((3)Sigma(g)(-)). NF degradation mainly occurs by reaction with superoxide radical anion O(2)(-) formed through two electron transfer steps: from NF to (3)Rf*, yielding Rf radical anion, and from this anion to O(2)((3)Sigma(g)(-)), regenerating ground state Rf. Although singlet molecular oxygen is also produced, NF only quenches this oxidative species in a physical mode. The global result is the photoprotection of the sensitiser and the photodegradation of NF.     

Assessment of application-rate dependent effects of a long-term fire retardant chemical (Fire Trol 934) on Typha domingensis germination

Although long-term fire retardants (LTR) gain increasingly acceptance as effective tools for wildfire management, recent studies indicate their potential harmfulness in the environment, especially in aquatic ecosystems. This study comprises a first laboratory impact assessment of LTR action in temporal Mediterranean wetlands, using seed germination of Typha domingensis as indicator of impact. Our aim was to identify application rates upon which seed germination could be significantly affected. We tested for low (1 l m(-2)) and high (3 l m(-2)) application rates of Fire Trol 934 which are recommended by the manufacturers as a function of fuel characteristics. In addition, we simulated the impact of a higher application rate of 5 l m(-2) because inhomogeneous dispersal of the LTR during fire control and prevention operations can result in locally elevated applications. Results of a microcosm experiment indicate that application rates of 1 or 3 l m(-2) can impact Typha germination rates in the short-term via indirect LTR-mediated effects on water quality, which suppressed necessary cues for germination. However, a subsequent experiment with Petri dishes, using seeds isolated from the LTR treated sediments did not show significantly different germination rates between the control and the treatments with application rates of 1 or 3 l m(-2). This suggests that retardant pre-application germination success could be recovered in nature once the retardant is eliminated. By contrast, seeds almost completely failed to germinate in the microcosm experiment and the subsequent Petri dish essay when an application rate of 5 l m(-2) was used. This suggests a critical level upon which Typha seed germination may be perpetually limited. Research should be extended to other plant species to provide fire managers with guidelines for environmentally safe use of LTR in the Mediterranean region.     

210Pb geochronology and trace metal fluxes (Cd, Cu and Pb) in the Gulf of Tehuantepec, South Pacific of Mexico

Distributions of Al, Cd, Cu, Fe, Li, Mn and Pb were analyzed in a sediment core collected in the Gulf of Tehuantepec, an important fisheries region located in the South Pacific of Mexico, where data on metal accumulation and accretion rates were previously almost nonexistent. Depth profiles of metal concentrations were converted to time-based profiles by using a 210Pb-derived vertical accretion rate, estimated to be 0.05 cm year(-1) on the average. Sediments were dated up to 8 cm depth, corresponding to a layer of ca. 140 years old. The historical changes of metal accumulation along the sediment core have shown a moderate enrichment of Cd, Cu and Pb concentrations at present, of about threefold the corresponding background concentrations. Chronological trace metal records showed that metal fluxes have increased over the last 20 years, reaching the maximum values at present of 2.5, 22.5 and 45.8 (microg cm(-2) year(-1)) for Cd, Pb and Cu, respectively. These increments in metal fluxes are likely influenced by the development of anthropogenic land-based activities since over this period of time oil production activities in the region have had a significant development.