UV-visible spectroscopy of organic carbon particulate sampled from ethylene/air flames

A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.     

Effects of long-term acclimation to environmental hypercapnia on extracellular acid–base status and metabolic capacity in Mediterranean fish <Emphasis Type="Italic">Sparus aurata</Emphasis>

In the context of future scenarios of anthropogenic CO₂ accumulation in marine surface waters, the present study addresses the effects of long-term hypercapnia on a Mediterranean fish, Sparus aurata. By equilibration with elevated CO₂ levels seawater pH was lowered to a value of 7.3, close to the maximum pH drop expected in marine surface waters from atmospheric CO₂ accumulation. Intra- and extracellular acid–base parameters as well as changes in enzyme profiles were studied in red and white muscles and the heart under both normocapnia and hypercapnia. The activities of pyruvate kinase (PK), lactate dehydrogenase (L-LDH), citrate synthase (CS), malate dehydrogenase and and 3-hydroxyacyl CoA dehydrogenase (HOAD) reflect the pathways and capacity of oxidative processes in metabolism. Long-term hypercapnia caused a transient reduction in blood plasma pH (pH_e) as well as in intracellular pH (pH_i). Compensation of the acidosis occurred through increased plasma and cellular bicarbonate levels. Changes in enzymatic activities, especially the increase in the activity of L-LDH, paralleled by a drop in CS activity in white and red muscles reflect a shift from aerobic to anaerobic pathways of substrate oxidation during long-term acclimation under hypercapnia. The present results suggest that moderate environmental hypercapnia changes the metabolic profile in tissues of S. aurata. Consequences for slow processes like growth and reproduction potential as well as potential harm at population, species and ecosystem levels require further investigation.     

Spatio-temporal distribution and migration of adult male loggerhead sea turtles (Caretta caretta) in the Mediterranean Sea: further evidence of the importance of neritic habitats off North Africa

Ten adult male loggerhead sea turtles, captured by trawlers or dip nets, were satellite-tracked from a neritic foraging ground in the Mediterranean in order to investigate adult spatio-temporal distribution and breeding migration. Five individuals migrated to potential breeding sites in Libya and one to Greece. The results complement previous studies and show that: (1) the Tunisian shelf may be more important for turtles from Libyan rookeries than previously thought; (2) male tracks corroborate a conservation hotspot previously identified for juveniles; (3) the north African coast represents a preferred migratory corridor, unless open sea routes are more direct; (4) adult males may exhibit high fidelity to relatively small areas, without evident seasonal differences; (5) adults home ranges were smaller and more neritic than juveniles frequenting the same area; (6) males may frequent multiple courtship areas; (7) the average remigration interval of males frequenting this region is longer than 1 year.     

Observation of volatile and semi-volatile carbonyls in an Algerian urban environment using dinitrophenylhydrazine/silica-HPLC and pentafluorophenylhydrazine/silica-GC-MS

Lower carbonyls and n-alkanals from C5 to C10 were measured from late autumn 2000 to summer 2001 in two urban areas in the Algerian territory: Algiers and Ouargla. They were collected on silica cartridges coated with dinitrophenylhydrazine (DNPH) and pentafluorophenylhydrazine (PFPH), which were analysed by HPLC-UV and high-resolution GC-MS. respectively. The two methods were used in parallel samplings in a suburban Algiers site and provided consistent results for semi-volatile congeners, as differences in the concentration data did not exceed 21% on average for individual carbonyl levels ranging from 0.0 to 0.5-2.6 microg m(-3). Concentrations of formaldehyde up to 27 and 5 microg m(-3) were monitored during 10 h samplings in the daytime in Algiers and Ouargla, respectively; acetaldehyde reached values of 13 and 5 microg m(-3), whilst acetone was the most abundant ketone with peak levels of 14 and 4 microg m(-3), respectively. High night-time levels of lower carbonyls were also measured at both locations. Among the semi-volatile alkanals, the highest levels were observed in suburban Algiers for hexanal and nonanal (2.2 microg m(-3)) and in downtown Algiers for valeraldehyde (2.6 microg m(-3)), whilst in Ouargla only hexanal and nonanal levels within the C5-C10 fraction exceeded 1 microg m(-3). Moreover, benzaldehyde concentrations as high as 5 microg m(-3) were measured in the centre of Algiers. Algiers data are comparable with those found in photochemically polluted urban areas of Europe and the USA. Strong correlations between formaldehyde and acetaldehyde and between formaldehyde and benzaldehyde were observed; by contrast, acetone did not show any correlation with the lower aldehydes, suggesting the existence of carbonyl sources other than vehicular traffic. Diurnal variations of almost all carbonyls suggested that motor vehicles were the most important source in the winter, whereas photochemical production appeared to predominate during the summer.     

Industrial point source CO<Subscript>2</Subscript> emission strength estimation with aircraft measurements and dispersion modelling

CO₂ remains the greenhouse gas that contributes most to anthropogenic global warming, and the evaluation of its emissions is of major interest to both research and regulatory purposes. Emission inventories generally provide quite reliable estimates of CO₂ emissions. However, because of intrinsic uncertainties associated with these estimates, it is of great importance to validate emission inventories against independent estimates. This paper describes an integrated approach combining aircraft measurements and a puff dispersion modelling framework by considering a CO₂ industrial point source, located in Biganos, France. CO₂ density measurements were obtained by applying the mass balance method, while CO₂ emission estimates were derived by implementing the CALMET/CALPUFF model chain. For the latter, three meteorological initializations were used: (i) WRF-modelled outputs initialized by ECMWF reanalyses; (ii) WRF-modelled outputs initialized by CFSR reanalyses and (iii) local in situ observations. Governmental inventorial data were used as reference for all applications. The strengths and weaknesses of the different approaches and how they affect emission estimation uncertainty were investigated. The mass balance based on aircraft measurements was quite succesful in capturing the point source emission strength (at worst with a 16% bias), while the accuracy of the dispersion modelling, markedly when using ECMWF initialization through the WRF model, was only slightly lower (estimation with an 18% bias). The analysis will help in highlighting some methodological best practices that can be used as guidelines for future experiments.     

Occurrence of imidacloprid,carbendazim, and other biocides in Italian house dust: Potential relevance for intakes in children and pets

The occurrence of pesticides intended for non-agricultural use was investigated in 206 dust samples drawn from vacuum-cleaner bags from residential flats in Italy. The multi-residue analysis targeted on 95 different active principles was performed with UPLC-MS/MS, with a Limit of Quantification (LOQ) of 0.008 μg/g dry weight. The results indicated the presence of imidacloprid (IMI) and carbendazim (CARB) in 30% and 26% of the samples, with a mean and P95 concentration between 1.6 and 39 and between 0.08 and 4.9 μg/g, respectively. Combined presence of two biocides was noted in 19.4% samples, of three biocides in 9.2% samples, of four biocides in 3.4% samples, and of five and six biocides in 0.5% and 1% samples, respectively. According to the estimated dust intake in infants/toddlers aged 6–24 months (16–100 mg d^?1) and cats (200 mg d^?1), it was possible to obtain risk characterization with respect to the Acceptable Daily Intake (ADI) for IMI of 0.060 mg/kg body weight (bw) proposed by the European Food Safety Authority (EFSA) and the chronic Population Adjusted Dose (cPAD) of 0.019 mg/kg bw d^?1 by US-EPA. Under the worst-case scenario, the presence of IMI in dust indicates potential exceedance of the cPAD in kittens, to be considered as sentinel also accounting for combined exposure. This study highlights the relevance of consumer empowerment about the responsible use of pesticides as biocidal products in indoor environment.     

A multi-lysimeter investigation on the mobility and persistence of pesticides in the loam soil of the Fucino Plain (Italy)

In order to evaluate the impact of intensive horticulture on the water resources of the Fucino Plain, one of the most important agricultural settlements of Central Italy, the mobility and persistence in the soil of five commonly used pesticides was investigated by means of multi-lysimeter experiments. The fate of simazine, carbaryl, dicloran, linuron and procymidone was evaluated in the laboratory under experimental conditions simulating as closely as possible both pesticide application and irrigation practices required by the local crops. An efficient extraction procedure followed by chromatographic analysis, allowing the simultaneous determination of the applied chemicals, was used to monitor the pesticide residues in the soil columns as a function of time from application and depth. The experiment, carried out for about 60 days, revealed that soil contamination apparently involves only the surface layer since none of the investigated pesticides was detected at depths greater than 20-30 cm. However, the five pollutants exhibit a quite different behaviour that can be related to their physico-chemical properties.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

New developments on emerging organic pollutants in the atmosphere

BACKGROUND: The continuous progress in analytical techniques has improved the capability of detecting chemicals and recognizing new substances and extended the list of detectable contaminants widespread in all environmental compartments by human activities. Most concern is focused on water contamination by emerging compounds. By contrast, scarce attention is paid to the atmospheric sector, which in most cases represents the pathway of diffusion at local or global scale. Information concerning a list of organic pollutants is provided in this paper. METHODS: The volatile methyl tert-butyl ether and siloxanes are taken as examples of information insufficient with regard to the potential risk induced by diffusion in the atmosphere. Illicit drugs, whose presence in the air was ascertained although by far unexpected, are considered to stress the needs of investigating not solely the environmental compartments where toxic substances are suspected to display their major influence. Finally, the identification of two recognized emerging contaminants, i.e., tris(2-chloroisopropyl) phosphate and N,N-diethyl-m-toluamide, in aerosols originally run to characterize other target compounds is presented with the purpose of underlining the wide diffusion of the organic emerging contaminants in the environment.     

Sampling and analytical methods for assessing the levels of organic pollutants in the atmosphere: PAH, phthalates and psychotropic substances: a short review

This short review presents the procedures used to monitor PAHs, phthalates and psychotropic substances in the air, and the results of some measurements made in Italy and abroad. Organic contaminants are characterized by a variety of physical and chemical properties, including aggregation phase, concentration level, and life time. This variety widens the spectrum of procedures developed to assess their occurrence in the environment and biota, but prevents the complete speciation of the "organic fraction" of air, waters and particulates, and attention is paid to a few substances. The progress in health sciences stimulates the concern on contaminants and the development of new instrumental apparatuses and methods; new chemicals are continuously identified or recognized as capable of injuring the environment and organisms. Persistent organic pollutants and persistent biologically active toxicants are subject to regulation and extensively measured by means of standard procedures. For instance, polycyclic aromatic hydrocarbons, polychlorobiphenyls and polychlorodibenzodioxins are recovered from air through phase partition, thermal desorption or solvent extraction, then separated and detected through GC-MS or HPLC-MS procedures. By contrast, dedicated methods must be still optimized to monitor candidates or possible candidates as emerging organic pollutants, e.g. phthalates, flame retardants and perfluoroalkanes. Also, psychotropic substances appear of potential concern. Legal and illicit substances are commonly detected in the urban air besides waste and surface waters. If nicotine, caffeine and cocaine will result to enough persistence in the air, their monitoring will become an important issue of global chemical watching in the next future.