Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

Atmospheric concentration characteristics and gas-particle partitioning of PCBs in a rural area of eastern Germany

Atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured in 14 successive daytime and nighttime air samples collected from Melpitz, a rural site in eastern Germany. The average total concentration of PCBs was 110+/-80 pg m-3 and they were predominately present in the gas phase (approximately 95%). Composition of individual congeners closely resembled those of Clophen A30 and Aroclor 1232. Partial vapor pressures of PCBs were well correlated with temperature and the steep slopes obtained from Clausius-Clapeyron plots (-4500 to -8000) indicated that evaporation from adjacent land surfaces still controls the atmospheric levels of these pollutants. Particle-gas partitioning coefficients (KP) of PCBs were well correlated with the respective sub-cooled vapor pressures (PLo), but the slopes obtained from logKP versus logPLo plots (-0.16 to -0.59) deviated significantly from the expected value of -1. Overall, gas-particle partitioning of PCBs was better simulated by Junge-Pankow than octanol/air partition coefficient-based model.     

Arsenic speciation in fish from Greek coastal areas

Arsenic speciation analysis was conducted on fish samples(sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf,Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to62.6 mg As/kg dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8 mg As/kg dry weight, accounting for67–95% of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072–0.956 mg As/kg dry weight.Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity,total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, are potentially correlated to As species concentrations. Furthermore, based on factor analysis, the biological parameters, such as fish weight, lipids, protein and ash content,that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

Spectral characterization of two bioaccumulated methoxylated polybrominated diphenyl ethers

Two methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were isolated from a True's beaked whale (Mesoplodon mirus) and identified by NMR (1H, 1H-1H and 1H-13C) and high resolution mass spectrometry as 2-(2',4'-dibromophenoxy)-3,5-dibromoanisole (6-MeO-BDE47) and 2-(2',4'-dibromophenoxy)-4,6-dibromoanisole (2'-MeO-BDE68). Previously the structures of these bioaccumulated compounds have been determined by comparison of their mass spectra and gas chromatographic (GC) retention times with those of authentic standards. While this method is accepted and generally successful, NMR of the isolated compounds allows us to definitively identify the congeners. Our characterizations are consistent with those made for MeO-PBDEs in other organisms, identified by chromatographic methods.     

Compound-specific chlorine isotope analysis of polychlorinated biphenyls isolated from Aroclor and Clophen technical mixtures

The combined electrochemical oxidation-solar-light/immobilized TiO₂ film process was conducted to degrade an azo dye, Reactive Black 5 (RB5). The toxicity was also monitored by the Vibrio fischeri light inhibition test. The electrochemical oxidation rapidly decolorized RB5 (55, 110 μM) with a supporting electrolyte of 2 g l⁻¹ NaCl at current density 277 A m⁻² and pH 4. However, TOC mineralization and A₃₁₀ removal were low. Additionally, the treated solution showed high biotoxicity. RB5 at 110 μM significantly retarded the de-colorization efficiency by using the solar-light/immobilized TiO₂ film process. The combined electrochemical oxidation-solar-light/immobilized TiO₂ process effectively increased the removal of color, A₃₁₀, and TOC. The toxicity was also significantly reduced after 3 h of solar irradiation. The results indicated that the low-cost combined process is a potential technique for rapid treatment of RB5.     

Beyond the cage: Ecosystem modelling for impact evaluation in aquaculture

An ecosystem modelling approach was used in two areas of the Eastern Mediterranean in order to examine the effects of aquaculture on the ecology of the water column. Aquaculture expansion to meet demands of a growing population is followed by concerns about keeping impacts within socially acceptable limits. Primarily the study aimed at investigating the fate of nutrients from finfish culture and evaluating changes in chemical and biological characteristics of the water body. The model used, Aquaculture Integrated Model (AIM), is based on a complex generic biogeochemical model coupled to a 3D hydrodynamic model. Selected areas included a finfish farm in the Northern Aegean, Greece and an aquaculture development area in Vassiliko, Cyprus. Ecosystem effects were evaluated on the basis of scale and importance. Scenarios under different production levels and hydrodynamic conditions were explored at the sites. Model results showed that farm discharges are rapidly dispersed from their point source in addition to a tendency for effluents to accumulate at distances not normally associated directly with farming activity. The wide range of parameters available in the model helped identify parameters more likely to be affected by the farming activities. There was a satisfactory correlation between observed and predicted model outputs. This study demonstrates the importance of approaching aquaculture impacts at an ecosystem level and the utility of a modelling tool to this end.     

Occurrence of gaseous and particulate polycyclic aromatic hydrocarbons in the urban atmosphere: study of sources and ambient temperature effect on the gas/particle concentration and distribution

The presence of polycyclic aromatic hydrocarbons (PAHs) in an urban region (Heraklion, Greece) and processes that govern their atmospheric fate were studied from November 2000 until February 2002. Sixteen samples were collected, by using an artifact-free sampling device, on a monthly basis and the concentration of PAHs in gas and particulate phase was determined. The most abundant members (gas + particles) were phenanthrene (20.0+/-7.0 ng m(-3)), fluoranthene (6.5+/-1.7 ng m(-3)), pyrene (6.6+/-2.4 ng m(-3)), and chrysene (3.1+/-1.5 ng m(-3)). Total concentration (gas+particulate) of PAH ranged from 44.3 to 129.2 ng m(-3), with a mean concentration of 79.3 ng m(-3). Total concentration of PAHs in gas phase ranged from 31.4 to 84.7 ng m(-3) with non-observable seasonal variation. Conversely, maximum PAH concentrations in the particulate phase occurred during winter months. Particulate concentration varied from 11.4 to 44.9 ng m(-3), with an average of 25.2 ng m(-3). PAH distribution between gas and particulate phase was in agreement with the sub-cooled vapor pressure. Shift in gas/particle distribution due to difference in ambient temperature elucidated to some extent the seasonal variation of the concentration of PAHs in particles.     

Annoyance due to aircraft noise has increased over the years—Results of the HYENA study

In the HYENA study (HYpertension and Exposure to Noise near Airports) noise annoyances due to aircraft and road traffic noise were assessed in subjects that lived in the vicinity of 6 major European airports using the 11-point ICBEN scale (International Commission on Biological Effects of Noise). A distinction was made between the annoyance during the day and during the night. L_den and L_night were considered as indicators of noise exposure. Pooled data analyses showed clear exposure–response relationships between the noise level and the noise annoyance for both exposures. The exposure–response curves for road noise were congruent with the EU standard curves used for predicting the number of highly noise annoyed subjects in European communities. Annoyance ratings due to aircraft noise, however, were higher than predicted by the EU standard curves. The data supports other findings suggesting that the people's attitude towards aircraft noise has changed over the years, and that the EU standard curve for aircraft noise should be modified.