Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Impact of European legislation on marketed pesticides — A view from the standpoint of health impact assessment studies

The very significant impact of European legislation (Directive 91/414/EEC) on the authorization of plant protection products is reviewed herein, which has resulted in withdrawal of 704 active substances (AS) out of 889 assessed so far. The list of currently approved 276 AS includes 194 AS “existing” in the market before 1993 and 82 “new” AS introduced during the last 15 years. Results of toxicity characterization of the approved AS are also summarized, utilizing several well-known databases. Although significant data gaps exist for a rather large part of the approved AS, it is found that 84 AS are positive for at least one health effect (after chronic and/or acute exposure) including carcinogenicity, reproductive and neuro-developmental disorders, as well as endocrine disruption. The toxicity characterization results of this study are compared to those of recent assessments by other organizations (KemI, the Swedish Chemicals Agency, and the Pesticide Safety Directorate of the UK), where interpretation and use is made of AS “cut-off” criteria foreseen in new EU legislation. These studies report a comparatively smaller AS number with positive toxicity characterization. The possibility of some additional AS withdrawal in the near future, combined with the rather small rate of new AS introduction (approx. 5 per year) suggest that the list of approved AS over the next 10–15 years may not change very drastically. Consideration of the above trends is necessary and instructive in evaluating results of existing health impact assessment (HIA) studies, as well as in planning new ones. Due to the very drastic change in the number and type of marketed AS, that took place within the past 8–9 years, it is suggested that new HIA studies (based on epidemiological data after year 2000) should focus on a rather short time frame and, therefore, on appropriate cohort groups, e.g. young children. For the same reason, results of epidemiological studies of the past (involving banned AS) should be carefully interpreted and used with caution.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Gas–particle partitioning of persistent organic pollutants in the Western Balkan countries affected by war conflicts

Background, aim, and scope  

Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas–particle partitioning behavior of various persistent organic pollutants.     

Rapid measurement of emissions from military aircraft turbine engines by downstream extractive sampling of aircraft on the ground: Results for C-130 and F-15 aircraft

Aircraft emissions affect air quality on scales from local to global. More than 20% of the jet fuel used in the U.S. is consumed by military aircraft, and emissions from this source are facing increasingly stringent environmental regulations, so improved methods for quickly and accurately determining emissions from existing and new engines are needed. This paper reports results of a study to advance the methods used for detailed characterization of military aircraft emissions, and provides emission factors for two aircraft: the F-15 fighter and the C-130 cargo plane. The measurements involved outdoor ground-level sampling downstream behind operational military aircraft. This permits rapid change-out of the aircraft so that engines can be tested quickly on operational aircraft. Measurements were made at throttle settings from idle to afterburner using a simple extractive probe in the dilute exhaust. Emission factors determined using this approach agree very well with those from the traditional method of extractive sampling at the exhaust exit. Emission factors are reported for CO₂, CO, NO, NO_x, and more than 60 hazardous and/or reactive organic gases. Particle size, mass and composition also were measured and are being reported separately. Comparison of the emissions of nine hazardous air pollutants from these two engines with emissions from nine other aircraft engines is discussed.     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

Investigations of an intense aerosol loading during 2007 cyclone SIDR – A study using satellite data and ground measurements over Indian region

Tropical cyclones are prominent weather systems characterized by high atmospheric pressure gradients and wind speeds. Intense tropical cyclones occur in India during the pre-monsoon (spring), early monsoon (early summer), or post-monsoon (fall) periods. Originating in both the Bay of Bengal (BoB) and the Arabian Sea (AS), these tropical cyclones often attain velocities of more than 100 km h^?1 and are notorious for causing intense rain and storm surge as they cross the Indian coast. In this study, we examine the changes in the aerosol properties associated with an intense tropical cyclone “SIDR”, that occurred during 11–16 November 2007 over BoB. This cyclone, accompanied with very strong surface winds reaching 223 km h^?1, caused extensive damage over Bangladesh. Ground-based measurements of Aerosol Optical Depth (AOD) in the neighboring urban environment of Hyderabad, India, showed significant variations due to changes in wind velocity and direction associated with the cyclone passage. The Terra-MODIS and AVHRR satellite images showed prevalence of dust particles mixed with emissions from anthropogenic sources and biomass-burning AS, while the aerosol loading over BoB was significantly lower. The positive values of Aerosol index (AI) obtained from the Ozone Monitoring Instrument (OMI) suggested the presence of an elevated aerosol layer over the West coast of India, AS and Thar Desert during and after the cyclone episode. Meteorological parameters from the MM5 mesoscale model were used to study the variations in winds associated with the cyclonic activity. Particulate matter loading over the region during the cyclone period increased by ～45% with an accompanying decrease in columnar aerosol optical depth. The variations in Angstrom parameters suggested coarse-mode particle loading due to dust aerosols as observed in satellite data.     

Atmospheric nitrogen deposition in south-east Scotland: Quantification of the organic nitrogen fraction in wet,dry and bulk deposition

Water soluble organic nitrogen (WSON) compounds are ubiquitous in precipitation and in the planetary boundary layer, and therefore are a potential source of bioavailable reactive nitrogen. This paper examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry + wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors are denoted in this paper as “standard rain gauges”, and they are the design used in the UK national network for monitoring precipitation composition. “Dry + wet” deposition collectors are flushing rain gauges and they are equipped with a rain detector (conductivity array), a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, dissolved organic nitrogen (DON) represented 23% of the total dissolved nitrogen (TDN) in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk rain gauges and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers.