Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

Synthesis and characterization of γ-ferric oxide nanoparticles and their effect on <Emphasis Type="Italic">Solanum lycopersicum</Emphasis>

γ-Ferric oxide nanoparticles are synthesized through modern and facile ayurvedic route followed by normal and special purification steps, which are both cost-effective and eco-friendly. These synthesized γ-ferric oxide nanoparticles were applied on Solanum lycopersicum to search the effect on chlorophyll content. This process involves multiple filtration and calcination steps. The synthesized samples were analyzed by X-ray diffraction (XRD), UV-visible (UV-vis) spectroscopy, transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), and particle size analysis (PSA) to identify the purification step’s influence on the structural, optical, morphological, magnetic, and particle size properties of ferric oxide nanoparticles (γ-phase). X-ray diffraction has revealed that ferric oxide nanoparticles have rhombohedral structure of α-phase (hematite) in initial purification process later transformed into cubic structure γ-phase (maghemite). UV-vis spectroscopy analysis has clearly shown that by repetitive purification steps, λ_max has increased from 230 to 340 nm. TEM result has an intercorrelation with XRD results. γ-Ferric oxide nanoparticles were tested on Solanum lycopersicum (tomato seeds). The changes in the contents of chlorophyll a, chlorophyll b, and total carotene were studied using spectral measurements at two different dosages—0.5 and 2 M. As a result, at 0.5-M concentration, magnetic nanoparticles exhibit fruitful results by increasing the crop yield and being more resistant to chlorosis.     

Concentrations of decabromodiphenyl ether in air from Southern Ontario: implications for particle-bound transport

Atmospheric concentrations are reported for the main component of the brominated flame retardant decaBDE (BDE-209) in air samples collected from Southern Ontario for the period January 23-June 06, 2002. Levels ranged from below detection to 105pgm(-3) with virtually all of BDE-209 being trapped by the filter and thus deduced to be sorbed to aerosol particles. Thus, it is likely that the long-range atmospheric transport (LRAT) of BDE-209 is controlled by the transport characteristics of the aerosols. This conclusion that BDE-209 does not have the same potential for LRAT as other more volatile PBDEs is subject to possible complications arising from the uncertainties about the LRAT potential of aerosols.     

Petrosia testudinaria as a biomarker for metal contamination at Gulf of Mannar, southeast coast of India

Coastal marine ecosystems in many parts of the world are under unrelenting stress caused by urban development, pollutants and other ecological impacts such as building of infrastructure, land reclamation for port and industrial development, habitat modification, tourism and recreational activities. The present work is a first extensive field study using the marine sponge, Petrosia testudinaria as a biomarker to detect heavy metal pollution between near and off shore environment of 'Gulf of Mannar', India. Sponges were collected from near shore (0.5-1 km) and offshore (5-7 km), locations and their metal concentrations were determined by inductively coupled plasma-mass spectrometry (ICPMS). Our results show that the near shore sponge accumulated greater concentrations of heavy metals (Al, Fe, Mn, As, Ni, Co, Cu, Se) ranging from 0.13 to 64 times higher concentration than the sponges located away from the shore. The results indicate that the accumulated metals alter the macromolecule composition (sugars, proteins and lipids) in near shore sponges. Frequent monitoring is necessary to assess the eco-health of the marine environment by choosing bioindicator species like sponges, which provide accurate, reliable measurement of environmental quality.     

Genotoxicity of organic extracts of urban airborne particulate matter: an assessment within a personal exposure study

Airborne particulate matter, PM(10) and PM(2.5), are associated with a range of health effects including lung cancer. Their complex organic fraction contains genotoxic and carcinogenic compounds such as polycyclic aromatic hydrocarbons (PAHs) and their derivatives. This study evaluates the genotoxicity of the PM(10) and PM(2.5) organic extracts that were sampled in the framework of a personal exposure study in three French metropolitan areas (Paris, Rouen and Strasbourg), using the comet assay, performed on HeLa S3 cells. In each city, 60-90 non-smoking volunteers composed of two groups of equal size (adults and children) carried the personal Harvard Chempass multi-pollutant sampler during 48h along two different seasons ('hot' and 'cold'). Volunteers were selected so as to live (home and work/school) in 3 different urban sectors contrasted in terms of air pollution within each city (one highly exposed to traffic emissions, one influenced by local industrial sources, and a background urban environment). Genotoxic effects are stronger for PM(2.5) extracts than for PM(10), and greater in winter than in summer. Fine particles collected by subjects living within the traffic proximity sector present the strongest genotoxic responses, especially in the Paris metropolitan area. This work confirms the genotoxic potency of particulate matter (PM(10) and PM(2.5)) organic extracts to which urban populations are exposed.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

Sublethal effects of monocrotophos on locomotor behavior and gill architecture of the mosquito fish, Gambusia affinis

Subacute studies of monocrotophos [Dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] on mosquito fish, Gambusia affinis, were carried out in vivo for 24 days to assess the locomotor behavior, structural integrity of gill, and targeted enzyme acetylcholinesterase (AChE, EC: 3.1.1.7) interactions. Monocrotophos (MCP) can be rated as moderately toxic to G. affinis, with a median lethal concentration (LC(50)) of 20.49 +/- 2.45 mgL(-1). The fish exposed to sublethal concentration of LC(10) (7.74 mgL(-1)) were under stress and altered their locomotor behavior, such as distance traveled per unit time (m min(-1)) and swimming speed (cm sec(-1)) with respect to the length of exposure. Inhibition in the activity of brain AChE and deformities in the primary and secondary lamellae of gill may have resulted in failure of exchange of gases. The maximum inhibition of 95% of AChE activity was observed on days 20 and 24.Morphological aberrations in the gills were also studied during exposure to the sublethal concentration of monocrotophos for a period ranging from 8 to 24 days. The extent of damage in gill was dependent on the duration of exposure. The findings revealed that inhibition in brain AChE activity and structural alteration in gill were responsible for altering the locomotor behavior of exposed fish.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.