Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

Beyond selectivity: Are behavioral avoidance and hormesis likely causes of pyrethroid-induced outbreaks of the southern red mite Oligonychus ilicis?

Secondary pest outbreak is a counterintuitive ecological backlash of pesticide use in agriculture that takes place with the increase in abundance of a non-targeted pest species after pesticide application against a targeted pest species. Although the phenomenon was well recognized, its alternative causes are seldom considered. Outbreaks of the southern red mite Oligonychus ilicis are frequently reported in Brazilian coffee farms after the application of pyrethroid insecticides against the coffee leaf miner Leucoptera coffeella. Selectivity favoring the red mite against its main predatory mites is generally assumed as the outbreak cause, but this theory has never been tested. Here, we assessed the toxicity (and thus the selectivity) of deltamethrin against both mite species: the southern red mite and its phytoseid predator Amblyseius herbicolus. Additionally, behavioral avoidance and deltamethrin-induced hormesis were also tested as potential causes of red mite outbreak using free-choice behavioral walking bioassays with the predatory mite and life-table experiments with both mite species, respectively. Lethal toxicity bioassays indicated that the predatory mite was slightly more susceptible than its prey (1.5×), but in more robust demographic bioassays, the predator was three times more tolerant to deltamethrin than its prey, indicating that predator susceptibility to deltamethrin is not a cause of the reported outbreaks. The predator did not exhibit behavioral avoidance to deltamethrin; however insecticide-induced hormesis in the red mite led to its high population increase under low doses, which was not observed for the predatory mite. Therefore, deltamethrin-induced hormesis is a likely cause of the reported red mite outbreaks.     

The Bag Filterhouse for Oil-Fired Power Plants

This Report, published as Informative Report No. 7 of the Air Pollution Control Association’s TI-5 Public Utilities Committee, began to move through the 14 step approval procedure of APCA’s Technical Council in February 1964 Comments made by members of the Technical Council were considered in the preparation of the final report. It is now published as representing the best thinking of the Association. It is an extremely timely and informative report.     

Automotive Exhaust Emission Levels by Geographic Area and Vehicle Make A Nationwide Survey

Gross average automotive exhaust emissions data collected by the Atlantic Richfield Clean Air Caravan during the summer of 1970 showed only slight geographical variations when the specific makes were ignored. When considering specific makes, significant differences were found on an average emissions basis. Vehicle population—emission distributions showed wide variations in the 50% population levels and in the percent of vehicles with emissions greater than specified values. Hydrocarbon (HC) and carbon monoxide (CO) data are given on a gross basis for the 1970, 1968-69, 1966-67, and pre-1966 model year group vehicles. Average HC and CO emissions and vehicle population-Idle emissions distribution curves are included for specific make vehicles in selected areas.     

Weekday-Weekend Pollutant Studies of the Los Angeles Basin

Pollutant data from the Los Angeles Basin were analyzed for weekday-weekend differences for the smog months of June through September 1972 and 1973. The pollutants investigated were oxidant, NO, NO₂, total hydrocarbons (HC), CO, and particulates. In order to maintain the diurnal variation, the concentration percentiles were calculated for each weekday and weekend hour.