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.     

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.     

Variance Design and Air Pollution Control

Confronted with shortages of low sulfur content residual fuel oil and, consequently, faced with the threat of social and economic upheaval, several air pollution control authorities in the Northeastern states were forced to relax hard-won air quality standards during the winter of 1972. The authorities did so by granting variances to their sulfur content standards for residual fuel oil. This paper examines the institutional characteristics of these variance policies from an economic incentive standpoint. After setting up desirable structural criteria for institutional design of such crisis policies, the authors examine the experience of the winter of 1972 and arrive at policy guidelines which recommend themselves for consideration in future periods of fuel oil shortages.     

Interregional Exchanges of Air Pollution: Model Types and Applications

Regional scale air quality simulation models covering spatial scales of thousands of kilometers are finding increasing applications in studies of acid deposition and other air pollution problems. The purpose of this paper is to familiarize the nonexpert with the characteristics of the major types of interregional air quality models currently in use: Eulerian grid, statistical trajectory, and Lagrangian trajectory. The basic features, advantages, and disadvantages of each of these modeling approaches are summarized, as are the important limitations and problems associated with interregional modeling in general. Typical applications are illustrated using examples from the use of a representative Lagrangian trajectory model, ENAMAP, over the eastern North American area.     

Use of Energy Scenarios in Addressing the CO2 Question

A reference scenario for CO₂ emissions was developed using a model of world energy supply and demand. In the reference scenario, world GNP and world energy demand increase at average rates of 2.1 percent per year and 1.5 percent per year, respectively during the period 1975-2100. The corresponding annual CO₂ emissions rise to a maximum of 16 gigatons of carbon around 2050 and then decline as a result of a transition to nonfossil fuel energy systems. A modified scenario for high CO₂ emissions was obtained by assuming an abundant supply of low cost coal, thus eliminating the transition. A low case was developed in which the low cost of alternative energy (i.e., solar, nuclear) induces an earlier shift away from fossil fuels.

Annual emissions of the three scenarios were used as input to a global carbon cycle model and the CO₂ buildup in the atmosphere during the period 1980-2100 was determined by the model. All three scenarios showed continuous rises in atmospheric CO₂ concentration. The reference scenario reached 775 ppm by 2100. The high CO₂ case resulted in concentrations of over 1040 ppm, and for the low case the 2100 concentration was just under 700 ppm. If the climate theory is correct, even 700 ppm is sufficient to give significant climate warming, but by experiencing the change gradually over a century, adaptation may not be painful. An early transition to nonfossil fuel supplies makes the problem less severe but does not eliminate it.     

Parts-per-trillion LC-MS(Q) analysis of herbicides and transformation products in surface water

The goal of this study was to develop a robust method of analyzing surface water samples for S-triazine herbicides, chloroacetanilide herbicides, and their transformation products (TPs) using solid-phase extraction (SPE) followed by liquid chromatograph-mass spectrometry (LC-MS) with electrospray ionization (ESI) by in-source collision-induced dissociation (ISCID) capability of an orthogonal electrospray ionization probe on a single quadrupole LC-MS system. The method developed here met the goals of the study and yielded estimated method detection limits (EMDLs) averaging 0.3 ± 0.1 ng L(-1) for S-triazines and their TPs and 0.7 ± 0.4 ng L(-1) for chloroacetanilides and TPs. Spiked filtered river water yielded SPE recoveries ranging from 94.2 % ± 4.8 % for S-triazines and TPs after eliminating three compounds with less that 65 % recovery from analysis and 95.9 % ± 19 % for chloroacetanilides and their TPs. The method was field-tested with filtered water samples collected from four sites over a four-month period. Detectible values of S-triazines and TPs ranged from 0.3 to 1540 ng L(-1) with a mean of 79.3 and a median of 19.4 ng L(-1). Detectible values for chloroacetanilides and TPs ranged from 0.31 to 3780 ng L(-1) with a mean of 252 and a median of 25.6 ng L(-1). An additional goal was to determine if the method was useful for microbial degradation studies using native bacterial communities. The bacteria transformed atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) solely into 2-hydroxy atrazine (2-hydroxy-4-ethylamino-6-isopropylamino-S-triazine) with concentrations of 78.4, 63.3 and 32.5 ng L(-1) after 12 days of incubation compared with 6.3 and 7.1 ng L(-1) for control dark and control sunlight respectively.