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Abstract: Ambient formaldehyde (HCHO), along with other volatile organic compounds (VOCs), was measured using proton-transfer reaction mass spectrometry (PTR-MS) at a ground site along the U.S.–Mexico border during the Cal-Mex 2010 air quality study. During the observation period, the HCHO mixing ratio varied between 1.0 ppbv and 13.7 ppbv. On average, a daily maximum of 6.3 ± 2.6 ppbv occurred around 10 AM and a minimum of 2.8 ± 1.3 ppbv was observed around midnight. The early onset of the HCHO daily maximum (∼ 3 h before the solar noon) indicated the presence of primary HCHO sources and a fast photolysis loss of HCHO, consistent with a measured low ratio of HCHO to acetaldehyde of (2.5 ± 0.8). Using the simulated photolysis rates, we estimated the contribution of OH radical production from HCHO photolysis relative to that from O3 photolysis, with a ratio from 0.8 to 18 and the highest values around traffic rush hours. Hence, our results indicate that HCHO plays a dominant role in regulating the OH radical budget in the area. [Copyright &y& Elsevier]

The photodegradation of six crop protection products (CPPs) was studied in 16 natural waters collected from across the midwest of the United States under simulated sunlight to determine the significance of indirect photolysis. The rate of degradation of five of the CPPs was faster in irradiated natural waters than in buffer systems, with the effect particularly significant with the relatively photostable compounds propiconazole and prometryn. Degradation rates were correlated with the concentration of one or more photosensitizers, or ratios thereof, by means of a Pearson's correlation and linear regression analysis. It was found that the photodegradation of chlorotoluron, pinoxaden, propiconazole and prometryn were linked to the concentration of nitrate, pointing to a significant role of hydroxyl radical (.OH) as a reactive intermediate. Increased concentrations of dissolved organic carbon (DOC) and bicarbonate relative to nitrate were found to decrease the rate of degradation of these compounds, consistent with a quenching role. Chlorothalonil appeared to be rapidly degraded by means of the carbonate radical (.CO3-), whereas the photodegradation of emamectin was particularly complex. Overall, indirect photolysis significantly enhanced the rate of CPP degradation and fate models based on these experiments appear to offer more realism than those that only take into account direct photolysis. Environ. Toxicol. Chem. 2010;29:575–581. © 2009 SETAC [ABSTRACT FROM AUTHOR]

Abstract: Impact of the excited nitrogen dioxide (NO2 ∗) chemistry on air quality in the U.S. is examined using the Community Multiscale Air Quality (CMAQ) model for a summer month. Model simulations were conducted with and without the NO2 ∗ chemistry. The largest impact of the NO2 ∗ chemistry in the eastern U.S. occurred in the northeast and in the western U.S. occurred in Los Angeles. While the single largest daily maximum 8-h ozone (O3) increased by 9 ppbv in eastern U.S. and 6 ppbv in western U.S., increases on most days were much lower. No appreciable change in model performance statistics for surface-level O3 predictions relative to measurements is noted between simulations with and without the NO2 ∗ chemistry. Based on model calculations using current estimates of tropospheric emission burden, the NO2 ∗ chemistry can increase the monthly mean daytime hydroxyl radicals (OH) and nitrous acid (HONO) by a maximum of 28% and 100 pptv, respectively. [Copyright &y& Elsevier]

Building occupants, including cleaning personnel, are exposed to a wide variety of airborne chemicals when cleaning agents and air fresheners are used in buildings. Certain of these chemicals are listed by the state of California as toxic air contaminants (TACs) and a subset of these are regulated by the US federal government as hazardous air pollutants (HAPs). California''s Proposition 65 list of species recognized as carcinogens or reproductive toxicants also includes constituents of certain cleaning products and air fresheners. In addition, many cleaning agents and air fresheners contain chemicals that can react with other air contaminants to yield potentially harmful secondary products. For example, terpenes can react rapidly with ozone in indoor air generating many secondary pollutants, including TACs such as formaldehyde. Furthermore, ozone–terpene reactions produce the hydroxyl radical, which reacts rapidly with organics, leading to the formation of other potentially toxic air pollutants. Indoor reactive chemistry involving the nitrate radical and cleaning-product constituents is also of concern, since it produces organic nitrates as well as some of the same oxidation products generated by ozone and hydroxyl radicals.Few studies have directly addressed the indoor concentrations of TACs that might result from primary emissions or secondary pollutant formation following the use of cleaning agents and air fresheners. In this paper, we combine direct empirical evidence with the basic principles of indoor pollutant behavior and with information from relevant studies, to analyze and critically assess air pollutant exposures resulting from the use of cleaning products and air fresheners. Attention is focused on compounds that are listed as HAPs, TACs or Proposition 65 carcinogens/reproductive toxicants and compounds that can readily react to generate secondary pollutants. The toxicity of many of these secondary pollutants has yet to be evaluated. The inhalation intake of airborne organic compounds from cleaning product use is estimated to be of the order of 10 mg d−1 person−1 in California. More than two dozen research articles present evidence of adverse health effects from inhalation exposure associated with cleaning or cleaning products. Exposure to primary and secondary pollutants depends on the complex interplay of many sets of factors and processes, including cleaning product composition, usage, building occupancy, emission dynamics, transport and mixing, building ventilation, sorptive interactions with building surfaces, and reactive chemistry. Current understanding is sufficient to describe the influence of these variables qualitatively in most cases and quantitatively in a few. [Copyright &y& Elsevier]

Advanced oxidation processes (AOPs) are an effective treatment technology for the removal of a variety of organic pollutants in both water and wastewater treatment. However, many background constituents in water are highly reactive towards hydroxyl radicals (HO) and decrease the efficiency of the process towards contaminant oxidation. Up to 95% of the HO scavenging can come from dissolved organic matter (OM). In this study, 28 wastewater effluent samples were analyzed to find correlations between the reactivity of HO with wastewater-derived OM (known as effluent organic matter, EfOM), water quality parameters, treatment train characteristics, and fluorescence-derived data. Rate constants for the reaction between HO and EfOM (kEfOM-HO) were measured using a bench scale UV-based AOP system with methylene blue as an HO probe and confirmed using an electron pulse radiolysis method for a subset of the samples. The EfOM was characterized using a series of physicochemical parameters, including polarity, average molecular size and fluorescence. The kinetic data were analyzed with principal component analysis and Akaike Information Criterion. Four predictors were identified as dominant: chemical oxygen demand, retention onto NH2 extraction medium, fluorescence index, and total organic carbon. These four variables accounted for approximately 62% of the variability in the value of kEfOM-HO The average kEfOM-HO value for EfOM in this study was 2.5 × 10(8) MC(-1) s(-1), which is about 31% lower than the 3.6 × 10(8) MC(-1) s(-1) value determined for natural organic matter isolates and commonly used in AOP modeling., (Copyright © 2013 Elsevier Ltd. All rights reserved.)