Fog Chemistry at an Urban Midwestern Site

This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from α-pinene ozonolysis (～100 ppb_v hydrocarbon [HC_x] with excess of O₃) within the University of California–Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO₃) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H₂O₂ (UV on), and N₂O₅ (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO₃ reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H₂O₂, or N₂O₅ is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO₃ radicals can further alter the chemical composition of SOA from α-pinene ozonolysis, which is proved to consist of first-generation products.

Implications: Secondary organic aerosol (SOA) may undergo aging processes once formed in the atmosphere, thereby altering the physicochemical and toxic properties of aerosol. This study discusses SOA aging of a major biogenic volatile organic compound (VOC; α-pinene) after it initially forms SOA. Aging of the α-pinene ozonolysis system by OH (through NO or H₂O₂ injection), NO₃ (through N₂O₅ injection), and photolysis is observed. Although the reaction rate appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) level of oxygenation on a 1-day scale, it is important that SOA aging be considered in ambient air quality models. Aging in this study is attributed to further oxidation of gas-phase oxidation products of α-pinene ozonolysis.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air &; Waste Management Association for information on the referenced α-pinene ozonolysis reaction and chamber reactor temperature.     

Effects of Instrument Precision and Spatial Variability on the Assessment of the Temporal Variation of Ambient Air Pollution in Atlanta,Georgia

Abstract

Data from the U.S. Environmental Protection Agency Air Quality System, the Southeastern Aerosol Research and Characterization database, and the Assessment of Spatial Aerosol Composition in Atlanta database for 1999 through 2002 have been used to characterize error associated with instrument precision and spatial variability on the assessment of the temporal variation of ambient air pollution in Atlanta, GA. These data are being used in time series epidemiologic studies in which associations of acute respiratory and cardiovascular health outcomes and daily ambient air pollutant levels are assessed. Modified semivariograms are used to quantify the effects of instrument precision and spatial variability on the assessment of daily metrics of ambient gaseous pollutants (SO₂, CO, NO_x, and O₃) and fine particulate matter ([PM_2.5] PM_2.5 mass, sulfate, nitrate, ammonium, elemental carbon [EC], and organic carbon [OC]). Variation because of instrument imprecision represented 7–40% of the temporal variation in the daily pollutant measures and was largest for the PM_2.5 EC and OC. Spatial variability was greatest for primary pollutants (SO₂, CO, NO_x, and EC). Population–weighted variation in daily ambient air pollutant levels because of both instrument imprecision and spatial variability ranged from 20% of the temporal variation for O₃ to 70% of the temporal variation for SO₂ and EC. Wind rose plots, corrected for diurnal and seasonal pattern effects, are used to demonstrate the impacts of local sources on monitoring station data. The results presented are being used to quantify the impacts of instrument precision and spatial variability on the assessment of health effects of ambient air pollution in Atlanta and are relevant to the interpretation of results from time series health studies that use data from fixed monitors.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.     

Population structure and phylogeography of an acorn barnacle with induced defense and its gastropod predator in the Gulf of California

Using sequence variation in the mitochondrial cytochrome oxidase I locus, we estimated the population structure and phylogeography of the intertidal acorn barnacle, Chthamalus anisopoma, and its gastropod predator, Mexacanthina lugubris angelica. Both are endemic to the Gulf of California, being derived from taxa on the Pacific coast of the Baja peninsula, and both exhibit phenotypic plasticity for traits affecting their coevolutionary interactions. Consistent with expectations based on differences in dispersal, C. anisopoma populations generally lack geographic structure, while those of M. l. angelica are more strongly structured. However, the variable degree of differentiation in both species suggests that the extent of reciprocal selection and local adaptation in the species will vary geographically, a result consistent with the concept of a geographic mosaic of coevolution. The pattern of variation in C. anisopoma shows clear evidence of recent spatial expansion, possibly due to increased habitat availability following the last glacial maximum. Phylogeographic analyses suggest that M. l. angelica diversified into three distinct clades after the colonization of the Gulf. Overall, our results illustrate how dispersal potential, geological and climatic events, and recent population growth have impacted the pattern of sequence variation in the two species.     

Modeling the stream water nitrate dynamics in a 60,000-km2 European catchment, the Garonne, southwest France

The spatial and temporal dynamics in the stream water NO(3)-N concentrations in a major European river-system, the Garonne (62,700 km(2)), are described and related to variations in climate, land management, and effluent point-sources using multivariate statistics. Building on this, the Hydrologiska Byr?ns Vattenbalansavdelning (HBV) rainfall-runoff model and the Integrated Catchment Model of Nitrogen (INCA-N) are applied to simulate the observed flow and N dynamics. This is done to help us to understand which factors and processes control the flow and N dynamics in different climate zones and to assess the relative inputs from diffuse and point sources across the catchment. This is the first application of the linked HBV and INCA-N models to a major European river system commensurate with the largest basins to be managed under the Water Framework Directive. The simulations suggest that in the lowlands, seasonal patterns in the stream water NO(3)-N concentrations emerge and are dominated by diffuse agricultural inputs, with an estimated 75% of the river load in the lowlands derived from arable farming. The results confirm earlier European catchment studies. Namely, current semi-distributed catchment-scale dynamic models, which integrate variations in land cover, climate, and a simple representation of the terrestrial and in-stream N cycle, are able to simulate seasonal NO(3)-N patterns at large spatial (>300 km(2)) and temporal (> or = monthly) scales using available national datasets.     

Using fisher-contributed secondary fins to fill critical shark-fisheries data gaps

Developing-world shark fisheries are typically not assessed or actively managed for sustainability; one fundamental obstacle is the lack of species and size-composition catch data. We tested and implemented a new and potentially widely applicable approach for collecting these data: mandatory submission of low-value secondary fins (anal fins) from landed sharks by fishers and use of the fins to reconstruct catch species and size. Visual and low-cost genetic identification were used to determine species composition, and linear regression was applied to total length and anal fin base length for catch-size reconstruction. We tested the feasibility of this approach in Belize, first in a local proof-of-concept study and then scaling it up to the national level for the 2017–2018 shark-fishing season (1,786 fins analyzed). Sixteen species occurred in this fishery. The most common were the Caribbean reef (Carcharhinus perezi), blacktip (C. limbatus), sharpnose (Atlantic [Rhizoprionodon terraenovae] and Caribbean [R. porosus] considered as a group), and bonnethead (Sphyrna cf. tiburo). Sharpnose and bonnethead sharks were landed primarily above size at maturity, whereas Caribbean reef and blacktip sharks were primarily landed below size at maturity. Our approach proved effective in obtaining critical data for managing the shark fishery, and we suggest the tools developed as part of this program could be exported to other nations in this region and applied almost immediately if there were means to communicate with fishers and incentivize them to provide anal fins. Outside the tropical Western Atlantic, we recommend further investigation of the feasibility of sampling of secondary fins, including considerations of time, effort, and cost of species identification from these fins, what secondary fin type to use, and the means with which to communicate with fishers and incentivize participation. This program could be a model for collecting urgently needed data for developing-world shark fisheries globally. Article impact statement: Shark fins collected from fishers yield data critical to shark fisheries management in developing nations.     

Anionic surfactant remediation of soil columns contaminated by nonaqueous phase liquids

A variety of column experiments have been completed for the purpose of selecting and evaluating suitable surfactants for remediation of nonaqueous phase liquids (NAPLs). The various NAPLs tested in the laboratory experiments were tetrachloroethylene (PCE), trichloroethylene (TCE), jet fuel (JP4) and a dense nonaqueous phase liquid from a site at Hill Air Force Base, UT. Both Ottawa sand and Hill field soil were used in these experiments. Surfactant candidates were first screened using phase behavior experiments and only the best ones were selected for the subsequent column experiments. Surfactants which showed high contaminant solubilization, fast coalescence times, and the absence of liquid crystal phases and gels during the phase behavior experiments were tested in soil column experiments. The primary objective of the soil column experiments was to identify surfactants that recovered at least 99% of the contaminant. The secondary objective was to identify surfactants that show low adsorption and little or no loss of hydraulic conductivity during the column experiments. Results demonstrated that up to 99.9% of the contaminants were removed as a result of surfactant flooding of the soil columns. The addition of xanthan gum polymer to the surfactant solution was shown to increase remediation efficiency as a lower volume of surfactant was required for recovering a given volume of NAPL. Based on these experimental results, guidelines for designing highly efficient and robust surfactant floods have been developed and applied to a field demonstration.     

A Study of Indoor Air Quality

As part of a larger program to investigate indoor sources of air pollution, an indoor/outdoor sampling program was carried out for NO, NO₂, and CO In four private houses which had gas stoves. The four houses chosen for study represented different surrounding land use, life styles, and house age and layout. The pollutant gases were measured essentially simultaneously at three indoor locations and one outdoor location. The results of the program showed that indoor levels of NO and NO₂ are directly related to stove use in the homes tested. Furthermore, these stoves often produced more NO₂ than NO. In some instances, the levels of NO₂ and CO in the kitchen exceeded the air quality standards for these pollutants if such outdoor standards were to be applied to indoors and the data for the sampling periods were typical of an entire year. A diffusion experiment conducted in one of the houses showed that the half-life for NO₂ was less than one-third that for either NO or CO. Oxidation of NO to NO₂ (based upon comparing the half-life of NO to CO) does not appear to occur to a significant degree indoors.     

Controlling Air Toxics Emissions From Remediation by Monitoring of Surrogate Parameters

Particulate matter (dust) from remediation and demolition sites may pose a potential risk to the nearby public due to the presence of various contaminants. Unfortunately, there are no good options for real‐time monitoring of metals, polychlorinated biphenyls, etc. in wind‐blown dust. A three‐tiered approach involving a combination of real‐time monitoring and off‐site analysis that has proved successful is described in this article. PM₁₀ is used as a surrogate parameter for metals and other nonvolatile pollutants, and real‐time monitoring is used to guide dust control measures. If dust emissions are controlled, air emissions of metals and other nonvolatile pollutants also are controlled. © 2014 Wiley Periodicals, Inc.