Determination of Levoglucosan in Atmospheric Fine Particulate Matter

Abstract

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-β-D-altro-heptulopyranose) in 20 μL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 ± 6% from five filters amended with 2 μg levoglu-cosan, and the reproducibility of the assay is 9%. The limit of detection is ～0.1 μg/mL, which is equivalent to ～3.5 ng/m³ for a 10 L/min sampler or ～8.7 ng/m³ for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m³) were identical irrespective of whether samples were collected by PM with aerodynamic diameter ≤2.5 μm or PM with aerodynamic diameter ≤10 μm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

Organizational justice,voluntary learning behavior,and job performance: A test of the mediating effects of identification and leader‐member exchange

This paper presents and tests an integrative model of voluntary learning behavior. Drawing on social exchange theory, we argue that individuals are more likely to pursue learning activities when they identify with their employing organization and have a high quality leader–member exchange (LMX) relationship with their supervisor. We further argue that organizational identification is enhanced by both distributive and procedural fairness, whereas LMX quality is enhanced by interpersonal and informational fairness. Moreover, we contend that effective learning behavior improves job performance. The model was tested with a sample of 398 employees from a large automobile dealership. Results supported most predictions. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigating the link between $$\hbox {PM}_{2.5}$$ and atmospheric profile variables via penalized functional quantile regression

Fine particulate matter (\(\hbox {PM}_{2.5}\)) events negatively affect the health of numerous persons globally each year. Previous works have described the association between air pollution and surface-level meteorological conditions; however, there has been less focus on the task of linking air pollution events with meteorological conditions at higher levels of the atmosphere. Working within the functional data framework, we develop a penalized functional quantile regression (PFQR) procedure to model conditional quantiles of a continuous response based on a functional covariate, with the ability to penalize selected derivatives of the estimated coefficient function. Our aim is to investigate the relationship between atmospheric profile variables (APVs), assumed to be functional, and key quantiles of the conditional distribution of surface-level \(\hbox {PM}_{2.5}\). Via a simulation study, we find that the performance of our PFQR procedure compares favorably to other related approaches. We conclude with an analysis of \(\hbox {PM}_{2.5}\) data at two Southeastern US locations, Columbia, SC and Tampa, FL, where we estimate the coefficient functions for the APVs corresponding to both ‘typical’ and ‘high’ \(\hbox {PM}_{2.5}\) events. As we believe that the true coefficient functions are smooth and may be exactly zero over subsets of their domains, we impose penalties on the 0th and 2nd derivatives. Our analysis indicates that the corresponding atmospheric conditions differ between the two locations, and that the conditions differ seasonally within location.     

Evaluation of Vegetation Near Coal-burning Power Plants in Southwestern Pennsylvania. II. Ozone Injury on Foliage of Hybrid Poplar

The objective of this study was to determine if the incidence or severity of foliar injury induced by regional, ambient ozone was influenced by local emissions from a complex of coal-burning power plants in southwestern Pennsylvania. Plantings of an ozonesensitive hybrid poplar clone {Populus maximowizii x trichocarpa, clone NE 388) were established in 1972 at various distances and directions from the power plants. Foliar injury caused by ambient ozone was evaluated annually from 1973 to 1990 in early to mid- August. Data are presented for the 12-year period, 1979 to 1990 inclusive, for which the most complete data sets were available. Injury from ambient ozone varied spatially and temporally, but with little relationship to power plant location. There was an apparent negative relationship between emission trends and ozone-induced symptoms, but only for one power plant. The correlation between annual mean levels of ozone-induced stipple and frequency of days (per year) with a 1-hr ozone maximum exceeding 0.04 ppm was weak, but significant. Ozone-induced bifacial necrosis was not observed on the foliage of the hybrid poplar during the drought year of 1988 in spite of record high levels of ozone; however, ozoneinduced stipple was observed.     

A Systematic Test of an Enterprise Strategy for Community-Based Biodiversity Conservation

Abstract: A commonly held belief is that if people can benefit financially from enterprises that depend on nearby forests, reefs, and other natural habitats, then they will take action to conserve and sustainably use them. The Biodiversity Conservation Network brought together conservation and development organizations and local communities to systematically test this hypothesis across 39 conservation project sites in Asia and the Pacific. Each project implemented one or more community-based enterprises such as setting up an ecotourism lodge, distilling essential oils from wild plant roots, producing jams and jellies from forest fruits, harvesting timber, or collecting marine samples to test for pharmaceutical compounds. Each project team collected the biological, enterprise, and social data necessary to test the network's hypothesis. We present the results of this test. We found that a community-based enterprise strategy can lead to conservation, but only under limited conditions and never on its own. We summarize the specific conditions under which an enterprise strategy will and will not work in a decision chart that can be used by project managers to determine whether this strategy might make sense at their site. We also found that an enterprise strategy can be subsidized and still create a net gain that pays for conservation. Based on our experiences, we recommend developing "learning portfolios" that combine action and research to test other conservation strategies.     

Preliminary assessment of polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment, including the Firth of Clyde

This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from 相似文献   

Assessing environmentally significant effects: a better strength-of-evidence than a single P value?

Interpreting a P value from a traditional nil hypothesis test as a strength-of-evidence for the existence of an environmentally important difference between two populations of continuous variables (e.g. a chemical concentration) has become commonplace. Yet, there is substantial literature, in many disciplines, that faults this practice. In particular, the hypothesis tested is virtually guaranteed to be false, with the result that P depends far too heavily on the number of samples collected (the ‘sample size’). The end result is a swinging burden-of-proof (permissive at low sample size but precautionary at large sample size). We propose that these tests be reinterpreted as direction detectors (as has been proposed by others, starting from 1960) and that the test’s procedure be performed simultaneously with two types of equivalence tests (one testing that the difference that does exist is contained within an interval of indifference, the other testing that it is beyond that interval—also known as bioequivalence testing). This gives rise to a strength-of-evidence procedure that lends itself to a simple confidence interval interpretation. It is accompanied by a strength-of-evidence matrix that has many desirable features: not only a strong/moderate/dubious/weak categorisation of the results, but also recommendations about the desirability of collecting further data to strengthen findings.