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.     

Elimination kinetics of perfluorohexanoic acid in humans and comparison with mouse,rat and monkey

Major fluorinated chemical manufacturers have developed new short-chain per- and polyfluorinated substances with more favorable environmental, health and safety profiles. This study provides the first evaluation of the elimination half-life of perfluorohexanoic acid (PFHxA) from the blood of humans. PFHxA biomonitoring data were obtained from a recently published study of professional ski wax technicians. These data were analyzed to provide estimates of the apparent half-life of PFHxA from humans, and comparisons were made with kinetic studies of PFHxA elimination from mice, rats and monkeys. The apparent elimination half-life of PFHxA in highly exposed humans ranged between 14 and 49 d with a geomean of 32 d. The half-lives of PFHxA in mice, rats, monkeys and humans were proportional to body weight with no differences observed between genders, indicating similar volumes of distribution and similar elimination mechanisms among mammalian species. Compared to long-chain perfluoroalkyl acid analogs, PFHxA is rapidly cleared from biota. The consistent weight-normalized elimination half-lives for PFHxA in mammalian species indicates that results obtained from animal models are suitable for establishment of PFHxA benchmark dose and reference dose hazard endpoints for use in human risk assessments.     

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.     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

A Population Viability Analysis for African Elephant (Loxodonta africana): How Big Should Reserves Be?

We present an age-structured, density-dependent model of elephant population dynamics in a fluctuating environment, drawing primarily upon the life history parameters obtained from studies in semi-arid land at Tsavo National Park, Kenya. Density regulation occurs by changes in the age of first reproduction and calving interval. We model environmental stochasticity with drought events affecting sex- and age-specific survivorships. Results indicate a maximum population growth rate of 3% per year and an equilibrium elephant density of 3.1/mile². Analysis of the demographic results and their sensitivity to changes in juvenile survivorship and drought frequencies, supported by genetic considerations, suggests that in semi-arid regions a minimum reserve size of 1000 mile² is necessary to attain a 99% probability of population persistence for 1000 years. The effect of age-independent culling on population viability is also analyzed.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

The Use of Geographic Information Systems for Resource Evaluation: A New Zealand Example

Over the last decade, New Zealand has implemented innovative reforms in respect of natural resource and environmental management. These include the Resource ManagementAct 1991 (RMA), a notable feature of which is the adoption of 'sustainable management' as the key principle guiding resource allocation and use. This and other features of the new administrative context for resource management strongly suggest a prominent role for geographicinformation systems (GIS) and related spatial information technology. In this paper we present an outline of the Regional Resource Evaluation Project (RREP), a project that has been established to explore and demonstrate the capabilities of GIS and related spatial information technology in the context of resource analysis and decision making. To date, the RREP has achieved important outcomes in terms of database design and development. An extensive information base which incorporates data on the physical and natural environment, patterns of human activity, and on social and demographic characteristics has been assembled. We describe the information systems, as well as some of the technical issues that attend to database design and development.We also provide brief reviews of two applications of the GIS to resource evaluation. One relates to the evaluation of changes in regional land use, with a focus on natural habitats. The other is concerned with land suitability assessment for plantation forestry.     

The behavioral component in the meaning of places

How do people think about the physical setting in the world around them? Part of the answer to this question may be in terms of the behaviors that occur there. To explore people's knowledge of behavior—place associations, twenty places (shown via color photographs) were assessed in five ways: (a) ratings of the place's suitability for each of eleven behaviors, (b) ratings of the expected frequency of occurrence of the eleven behaviors, (c) free listings of reasons for going to each place, (d) free listings of activities-while-there and (e) free listings of activities associated with the place. Results showed that people can distinguish places on the basis of behaviors, that the behavioral component of place meaning is composed of distinct aspects, and that knowledge of behavior is related to a global, overall representation of a place.     

The epidemiology of lawn trimmer injuries in the United States: 2000-2009

IntroductionYard maintenance equipment is potentially dangerous, and some of the more frequency used equipment (e.g., lawn mowers) has been extensively studied. However, the extent of lawn trimmers as a source of injury has not previously been explored.MethodsData from the Consumer Product Safety Commission's National Electronic Injury Surveillance System were used to estimate the number of patients treated in U.S. emergency departments for lawn trimmer-related injuries. Injury rates were calculated according to age, sex, and race, and characteristics of the injury event were determined.ResultsAn estimated 81,907 injuries involving a lawn trimmer occurred from 2000–2009. The incidence generally increased over time. Men, people aged 40–49, and Caucasians were the groups most likely to be injured. The most commonly injured body part was the head, specifically the eye, accounting for 42.5% of the injuries. Contusions and abrasions were the most common type of injury to the head, but lacerations were the most common injury to the extremities, and strains/sprains were the most common injury to the trunk.DiscussionAlthough previous research on lawn trimmers has focused exclusively on injuries to the eyes, the results of the current study show that such injuries are one component of the problem. Because most of the injuries were due to foreign objects, it is important that the use of adequate safety gear be emphasized when operating lawn trimmers.Impact on IndustryResults suggest that lawn trimmer design changes and better safety education for trimmer use can reduce the rate of injury and reverse the current trend.     

Characteristics of animal-related motor vehicle crashes in select National Park Service units—United States, 1990–2013

Objectives: Nationally, animal–motor vehicle crashes (AVCs) account for 4.4% of all types of motor vehicle crashes (MVCs). AVCs are a safety risk for drivers and animals and many National Park Service (NPS) units (e.g., national park, national monument, or national parkway) have known AVC risk factors, including rural locations and substantial animal densities. We sought to describe conditions and circumstances involving AVCs to guide traffic and wildlife management for prevention of AVCs in select NPS units.

Methods: We conducted an analysis using NPS law enforcement MVC data. An MVC is a collision involving an in-transit motor vehicle that occurred or began on a public roadway. An AVC is characterized as a collision between a motor vehicle and an animal. A non-AVC is a crash between a motor vehicle and any object other than an animal or noncollision event (e.g., rollover crash). The final data for analysis included 54,068 records from 51 NPS units during 1990–2013. Counts and proportions were calculated for categorical variables and medians and ranges were calculated for continuous variables. We used Pearson’s chi-square to compare circumstances of AVCs and non-AVCs. Data were compiled at the park regional level; NPS parks are assigned to 1 of 7 regions based on the park’s location.

Results: AVCs accounted for 10.4% (5,643 of 54,068) of all MVCs from 51 NPS units. The Northeast (2,021 of 5,643; 35.8%) and Intermountain (1,180 of 5,643; 20.9%) regions had the largest percentage of the total AVC burden. November was the peak month for AVCs across all regions (881 of 5,643; 15.6%); however, seasonality varied by park geographic regions. The highest counts of AVCs were reported during fall for the National Capital, Northeast/Southeast, and Northeast regions; winter for the Southeast region; and summer for Intermountain and Pacific West regions.

Conclusions: AVCs represent a public health and wildlife safety concern for NPS units. AVCs in select NPS units were approximately 2-fold higher than the national percentage for AVCs. The peak season for AVCs varied by NPS region. Knowledge of region-specific seasonality patterns for AVCs can help NPS staff develop mitigation strategies for use primarily during peak AVC months. Improving AVC data collection might provide NPS with a more complete understanding of risk factors and seasonal trends for specific NPS units. By collecting information concerning the animal species hit, park managers can better understand the impacts of AVC to wildlife population health.