Variations in the Emissions of Volatile Organic Compounds from the Toner for a Specific Photocopier

ABSTRACT

A laboratory thermal desorption apparatus was used to measure emissions from a number of nominally identical photocopier toners—manufactured to meet the specifications of one specific model copier—when these toners were heated to fuser temperature (180-200 °C). The objective was to assess how potential volatile organic compound (VOC) emissions from the toner for a given copier can vary, depending upon the production run and the supplier. Tests were performed on a series of toner (and associated raw polymer feedstock) samples obtained directly from a toner manufacturer, representing two production runs using a nonvented extrusion process, and on toner cartridges purchased from two local retailers, representing three different production lots (histories unknown). The results showed that the retailer toners consistently had up to 350% higher emissions of some major compounds (expressed as |ig of compound emit-ted/g of toner), and up to 100% lower emissions of others, relative to the manufacturer toners (p ≤ 0.01). The manufacturer toners from one production run had emissions of certain compounds, and of total VOCs, that were modestly higher (13-18%) than those from the other run (p ≤ 0.01). The emission differences between the retailer and manufacturer toners are probably due to differences     

Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Effects of feed-supplementation and hide-spray application of two sources of tannins on enteric and hide bacteria of feedlot cattle

Pathogenic bacteria attached to the hide or shed in the feces of cattle at slaughter can contaminate carcasses intended to be processed for human consumption. Therefore, new pre-harvest interventions are needed to prevent the carriage and excretion of foodborne pathogens in cattle presented to the processing plant. The objectives of this study were to examine the antimicrobial effects of hydrolysable tannin-rich chestnut and condensed tannin-rich mimosa extracts on bacterial indicators of foodborne pathogens when applied as a hide-intervention and as a feed additive to feedlot cattle. Water (control) or solutions (3 % wt/vol) of chestnut- and mimosa-extract treatments were sprayed (25 mL) at the left costal side of each animal to a 1000 cm² area, divided in four equal quadrants. Hide-swabs samples obtained at pre-, 2-min, 8-h, and 24-h post-spray application were cultured to enumerate Escherichia coli/total coliforms and total aerobic plate counts. In a second experiment, diets supplemented without (controls) or with (1.5 % of diet dry matter) chestnut- or mimosa-extracts were fed during a 42–day experimental feeding period. Weekly fecal samples starting on day 0, and rumen fluid obtained on days 0, 7, 21 or 42 were cultured to enumerate E.coli/total coliforms and Campylobacter. Tannin spray application showed no effect of treatment or post-application-time (P> 0.05) on measured bacterial populations, averaging 1.7/1.8, 1.5/1.6 and 1.5/1.7 (log₁₀ CFU/cm²) for E. coli/total coliforms, and 4.0, 3.4 and 4.2 (log₁₀CFU/cm²) in total aerobes for control, chestnut and mimosa treatments, respectively. Mean (± SEM) ruminal E. coli and total coliform concentrations (log₁₀ CFU/mL) were reduced (P< 0.01) in steers fed chestnut-tannins (3.6 and 3.8 ± 0.1) in comparison with the controls (4.1 and 4.2 ± 0.1). Fecal E. coli concentrations were affected by treatment (P< 0.01), showing the highest values (log₁₀ CFU/g) in fecal contents from mimosa-fed steers compared to controls (5.9 versus 5.6 ± 0.1 SEM, respectively). Total coliforms (log CFU/g) showed the highest values (P< 0.01) in feces from chestnut- and mimosa-fed steers (6.0 and 6.1 ± 0.1 respectively) in comparison with controls (5.7 ± 0.1). Fecal Campylobacter concentrations (log₁₀CFU/g) were affected by treatment (P< 0.05), day (P< 0.001) and their interaction (P< 0.01) with the controls having lower concentrations than chestnut- and mimosa-fed steers (0.4, 1.0, and 0.8 ± 0.3, respectively). It was concluded that under our research conditions, tannins were not effective in decreasing measured bacterial populations on beef cattle hides. Additionally, chestnut tannin reduced E. coli and total coliforms within the rumen but the antimicrobial effect was not maintained in the lower gastrointestinal tract. Further research is necessary to elucidate the possible antimicrobial effects of tannins at site-specific locations of the gastrointestinal tract in beef cattle fed high-grain and high-forage diets.     

Effects of pen bedding and feeding high crude protein diets on manure composition and greenhouse gas emissions from a feedlot pen surface

Greenhouse gas (GHG) emissions from concentrated animal feeding operations vary by stage of production and management practices. The objective of this research was to study the effect of two dietary crude protein levels (12 and 16%) fed to beef steers in pens with or without corn stover bedding. Manure characteristics and GHG emissions were measured from feedlot pen surfaces. Sixteen equal-sized feedlot pens (19?×?23 m) were used. Eight were bedded approximately twice a week with corn stover and the remaining eight feedlot pens were not bedded. Angus steers (n = 138) were blocked by live weights (lighter and heavier) with 7 to 10 animals per pen. The trial was a 2?×?2 factorial design with factors of two protein levels and two bedding types (bedding vs. non bedding), with four replicates. The study was conducted from June through September and consisted of four ?28-day periods. Manure from each pen was scrapped once every 28 days and composite manure samples from each pen were collected. Air samples from pen surfaces were sampled in Tedlar bags using a Vac-U-Chamber coupled with a portable wind tunnel and analyzed with a greenhouse gas gas chromatograph within 24 hr of sampling. The manure samples were analyzed for crude protein (CP), total nitrogen (TN), ammonia (NH₃), total volatile fatty acid (TVFA), total carbon (TC), total phosphorus (TP), and potassium (K). The air samples were analyzed for methane (CH₄), carbon dioxide (CO₂), and nitrous oxide (N₂O) concentrations. The concentration of TN was significantly higher (p < 0.05) in manure from pens with cattle fed the high protein diets. The volatile fatty acids (VFAs) such as acetic, propionic, isobutyric, butyric, isovaleric, and valeric acids concentrations were similar across both treatments. There were no significant differences in pen surface GHG emissions across manure management and dietary crude protein levels.

Implications: Livestock manure produces odor and emits GHGs (CO₂, CH₄, and N₂O) at different stages of production and management practices that have significant environmental concerns. Thus, it is important to measure GHG contributions from different sources and develop appropriate mitigation strategies for minimizing GHG contribution from livestock production facilities. Two dietary protein levels (12 and 16%) fed to beef steers in pens with or without corn stover bedding were studied. The results indicated that dietary protein levels and bedding vs. no bedding had very little effect on GHG emissions and manure composition under open feedlot conditions in North Dakota climatic conditions and management practices.     

Evaluating Sources of Indoor Air Pollution

Evaluation of Indoor air pollution problems requires an understanding of the relationship between sources, air movement, and outdoor air exchange. Research is underway to investigate these relationships. A three-phase program is being implemented: 1) Environmental chambers are used to provide source emission factors for specific indoor pollutants; 2) An IAQ (Indoor Air Quality) model has been developed to calculate indoor pollutant concentrations based on chamber emissions data and the air exchange and air movement within the indoor environment; and 3) An IAQ test house is used to conduct experiments to evaluate the model results. Examples are provided to show how this coordinated approach can be used to evaluate specific sources of indoor air pollution. Two sources are examined: 1) para-dichlorobenzene emissions from solid moth repellant; and 2) particle emissions from unvented kerosene heaters.

The evaluation process for both sources followed the three-phase approach discussed above. Para-dichlorobenzene emission factors were determined by small chamber testing at EPA’s Air and Energy Engineering Research Laboratory. Particle emission factors for the kerosene heaters were developed In large chambers at the J. B. Pierce Foundation Laboratory. Both sources were subsequently evaluated in EPA’s IAQ test house. The IAQ model predictions showed good agreement with the test house measurements when appropriate values were provided for source emissions, outside air exchange, in-house air movement, and deposition on “sink” surfaces.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

Elk decision-making rules are simplified in the presence of wolves

The risk of predation drives many behavioral responses in prey. However, few studies have directly tested whether predation risk alters the way other variables influence prey behavior. Here we use information theory (Akaike’s Information Criterion, AICc) in a novel way to test the hypothesis that the decision-making rules governing elk behavior are simplified by the presence of wolves. With elk habitat use as the dependent variable, we test whether the number of independent variables (i.e., the size of the models) that best predict this behavior differ when wolves are present vs absent. Thus, we use AICc scores simply to determine the number of variables to which elk respond when making decisions. We measured habitat use using 2,288 locations from GPS collars on 14 elk, over two winters (14 elk winters), in the Gallatin Canyon portion of the Greater Yellowstone Ecosystem. We found that the use of three major habitat components (grass, conifer, sage) was sensitive to many variables on days that wolves were locally absent, with the best models (ΔAICc≤2) averaging 7.4 parameters. In contrast, habitat use was sensitive to few variables on days when wolves were present: the best models averaged only 2.5 parameters. Because fewer variables affect elk behavior in the presence of wolves, we conclude that elk use simpler decision-making rules in the presence of wolves. This simplification of decision-making rules implies that predation risk imposes selection pressures that do not allow prey to respond to other pressures in ways that they otherwise would. If the affected processes are important, then this indirect effect of predation is likely to be important.     

On the Estimation of Dispersal Kernels from Individual Mark-Recapture Data

We present a new method for estimating a distribution of dispersal displacements (a dispersal kernel) from mark-recapture data. One conventional method of calculating the dispersal kernel assumes that the distribution of displacements are Gaussian (e.g. resulting from a diffusion process) and that individuals remain within sampled areas. The first assumption prohibits an analysis of dispersal data that do not exhibit the Gaussian distribution (a common situation); the second assumption leads to underestimation of dispersal distance because individuals that disperse outside of sampling areas are never recaptured. Our method eliminates these two assumptions. In addition, the method can also accommodate mortality during a sampling period. This new method uses integrodifference equations to express the probability of spatial mark-recapture data; associated dispersal, survival, and recapture parameters are then estimated using a maximum likelihood method. We examined the accuracy of the estimators by applying the method to simulated data sets. Our method suggests designs for future mark-recapture experiments. Received: January 2004 / Revised: July 2005