Continuous and filter-based measurements of PM2.5 nitrate and sulfate at the Fresno Supersite

PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.     

Design and Testing of a New Size Classifying Isokinetic Sequential Aerosol Sampler

Two versions of a size-classifying isokinetic sequential aerosol sampler (SCISAS) have been designed, built, tested, and deployed in a field program in the southwestern United States. The SCISAS units can operate at unattended sites, exposing four or more filter types simultaneously, in two size ranges, for six sampling time Intervals. Design considerations included theoretical estimates of aerosol particle losses in the 0-15 μm size range.

SCISAS prototypes have been tested to evaluate their sampling efficiency as a function of flow rate, the sensitivity of the sampling efficiency to isokinetic matching within the SCISAS sampling stack, the equivalency of their sampling ports, and their passive deposition characteristics. The prototypes were also compared to several other types of aerosol filtration samplers already in common use. These tests show that particle loss mechanisms within the SCISAS usually cause no more than 5 percent losses, and that the SCISAS units agree, within one to two measurement uncertainty intervals, with other types of aerosol samplers.     

Air Quality Measurements from the Fresno Supersite

ABSTRACT

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, HNO₃, peroxyacetyl nitrate [PAN], NH₃); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

A Special Issue from the NARSTO Symposium on Tropospheric Aerosols

This dedicated issue of the Journal of the Air & Waste Management Association contains nine peer-reviewed scientific papers that were presented at the NARSTO Symposium on Tropospheric Aerosols: Science and Decisions in an International Community, held October 24-26, 2000, in Querétaro, Mexico.¹ Other peer-reviewed papers^2-9 appear in a companion issue of Science of the Total Environment to be published in February 2002. More than 130 papers were presented in platform and poster sessions at the meeting. Approximately 28% of the technical presentations dealt with topics from Mexico, and 15% related to Canada, with the remainder discussing U.S. and global topics.     

Measurement of Ultrafine Particle Size Distributions from Coal-, Oil-, and Gas-Fired Stationary Combustion Sources

Abstract

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h^?1 and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Ammonium Nitrate,Nitric Acid,and Ammonia Equilibrium in Wintertime Phoenix,Arizona

A secondary aerosol equilibrium model, SEQUILIB, is applied to evaluate the effects of emissions reductions from precursor species on ambient concentrations during the winter in Phoenix, Arizona. The model partitions total nitrate and total ammonia to gas-phase nitric acid and ammonia and to particle-phase ammonium nitrate. Agreement between these partitions and ambient measures of these species was found to be satisfactory. Equilibrium isopleths were generated for various ammonium nitrate concentrations corresponding to high and low humidity periods which occurred during sampling. These diagrams show that ammonia is so abundant in Phoenix that massive reductions in its ambient concentrations would be needed before significant reductions in particulate ammonium nitrate would be observed. When total nitrate is reduced by reductions in its nitrogen oxides precursor, proportional reductions in particulate nitrate are expected. Many of the complex reactions in SEQUILIB do not apply to Phoenix, and its ability to reproduce ambient data in this study does not guarantee that it will be as effective in areas with more complex chemistry. Nevertheless, the nitrate chemistry in SEQUILIB appears to be sound, and it is a useful model for addressing the difficult apportionment of secondary aerosol to its precursors.     

The destruction of ground water threatening pesticides using high intensity UV light

Abstract

A high‐intensity short‐wavelength UV light system was studied for its ability to degrade the pesticides carbofuran, fenamiphos sulfoxide (nemacur sulfoxide), and propazine in aqueous solutions. Half‐lives, rate constants, and breakdown products were determined for all chemicals. The presence of hydrogen peroxide, an oxidant and potential source of hydroxyl radicals, had no effect on the rate of breakdown of any of the chemicals investigated. Short‐wavelength UV light appears to be solely responsible for the observed pesticide breakdown. The breakdown of all three pesticides followed first order kinetics. Carbofuran, nemacur sulfoxide, and propazine had half lives of 3.9, 1.1, and 3.9 minutes, respectively. Breakdown product analysis was performed using capillary gas chromatography/mass spectrometry.     

Response of Algal Biomass to Large‐Scale Nutrient Controls in the Clark Fork River,Montana, United States1

Suplee, Michael W., Vicki Watson, Walter K. Dodds, and Chris Shirley, 2012. Response of Algal Biomass to Large‐Scale Nutrient Controls in the Clark Fork River, Montana, United States. Journal of the American Water Resources Association (JAWRA) 48(5): 1008‐1021. DOI: 10.1111/j.1752‐1688.2012.00666.x Abstract: Nutrient pollution is an ongoing concern in rivers. Although nutrient targets have been proposed for rivers, little is known about long‐term success of programs to decrease river nutrients and algal biomass. Twelve years of summer data (1998‐2009) collected along 383 km of the Clark Fork River were analyzed to ascertain whether a basin‐wide nutrient reduction program lowered ambient total nitrogen (TN) and total phosphorus (TP) concentrations, and bottom‐attached algal biomass. Target nutrient and algal biomass levels were established for the program in 1998. Significant declines were observed in TP but not TN along the entire river. Downstream of the city of Missoula, TP declined below a literature‐derived TP saturation breakpoint and met program targets after 2005; TN was below targets since 2007. Algal biomass also declined significantly below Missoula. Trends there likely relate to the city’s wastewater facility upgrades, despite its 20% population increase. Upstream of Missoula, nutrient reductions were less substantial; still, TP and TN declined toward saturation breakpoints, but no significant reductions in algal biomass occurred, and program targets were not met. The largest P‐load reduction to the river was from a basin‐wide phosphate laundry detergent ban set 10 years before, in 1989. We document that nutrient reductions in rivers can be successful in controlling algal biomass, but require achievement of concentrations below saturation and likely close to natural background.