Ozone Air Quality over North America: Part II—An Analysis of Trend Detection and Attribution Techniques

ABSTRACT

Assessment of regulatory programs aimed at improving ambient O₃ air quality is of considerable interest to the scientific community and to policymakers. Trend detection, the identification of statistically significant long-term changes, and attribution, linking change to specific clima-tological and anthropogenic forcings, are instrumental to this assessment. Detection and attribution are difficult because changes in pollutant concentrations of interest to policymakers may be much smaller than natural variations due to weather and climate. In addition, there are considerable differences in reported trends seemingly based on similar statistical methods and databases. Differences arise from the variety of techniques used to reduce nontrend variation in time series, including mitigating the effects of meteorology and the variety of metrics used to track changes. In this paper, we review the trend assessment techniques being used in the air pollution field and discuss their strengths and limitations in discerning and attributing changes in O₃ to emission control policies.     

Ozone Air Quality over North America: Part I—A Review of Reported Trends

ABSTRACT

Ozone and precursor trends can be used to measure the effectiveness of regulatory programs that have been implemented. In this paper, we review trends in the concentrations of O₃, NO_x, and HCs over North America that have been reported in the literature. Although most existing trend studies are confounded by meteorological variability, both the raw data trends and the trends adjusted for meteorology collectively indicate a general decreasing trend in O concentrations in most areas of the United States during 1985-1996. In Canada, mean daily maximum 1-hr O₃ concentrations at urban sites show mixed trends with a majority of sites showing an increase from 1980 to 1993. Mean daily maximum 1-hr O₃ at most regionally representative Canadian sites appears to decrease from 1985 to 1993 or shows no significant change. There are far fewer data and analyses of NO_x and HC trends. Available studies covering various ranges of years indicate decreases in ambient NO_x and HC concentrations in Los Angeles, CA, decreases in HC concentrations in northeastern U.S. cities, and decreases in NO concentrations in Canadian cities. Two key needs are long-term HC and NO_x measurements, particularly at rural sites, and a systematic comparison of trend detection techniques on a reference data set.     

Design Scenario for the Radioisotopic Estimation of the Biogenic Component of Airborne Particles

Abstract

An experimental design is described to estimate the fraction of secondary fine particle from the biogenic component of volatile organic compounds (VOCs) in the atmosphere using radiocarbon isotopic abundance ratios. The method distinguishes between “modern” carbon (C), and “old” C of primary and secondary origins based on three components, condensed-phase organic carbon (OC), semi-volatile particulate compounds (SVOCs), and VOCs. The method depends on interpretation of diurnal and seasonal variation in OC, SVOC, and VOC concentrations. Sampling employs a filter-denuder unit, which collects the three C components for isotopic analysis. The samples are collected repetitively for a daily sequence of the same hourly intervals covering diurnal periods with similar meteorological conditions. Collected C is thermally treated to separate OC from black carbon on filters and VOCs or SVOCs from adsorbents, with all four fractions individually oxidized to carbon dioxide to determine the radiocarbon content by accelerator mass spectrometry. Using C isotope abundance, the data are interpreted for fractions of primary modern C and secondary modern C as estimated from averaging diurnal and seasonal variations in the concentration data. As support for interpretation, samples of OC, SVOCs, and VOCs would be analyzed for speciation to identify source indicator species present.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Quality Science in the Courtroom: U.S. EPA Data Quality and Peer Review Policies and Procedures Compared to the Daubert Factors

Protection of the environment is critically dependent on the quality of data used in decision making. Whether the decisions are part of the scientific process or relate to application of the laws governing people and their living conditions, good quality data are required/needed by two disciplines with distinct differences. This paper examines some differences between science and the law, provides a brief history of science in law, discusses the effects of law on science, compares United States Environmental Protection Agency (U.S. EPA) guidance and U.S. Supreme Court credible science criteria. This paper further speculates on the future use of science data by the courts.     

Air Pollution Control Measures for Hot Dip Galvanizing Kettles

ABSTRACT

Three commercially available conversion varnish coating “systems” (stain, sealer, and topcoat) were selected for an initial scoping study. The total volatile content of the catalyzed varnishes, as determined by U.S. Environmental Protection Agency (EPA) Method 24, ranged from 64 to 73 weight%. Uncombined (free) formaldehyde concentrations, determined by a sodium sulfite titration method, ranged from 0.15 to 0.58 weight% of the uncatalyzed varnishes. Each sealer and topcoat was also analyzed by gas chromatography (EPA Method 311). The primary volatile organic constituents included methyl ethyl ketone (MEK), isobutanol, n-butanol, methyl isobutyl ketone (MIBK), toluene, ethylbenzene, the xylenes, and 1,2,4-trimethylbenzene.     

Odor Determination Techniques for Air Pollution Control

Abstract

An airborne lidar was used to study the smoke plume from the burning of a controlled oil spill on the ocean. The ratio of the amount of light (at a wavelength, λ, of 0.532 u.m) backscattered by the smoke to the amount of light extinguished by the smoke was determined by measuring the strength of a laser beam after it had passed through the smoke plume, been reflected from the ocean, and passed through the smoke plume again, and comparing this to the strength of the laser beam reflected directly from the ocean. The optical depth of the smoke (at λ = 0.532 µm) was typically between 0.2 and 0.5. The mass fluxes of smoke particles that passed through four vertical cross sections of the (nonsteady state) smoke plume were estimated from lidar measurements to be 142, 175, 423, and 414 g ^s-1, compared to an average smoke mass production rate of ~770 g s^-1. The spatial distribution of smoke mass along the long axis of the plume was also estimated from the lidar measurements; derived smoke mass concentrations were generally <300 µg ^m-3, with a few isolated values up to ~800 µg ^m-3.     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 × 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre^?1, six plots were mixed with sewage sludge (SS) at 15 t acre^?1, and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO₃, NH₄, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO₃-N and NH₄-N) in runoff water than SS treatments. Total marketable yield (lbs acre^?1) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

An Empirical Model for Forecasting Maximum Daily Ozone Levels in the Northeastern U.S.

A stepwise multiple regression procedure was employed to develop the best .fit equation relating maximum afternoon ozone concentrations to meteorological and emission factors along a 24h upwind air parcel trajectory. The equation was developed using ozone data from receptor sites in Northern New Jersey and the resulting correlation coefficient was 0.96. The four most significant variables were the upwind ozone maximum on the previous day, today’s maximum temperature, the previous day’s upwind maximum temperature and the mean wind speed from the surface to 1000 m. The model was also successfully tested at 5 other sites in the Northeastern Quadrant of the United States. The results indicate that the model could be a potentially useful tool for air pollution forecasters in predicting maximum ozone concentrations in this quadrant of the country.