Temporal variability of selected air toxics in the United States

Ambient measurements of hazardous air pollutants (HAPs, air toxics) collected in the United States from 1990 to 2005 were analyzed for diurnal, seasonal, and/or annual variability and trends. Visual and statistical analyses were used to identify and quantify temporal variations in air toxics at national and regional levels. Sufficient data were available to analyze diurnal variability for 14 air toxics, seasonal variability for 24 air toxics, and annual trends for 26 air toxics. Four diurnal variation patterns were identified and labeled invariant, nighttime peak, morning peak, and daytime peak. Three distinct seasonal patterns were identified and labeled invariant, cool, and warm. Multiple air toxics showed consistent decreasing trends over three trend periods, 1990–2005, 1995–2005, and 2000–2005. Trends appeared to be relatively consistent within chemically similar pollutant groups. Hydrocarbons such as benzene, 1,3-butadiene, styrene, xylene, and toluene decreased by approximately 5% or more per year at more than half of all monitoring sites. Concentrations of carbonyl compounds such as formaldehyde, acetaldehyde, and propionaldehyde were equally likely to have increased or decreased at monitoring sites. Chlorinated volatile organic compounds (VOCs) such as tetrachloroethylene, dichloromethane, and methyl chloroform decreased at more than half of all monitoring sites, but decreases among these species were much more variable than among the hydrocarbons. Lead particles decreased in concentration at most monitoring sites, but trends in other metals were not consistent over time.     

Reproducibility of regional apportionments of pollution aerosol in the Northeastern United States

Regional apportionments of sulfate and Se in pollution aerosol have been reproduced to within 10% for winter and summer at Narragansett, RI, and for summer at Underhill, VT, over a 3-yr period. Agreement of observed variability of apportionments with earlier estimates of their uncertainties served to empirically confirm both error-propagation methods and original uncertainties assigned to regional signatures. Winter apportionments at Underhill were more variable because of systematic differences in meteorology.     

Spatial distribution of source locations for particulate nitrate and sulfate in the upper-midwestern United States

Two back-trajectory analysis methods designed to be used with multiple site data, simplified quantitative transport bias analysis (SQTBA) and residence time weighted concentration (RTWC), were applied to nitrate and sulfate concentration data from two rural sites (the Mammoth Cave National Park and the Great Smoky Mountain National Park) and five urban sites (Chicago, Cleveland, Detroit, Indianapolis, and St. Louis) for an intensive investigation on the spatial patterns of origins for these two species in the upper-midwestern area. The study was made by dividing the data into five categories: all sites and all seasons, rural sites in summer, rural sites in winter, urban sites in summer, and urban sites in winter. A general conclusion was that the origins of the nitrate in these seven sites were mainly in the upper-midwestern areas, while the sulfate in these seven sites were mainly from the Ohio and Tennessee River Valley areas. The upper-midwestern areas are regions of high ammonia emissions rather than high NO_x emissions. In the winter, metropolitan areas showed the highest nitrate emission potential suggesting the importance of local NO_x emissions. In the summer, ammonia emissions from fertilizer application in the lower midwestern area made a significant contribution to nitrate in the rural sites of this study. The impact of the wind direction prevalence on the source spatial patterns was observed by comparing the urban and rural patterns of the summer. The differences between the results of two methods are discussed and suggestions for applying these methods are also provided.     

Detection and quantification of 2-methyltetrols in ambient aerosol in the southeastern United States

Filters collected from the Southeastern Aerosol Research and Characterization (SEARCH) air monitoring network were analyzed for the presence of 2-methyltetrols, namely 2-methylthreitol and 2-methylerythritol, two compounds that are products of the photooxidation of isoprene and have been detected in aerosol at a variety of sites around the globe. The 2-methytetrols were detected in ambient filter samples collected at the four SEARCH sites, Birmingham, AL, Centreville, AL, Pensacola, FL, and at Jefferson Street in Atlanta, GA, in late June 2004. Average atmospheric concentrations of 11.9 and 4.8 ng m⁻³ were measured for 2-methylerythritol and 2-methylthreitol, respectively, at the inland sampling sites, whereas average concentrations of 4.9 and 1.6 ng m⁻³ were measured at the coastal sampling location (Pensacola). On average, the aerosol loading from these two compounds accounts for approximately 0.42% and 0.21% of the organic mass collected on a given sampling day at the inland and coastal sites, respectively. The present data on these compounds, which are particulate-phase fingerprints of isoprene photooxidation, add to the growing body of ambient data on secondary organic aerosol from isoprene.     

Spatial and temporal distributions of airborne sulfate in parts of the United States

The current knowledge of the spatial and temporal distribution of airborne, water soluble sulfate is surveyed for two “scales” of atmospheric activity. The “urban” scale with episodes extending over a day or two over distances of about 100 km is illustrated for two comparable American cities, Los Angeles and New York. The regional scale with episodes extending up to several days over distances of 1000 km is exemplified by case studies in the greater eastern United States. Examination of available data reveals several features of the spatial and temporal variation in sulfate occurrence, including seasonal changes, and correlations with aerometric parameters. The importance of water vapor and air mass character on sulfate concentrations is assessed in both the urban and regional conditions. The results of initial attempts to simulate the impact of sulfur oxide emissions on ambient sulfate distributions are compared with an episode case extending over several days in July 1974.     

A survey of polycyclic musks in selected household commodities from the United States

Occurrence of the polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronapthalene (AHTN), in wastewater influent and effluent, as well as in surface waters, has been reported. HHCB and AHTN were also reported to occur in human and wildlife tissues. The major sources for HHCB and AHTN to wastewater are thought to be consumer products such as shampoos, deodorants, laundry detergents, and household surface cleaners. However, the levels of HHCB and AHTN in consumer products are not known. For evaluation of the sources of human and environmental exposures, characterization of levels of HHCB and AHTN in consumer products is needed. In this study, we measured concentrations of HHCB (Galaxolide), AHTN (Tonalide), and HHCB-lactone (Galaxolidone) from a variety of consumer products, including perfumes, body lotions, and deodorants. Concentrations of HHCB, AHTN, and HHCB-lactone in consumer products ranged from <5 ng/g to over 4000 microg/g, <5 ng/g to 451 microg/g, and <5 ng/g to 217 microg/g, respectively. The highest concentrations were found in perfumes, body creams and lotions, and deodorants. The results suggest that a wide variety of source materials exist for HHCB and AHTN, and that these materials are used on a daily basis.     

Fire and biofuel contributions to annual mean aerosol mass concentrations in the United States

We estimate the contributions from biomass burning (summer wildfires, other fires, residential biofuel, and industrial biofuel) to seasonal and annual aerosol concentrations in the United States. Our approach is to use total carbonaceous (TC) and non-soil potassium (ns-K) aerosol mass concentrations for 2001–2004 from the nationwide IMPROVE network of surface sites, together with satellite fire data. We find that summer wildfires largely drive the observed interannual variability of TC aerosol concentrations in the United States. TC/ns-K mass enhancement ratios from fires range from 10 for grassland and shrub fires in the south to 130 for forest fires in the north. The resulting summer wildfire contributions to annual TC aerosol concentrations for 2001–2004 are 0.26 μg C m⁻³ in the west and 0.14 μg C m⁻³ in the east; Canadian fires are a major contributor in the east. Non-summer wildfires and prescribed burns contribute on an annual mean basis 0.27 and 0.31 μg C m⁻³ in the west and the east, highest in the southeast because of prescribed burning. Residential biofuel is a large contributor in the northeast with annual mean concentration of up to 2.2 μg C m⁻³ in Maine. Industrial biofuel (mainly paper and pulp mills) contributes up to 0.3 μg C m⁻³ in the southeast. Total annual mean fine aerosol concentrations from biomass burning average 1.2 and 1.6 μg m⁻³ in the west and east, respectively, contributing about 50% of observed annual mean TC concentrations in both regions and accounting for 30% (west) and 20% (east) of total observed fine aerosol concentrations. Our analysis supports bottom-up source estimates for the contiguous United States of 0.7–0.9 Tg C yr⁻¹ from open fires (climatological) and 0.4 Tg C yr⁻¹ from biofuel use. Biomass burning is thus an important contributor to US air quality degradation, which is likely to grow in the future.     

Characterization of fine primary biogenic organic aerosol in an urban area in the northeastern United States

Scanning electron microscopy coupled to energy-dispersive x-ray spectroscopy (SEM/EDX) was used to quantify individual bioparticles in PM_2.5 samples collected during the Pittsburgh Air Quality Study. Microscopy-based estimates of primary biogenic organic aerosol (PBOA) mass were compared to carbohydrate mass associated with PM_2.5. Carbohydrates show substantial seasonal variations, with higher concentrations in the spring and the fall. During the summer, carbohydrates were about 30% of the estimated PBOA concentrations, but in the winter carbohydrate concentrations often greatly exceeded the PBOA mass estimate. Spores and insect detritus were the most abundant PBOA types in the summer samples, while winter samples were comprised predominantly of a mixture of microorganisms, insect and vegetative detritus. During the summer PBOA contributed on average 6.9 ± 5.4% by mass of the PM_2.5 versus 3.3 ± 1.4% of the PM_2.5 mass during the winter.     

Nitrogen use in the United States from 1961-2000 and potential future trends

Nitrogen inputs to the US from human activity doubled between 1961 and 1997, with most of the increase in the 1960s and 1970s. The largest increase was in use of inorganic N fertilizer, but emissions of NOx from fossil-fuel combustion also increased substantially. In 1961, N fixation in agricultural systems was the largest single source of reactive N in the US. By 1997, even though N fixation had increased, fertilizer use and NOx emissions had increased more rapidly and were both larger inputs. In both 1961 and 1997, two thirds of reactive N inputs were denitrified or stored in soils and biota, while one third was exported. The largest export was in riverine flux to coastal oceans, followed by export in food and feeds, and atmospheric advection to the oceans. The consumption of meat protein is a major driver behind N use in agriculture in the US Without change in diet or agricultural practices, fertilizer use will increase over next 30 years, and fluxes to coastal oceans may increase by another 30%. However, substantial reductions are possible.     

Spatial and temporal trends of precipitation chemistry in the United States, 1985-2002

A Seasonal Kendall Trend (SKT) test was applied to precipitation-weighted concentration data from 164 National Atmospheric Deposition Program National Trends Network (NADP/NTN) sites operational from 1985 to 2002. Analyses were performed on concentrations of ammonium, sulfate, nitrate, dissolved inorganic nitrogen (DIN, sum of nitrogen from nitrate and ammonium), and earth crustal cations (ECC, sum of calcium, magnesium, and potassium). Over the 18-year period, statistically significant (p< or =0.10) increases in ammonium concentrations occurred at 93 sites (58%), while just three sites had statistically significant ammonium decreases. Central and northern Midwestern states had the largest ammonium increases. The generally higher ammonium concentrations were accompanied by significant sulfate decreases (139 sites, 85%), and only one significant increase which occurred in Texas. In the west central United States there were significant nitrate increases (45 sites, 27%), while in the northeastern United States there were significant decreases (25 sites, 15%). Significant DIN decreases were observed in the northeastern United States (11 sites, 7%); elsewhere there were significant increases at 75 sites (46%). ECC decreased significantly at 65 sites (40%), predominantly in the central and southern United States, and increased at 11 sites (7%). The concentrations of sulfate, nitrate, and ammonium in precipitation have changed markedly over the time period studied. Such trends indicate changes in the mix of gases and particles scavenged by precipitation, possibly reflecting changes in emissions, atmospheric chemical transformations, and weather patterns.     

Geographic distribution of selected elements in the livers of polar bears from Greenland, Canada and the United States

To assess geographic distributions of elements in the Arctic we compared essential and non-essential elements in the livers of polar bears (Ursus maritimus) collected from five regions within Canada in 2002, in Alaska between 1994 and 1999 and from the northwest and east coasts of Greenland between 1988 and 2000. As, Hg, Pb and Se varied with age, and Co and Zn with gender, which limited spatial comparisons across all populations to Cd, which was highest in Greenland bears. Collectively, geographic relationships appeared similar to past studies with little change in concentration over time in Canada and Greenland for most elements; Hg and Se were higher in some Canadian populations in 2002 as compared to 1982 and 1984. Concentrations of most elements in the polar bears did not exceed toxicity thresholds, although Cd and Hg exceeded levels correlated with the formation of hepatic lesions in laboratory animals.     

Characterization of spatially homogeneous regions based on temporal patterns of fine particulate matter in the continental United States

Statistical analyses of time-series or spatial data have been widely used to investigate the behavior of ambient air pollutants. Because air pollution data are generally collected in a wide area of interest over a relatively long period, such analyses should take into account both spatial and temporal characteristics. The objective of this study is 2-fold: (1) to identify an efficient way to characterize the spatial variations of fine particulate matter (PM2.5) concentrations based solely upon their temporal patterns, and (2) to analyze the temporal and seasonal patterns of PM2.5 concentrations in spatially homogenous regions. This study used 24-hr average PM2.5 concentrations measured every third day during a period between 2001 and 2005 at 522 monitoring sites in the continental United States. A k-means clustering algorithm using the correlation distance was used to investigate the similarity in patterns between temporal profiles observed at the monitoring sites. A k-means clustering analysis produced six clusters of sites with distinct temporal patterns that were able to identify and characterize spatially homogeneous regions of the United States. The study also presents a rotated principal component analysis (RPCA) that has been used for characterizing spatial patterns of air pollution and discusses the difference between the clustering algorithm and RPCA.     

Trends in atmospheric reactive nitrogen for the Eastern United States

Reactive nitrogen can travel far from emission sources and impact sensitive ecosystems. From 2002 to 2006, policy actions have led to decreases in NO(x) emissions from power plants and motor vehicles. In this study, atmospheric chemical transport modeling demonstrates that these emissions reductions have led to a downward trend in ambient measurements of transported reactive nitrogen, especially atmospheric concentrations and wet deposition of nitrate. The trend in reduced nitrogen, namely ammonium, is ambiguous. As reduced nitrogen becomes a larger fraction of the reactive nitrogen budget, wide-spread NH(3) measurements and improved NH(3) emissions assessments are a critical need.     

Effects of changes in sulfate,ammonia, and nitric acid on particulate nitrate concentrations in the southeastern United States

A thermodynamic equilibrium model, Simulating Composition of Atmospheric Particles at Equilibrium (SCAPE2), was used to investigate the response of fine particulate NO3(-) to changes in concentrations of HNO3, NH3, and SO4(2-) in the southeastern United States. The data consisted of daily, 24-hr time resolution measurements from the Aerosol Research Inhalation Epidemiology Study (ARIES) Jefferson Street (Atlanta) site and five other sites of the Southeastern Aerosol Research and Characterization Project (SEARCH). Reductions of total NH3 (gas-phase NH3 plus particulate NH4(+)), total NO3(-) (HNO3 plus particulate NO3(-)), SO4(2-), or combined total NO3(-) (HNO3 plus particulate NO3(-)) with SO4(2-) were used to estimate the effects of changing emission levels. The conversion of SO2 to SO4(2-) and NO2 to HNO3 involves additional nonlinear reactions not incorporated into the model. For all sites, fine particulate NO3(-) concentrations decreased in response to reductions of either NH3 or total NO3(-), but the particulate NO3(-) decreases were greater for the NH3 reductions than for the total NO3(-) reductions. Particulate NO3(-) concentrations increased in response to reductions of SO4(2-). For the combined reduction (total NO3(-) plus SO4(2-)), the resulting particulate NO3(-) concentrations were on average no different than the base-case NO3(-) levels. Measurements of fine particulate NO3(-) and HNO3 support the modeling conclusions and indicate that particulate NO3(-) formation is limited by the availability of NH3 at most times at all SEARCH sites.     

Elemental carbon and sulfate aerosols over a rural mountain site in the northeastern United States: Regional emissions and implications for climate change

The effect of elemental carbon (EC) on global as well as regional climate forcing is potentially very important. However, the EC data for northeastern U.S. is sparse. Daily EC concentrations, [EC], and [SO₄] were measured in the northeastern U.S. at a regionally representative rural site, Whiteface Mountain (WFM; 44.366°N, 73.903°W, 1.5 km amsl, above mean sea level), New York (NY), for 1997. The air mass origin was determined using 6-h backward in time air trajectories obtained from the Hybrid Single-Particle Lagrangian Integrated Trajectory Model (HYSPLIT 4). [EC] and [SO₄] were highly variable and influenced by synoptic–scale meteorology (rainy vs dry periods). The maximum daily [EC] and [SO₄] were 364 ± 55 and 28,800 ± 3000 ng m^?3, respectively. [EC] and [SO₄] also showed seasonal variations at WFM. Occurrences of high daily [EC] were mainly in spring months, while peak daily [SO₄] concentrations occurred in summer months. This behavior of aerosols is due to the fact that the sources of EC and SO₄ are not the same and also due to the enhanced photochemical activity during summer months that increased the production of SO₄ from SO₂. High [EC] and [SO₄] values were associated with westerly air flow from the industrialized Midwestern U.S. Sector analysis using HYSPLIT 4 air trajectories showed that regions lying between the southwest and northwest of the WFM contributed 81% and 83% of the [EC] and [SO₄], respectively. The monthly net direct radiative forcing for shortwave (SW) due to EC and SO₄ aerosols at the top of the atmosphere (TOA) varied from ?0.05 to ?0.50 W m^?2, with an annual average of ?0.20 ± 0.15 W m^?2 that gives a net cooling effect. Average net radiative forcing at WFM for clear sky is lower than the global average radiative forcing reported by IPCC (Foster and Ramaswamy, 2007).     

Particulate Air Pollution In the United States

A study was conducted to identify, characterize, and quantify the national particulate air pollution problem from stationary sources. Particulate emissions from stationary sources were determined from data on emission factors, grain loadings, and material balances. The principal method used for establishing the tonnage emitted by an industry utilized uncontrolled emission factors. Total tonnage emitted by a given industry was calculated from four quantities: (1) an emission factor for the uncontrolled source; (2) the total tonnage processed per year by the industry; (3) the efficiency of control equipment used; and (4) the percentage of production capacity equipped with control devices.

Particulate emissions from stationary sources in the United States currently total approximately 18 X 10⁶ ton/yr. The major stationary sources of particulates include electric power generation plants, the crushed stone industry, the forest products industry, agriculture and related operations, the cement industry, and the iron and steel industry.

Three methods were developed to project the total quantity of particulate pollutants emitted up to the year 2000. In making these forecasts, these factors were considered (1) changes in production capacity; (2) improvements in control devices; and (3) regulatory action to enforce installation of control equipment.

These forecasts indicate that particulate emissions can be reduced from the current level of 18 X 10⁶ ton/yr to 3 X 10⁶ ton/yr by 2000 based on the most optimistic forecast. The projections also suggest that major reductions of particulate matter will most likely occur by installation of control equipment on uncontrolled sources and by shifts to more efficient types of collection equipment on existing controlled sources.     

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States

Although the use of the insecticide γ-hexachlorocyclohexane (HCH) is now prohibited in many countries because of its hazardousness, stockpiles of γ-HCH still exist. In this study, we subjected γ-HCH to mechanochemical (MC) treatment with a planetary ball mill in the presence of CaO to investigate the feasibility of using this method for the treatment of γ-HCH stockpiles. We confirmed the degradation of γ-HCH and investigated the degradation mechanism. The major intermediates were identified to be 1,3,4,5,6-pentachlorocyclohexene (γ-PCCH) and chlorobenzenes (CBzs). Analysis of the steric structure of γ-HCH and identification of the degradation intermediates suggested that successive dehydrochlorination led to the formation of trichlorobenzenes. Products of further degradation (dichlorobenzenes, monochlorobenzene, and benzene) were also detected. Surprisingly, methane and ethane were also detected, which suggests cleavage of the C-C bonds of the cyclohexane ring and hydrogenation. All of the chlorine atoms in the γ-HCH could be transformed into inorganic chloride compounds by the MC treatment with CaO. Our results indicate that γ-HCH can be completely dechlorinated by MC treatment.     

The Gas Supply Situation in the United States

The body of information presented in this paper is directed to those individuals who require information on the present natural gas supply and demand relationship and the prospects for future changes, including individuals concerned with air quality control and the use of natural gas for combating air pollution.

If natural gas could continue to capture large shares of the energy market, as in the past when supply was not a growth inhibiting factor, annual demand for gas is projected to increase to 34.5 and 46.4 trillion cubic feet in 1980 and 1990, respectively. Annual production levels which could be supported by presently proven reserves and anticipated future reserve additions are estimated to peak in the mid-1970’s and decline to about 18 trillion cubic feet in 1990.

When viewed from the perspective of anticipated indigenous supply deficiencies, the acquisition of supplemental sources of gas becomes of paramount importance. Pipeline imports, the only substantive supplemental source presently available, could almost double by 1980 and be about 2 trillion cubic feet annually in 1990.

Available volumes of gas from Alaska could be 0.7 trillion cubic feet in 1980 and could increase to 2.3 trillion cubic feet annually by 1990. Actual initial deliveries of gas are inextricably related to construction of an oil pipeline from Prudhoe Bay. Construction delays postpone initial delivery dates for gas as well as oil.

Advancements in cryogenic transportation and storage technologies have made the heretofore largely untapped supplies of gas from several countries with limited internal markets available to the United States as LNG. Annual LNG imports could be about 0.3 trillion cubic feet in 1975 and perhaps 2 and 4 trillion cubic feet by 1980 and 1990, respectively.

Pipeline quality gas from coal presents the prospect for a supplemental source of gaseous fuel independent of foreign sources and free from balance of payments problems. The first pipeline quality gas from coal may be expected by 1976, and by 1980 perhaps 0.3 trillion cubic feet could be provided annually from this source; in 1990, 3.3 trillion cubic feet might be available. An additional, but presently unqualified, source of synthetic gas will be the conversion of liquid hydrocarbons.

In the aggregate, supplemental gas supplies are anticipated to total about 4.6 and 11.5 trillion cubic feet annually by 1980 and 1990, respectively. While demand for gas is anticipated to increase, domestic conventional gas production is projected to peak in the mid-1970’s and decrease somewhat thereafter. As a consequence, a continuing gas supply-demand imbalance is anticipated.