Chemical behavior of residential lead in urban yards in the United States

Long after federal regulations banned the use of lead-based paints and leaded gasoline, residential lead remains a persistent challenge. Soil lead is a significant contributor to this hazard and an improved understanding of physicochemical properties is likely to be useful for in situ abatement techniques such as phytoremediation and chemical stabilization. A laboratory characterization of high-lead soils collected from across the United States shows that the lead contaminants were concentrating in the silt and clay fractions, in the form of discrete particles of lead, as observed by scanning electron microscopy coupled with energy dispersive X-ray analysis. Soil lead varied widely in its solubility behavior as assessed by sequential and chelate extractions. Because site-specific factors (e.g., soil pH, texture, etc.) are believed to govern the solubility of the lead, understanding the variability in these characteristics at each site is necessary to optimize in situ remediation or abatement of these soils.     

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.     

Dibenzo-p-dioxins in the environment from ceramics and pottery produced from ball clay mined in the United States

Processed ball clay samples used in the production of ceramics and samples of the ceramic products were collected and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs). The processed ball clay had average PCDD concentrations of 3.2 ng/g toxic equivalents, a congener profile, and isomer distribution consistent with those found previously in raw ball clay. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. The final fired ceramic products were found to be free of PCDDs/PCDFs at the LODs. A consideration of the conditions involved in the firing process suggests that the PCDDs, if not destroyed, may be released to the atmosphere and could represent an as yet unidentified source of dioxins to the environment. In addition, the PCDDs in clay dust generated during manufacturing operations may represent a potential occupational exposure.     

Dibenzo-p-dioxins in the environment from ceramics and pottery produced from ball clay mined in the United States

Processed ball clay samples used in the production of ceramics and samples of the ceramic products were collected and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs). The processed ball clay had average PCDD concentrations of 3.2 ng/g toxic equivalents, a congener profile, and isomer distribution consistent with those found previously in raw ball clay. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. The final fired ceramic products were found to be free of PCDDs/PCDFs at the LODs. A consideration of the conditions involved in the firing process suggests that the PCDDs, if not destroyed, may be released to the atmosphere and could represent an as yet unidentified source of dioxins to the environment. In addition, the PCDDs in clay dust generated during manufacturing operations may represent a potential occupational exposure.     

Ozone in the urban southeastern United States

Ozone measurements (daily maximum values) from the Aerometric Information Retrieval System database are analyzed for selected sites, during 1980 to 1988, in southeastern USA. Frequency distributions, for most sites during most years, show a typical bell-shaped curve with the higher frequency around the yearly daily maximum ozone mean of about 100 to about 110 microg m(-3) (50-55 ppbv). Abnormal years in ozone concentration may skew the distribution as the mean shifts. A correlation of daily maximum ozone concentrations above 140 microg m(-3) (70 ppbv) between sites shows a division between the sites in the northern protion of the region and those in the southern portion of the region. Variations in ozone levels are well correlated over distances of several hundred kilometers, suggesting that high values are associated with synoptic scale episodes. An ozone exposure analysis also shows higher ozone exposures (250-300 ppm days) in the northerly sites as compared to the southerly sites (150-170 ppm days).     

Rural ozone in the southeastern United States

Ozone measurements are reported for five rural sites in the Tennessee Valley region of the southeastern U.S. for periods ranging from 18 to 83 months during the years 1977 through 1984. Rural ozone (O₃) levels were found to equal or exceed urban values for the same region. The daily maximum 1-h average concentration was found to peak during the summer months, while the 24-h average concentrations were greatest in the spring. The annual cycle of daily maximum concentrations is related to the seasonal photochemical cycle. The annual cycle in 24-h average concentrations is best explained by the combined effects of the annual cycles in solar intensity and noctural O₃ depletion. There was no indication that stratospheric intrusions exhibited a significant influence on the annual O₃ cycles. Evidence was found for elevated O₃ levels during touchdown of plumes from large power plants. No long-term trend in rural O₃ concentrations, either daily maxima or means, was discernible.     

Real-time bias-adjusted O3 and PM2.5 air quality index forecasts and their performance evaluations over the continental United States

The National Air Quality Forecast Capacity (NAQFC) system, which links NOAA’s North American Mesoscale (NAM) meteorological model with EPA’s Community Multiscale Air Quality (CMAQ) model, provided operational ozone (O₃) and experimental fine particular matter (PM_2.5) forecasts over the continental United States (CONUS) during 2008. This paper describes the implementation of a real-time Kalman Filter (KF) bias-adjustment technique to improve the accuracy of O₃ and PM_2.5 forecasts at discrete monitoring locations. The operational surface-level O₃ and PM_2.5 forecasts from the NAQFC system were post-processed by the KF bias-adjusted technique using near real-time hourly O₃ and PM_2.5 observations obtained from EPA’s AIRNow measurement network. The KF bias-adjusted forecasts were created daily, providing 24-h hourly bias-adjusted forecasts for O₃ and PM_2.5 at all AIRNow monitoring sites within the CONUS domain. The bias-adjustment post-processing implemented in this study requires minimal computational cost; requiring less than 10 min of CPU on a single processor Linux machine to generate 24-h hourly bias-adjusted forecasts over the entire CONUS domain.The results show that the real-time KF bias-adjusted forecasts for both O₃ and PM_2.5 have performed as well as or even better than the previous studies when the same technique was applied to the historical O₃ and PM_2.5 time series from archived AQF in earlier years. Compared to the raw forecasts, the KF forecasts displayed significant improvement in the daily maximum 8-h O₃ and daily mean PM_2.5 forecasts in terms of both discrete (i.e., reduced errors, increased correlation coefficients, and index of agreement) and categorical (increased hit rate and decreased false alarm ratio) evaluation metrics at almost all locations during the study period in 2008.     

Vegetation exposure to ozone over the continental United States: Assessment of exposure indices by the Eta-CMAQ air quality forecast model

The main use of air quality forecast (AQF) models is to predict ozone (O₃) exceedances of the primary O₃ standard for informing the public of potential health concerns. This study presents the first evaluation of the performance of the Eta-CMAQ air quality forecast model to predict a variety of widely used seasonal mean and cumulative O₃ exposure indices associated with vegetation using the U.S. AIRNow O₃ observations. These exposure indices include two concentration-based O₃ indices, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations, respectively), and three cumulative exposure-based indices, SUM06 (the sum of all hourly O₃ concentrations ≥ 0.06 ppm), W126 (hourly concentrations weighed by a sigmoidal weighting function), and AOT40 (O₃ concentrations accumulated over a threshold of 40 ppb during daylight hours). During a three-month simulation (July–September 2005), the model over predicted the M7 and M12 values by 8–9 ppb, or a NMB value of 19% and a NME value of 21%. The model predicts a central belt of high O₃ extending from Southern California to Middle Atlantic where the seasonal means, M7 and M12 (the seasonal means of daytime 7-h and 12-h O₃ concentrations), are higher than 50 ppbv. In contrast, the model is less capable of reproducing the observed cumulative indices. For AOT40, SUM06 and W126, the NMB and NME values are two- to three-fold of that for M7, M12 or peak 8-h O₃ concentrations. The AOT40 values range from 2 to 33 ppm h by the model and from 1 to 40 ppm h by the monitors. There is a significantly higher AOT40 value experienced in the United States in comparison to Europe. The domain-wide mean SUM06 value is 14.4 ppm h, which is about 30% higher than W126, and 40% higher than AOT40 calculated from the same 3-month hourly O₃ data. This suggests that SUM06 and W126 represent a more stringent standard than AOT40 if either the SUM06 or the W126 was used as a secondary O₃ standard. Although CMAQ considerably over predicts SUM06 and W126 values at the low end, the model under predicts the extreme high exposure values (>50 ppm h). Most of these extreme high values are found at inland California sites. Based on our analysis, further improvement of the model is needed to better capture cumulative exposure indices.     

Development of continental scale multimedia contaminant fate models: integrating GIS

The incentives and approaches for modelling chemical fate at a continental scale are discussed and reviewed. It is suggested that a multi-media model consisting of some 20-30 regions, each of which contains typically seven environmental compartments represents a reasonable compromise between the issues of the need for detailed resolution, avoidance of excessive data demands and inherent complexity and transparency. Strategies adopted in compiling the Berkley-Trent (BETR) model for North America are discussed and used to illustrate the issues of selecting appropriate number and nature of segments, treatment of air and water flows and the acquisition of environmental data. It is suggested that GIS software can play a valuable role in gathering and processing such data and in the display and interpretation of the results of the model assessment. The BETR model will be a useful tool for describing the nature of persistence and long-range transport of chemicals of concern in the North American environment.     

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.     

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.     

The legacy of large dams in the United States

The sustainability of large dams has been questioned on several grounds. One aspect that has been less explored is that the development of dams and reservoirs often enables agricultural expansion and urban growth, which in turn increase water consumption. As such, dam development influences, while being influenced by, the spatial and temporal distribution of both supply and demand of water resources. In this paper, we explore the interplay between large dams, patterns of population growth and agricultural expansion in the United States over the past two centuries. Based on a large-scale analysis of spatial and temporal trends, we identify three distinct phases, in which different processes dominated the interplay. Then, we focus on agricultural water use in the Southwest region (Arizona, California and Nevada) and explore chicken-and-egg dynamics where water supply partly meets and partly fuels water demand. Lastly, we show that the legacy of dams in the United States consists of a lock-in condition characterized by high levels of water consumption, especially in the Southwest, which leads to severe water crises and groundwater overexploitation when droughts occur.     

Regional visibility modeling for the Eastern United States

Visibility modeling over long transport distances is complicated not only by the chemical and removal processes, but also by the multiplicity of sources from different areas that contribute to the particle and gaseous concentrations—and visibility impairment—at specific locations. To study interregional pollutant exchanges and their effect on visibility, a regional model has been developed and applied to the eastern United States and the visibility reduction budgeted according to area of origin. The new model, called VISMAP-1, produces short-term (three-hour) and long-term (monthly) sulfate concentrations; visibility calculations are made by applying a mass-to-light-scattering function to the aerosol concentrations. This function is weighted according to relative humidity to account for hygroscopic particle growth. One of the most useful features of this model is its capability to budget fine-particulate and gaseous concentrations in various receptor regions according to the contribution of source regions.In this analysis for visibility effects, three-hour SURE (Sulfate Regional Experiment) sulfate measurements for July 1978 are compared to fine-particle calculations to evaluate the model's ability to predict the transport of aerosol sulfur for the shorter averaging period. Visibility is modeled from the sulfate calculations using an empirical mass-to-light-scattering function. This technique is commonly used to determine aerosol light-scattering properties at given relative humidities. National Weather Service visual range observations have been compared with the model's visibility calculations; both regional patterns of visibility degradation and the absolute magnitude of the reduction in visual range are evaluated. Preliminary results are encouraging and the VISMAP modeling approach appears to be a useful step toward identifying long-range source/receptor relationships that affect visibility.     

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.     

Soil-air exchange of organochlorine pesticides in the Southern United States

Soil samples were collected from 30 farms in Alabama, Louisiana and Texas during 1999-2000 to determine residues of organochlorine pesticides (OCPs). One or more of the DDT compounds (p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDE) was above the quantitation limit (0.1 ng g(-1) dry weight) in every soil, and toxaphene was above the quantitation limit (3 ng g(-1)) in 26 soils. Chlordanes, dieldrin and hexachlorocyclohexane (HCH) isomers occurred less frequently (quantitation limits 0.1 ng g(-1) for dieldrin and 0.05 ng g(-1) for chlordanes and HCHs). OCPs were measured in air at 40 cm above the soil at selected farms to investigate soil-air partitioning. Concentrations of OCPs in air were positively and significantly (P<0.001-0.004) correlated to soil concentrations for toxaphene, p,p'-DDT, o,p'-DDT, p,p'-DDE, dieldrin, and trans-nonachlor. The regression was weaker (P=0.022) for cis-chlordane and not significant for trans-chlordane (P=0.43) nor gamma-HCH (P=0.80). Approach to soil-air equilibrium was assessed by calculating fugacities in the soil and air (f(s) and f(a)) for samples with quantifiable residues in both compartments. The fugacity fraction f(s)=0.5 at equilibrium and is <0.5 or >0.5 for net deposition and net volatilisation, respectively. Fugacity fractions varied greatly for different soil-air pairs, reflecting generally disequilibrium conditions. Mean fugacity fractions indicated near-equilibrium for some OCPs (p,p'-DDE, chlordanes, trans-nonachlor and dieldrin) and net volatilisation for others (p,p'-DDT, o,p'-DDT, toxaphene, gamma-HCH). Chiral analysis showed that enantioselective degradation of (+) or (-) o,p'-DDT in soil was accompanied by enrichment or depletion of the corresponding enantiomers in the overlying air, although there appeared to be some dilution by racemic o,p'-DDT from regional air transport.