Demonstrating attainment of the air quality standards: integration of observations and model predictions into the probabilistic framework

This paper introduces an integrated observational-modeling approach to transform the deterministic nature of attainment demonstrations of the National Ambient Air Quality Standard (NAAQS) into the probabilistic framework. While the methods presented here can be used to address any air quality standard that is based on extreme values, this paper focuses on the application to the 1-hr and 8-hr NAAQS for ozone. Extreme value statistics and resampling techniques are applied to estimate the probability of exceeding the NAAQS for both 1-hr and 8-hr ozone concentrations. Within the integrated observation-modeling analysis approach, we show that the model-to-model differences in the predicted responses to emission reductions are smaller than the model-to-model differences in predicted absolute ozone concentrations. We illustrate that the emission reductions stemming from a real-world emission control strategy would substantially reduce the probability of exceeding the NAAQS over a large portion of the eastern United States, especially for the 8-hr average ozone concentrations.     

Washing of marine coastal sand in a batch reactor: sorption and desorption of BTEX

This study addresses the issues related to decontamination of marine beach sand accidentally contaminated by petroleum products. Sorption and desorption of BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) onto the sand from Uran Beach, located near the city of Mumbai, India, were studied, and isotherms were determined using the bottle point method to estimate sorption coefficients. Alternatively, QSARs (i.e., quantitative structure activity relationships) were developed and used to estimate the sorption coefficients. Experiments for kinetics of volatilization as well as for kinetics of sorption and desorption in the presence of volatilization were conducted in a fabricated laboratory batch reactor. A mathematical model describing the fate of volatile hydrophobic organic pollutants like BTEX (via sorption and desorption in presence of volatilization) in a batch sediment-washing reactor was proposed. The experimental kinetic data were compared with the values predicted using the proposed models for sorption and desorption, and the optimum values of overall mass transfer coefficients for sorption (K(s)a(s)) and desorption (K(d)a(d)) were estimated. This was achieved by minimization of errors while using the sorption coefficients (Kp) obtained from either laboratory isotherm studies or the QSARs developed in the present study. Independent experimental data were also collected and used for calibration of the model for volatilization, and the values of the overall mass transfer coefficient for volatilization (K(g)a(g)) were estimated for BTEX. In these exercises of minimization of errors, comparable cumulative errors were obtained from the use of Kp values derived from experimental isotherms and QSARs.     

Beryllium-7 measurements in the Houston and Phoenix urban areas: an estimation of upper atmospheric ozone contributions

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O3) and aerosols in the troposphere. Beryllium-7 (7Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. 7Be has a 53.29-day half-life (478 keV gamma) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O3 from aloft can be transported into rural and urban regions during stratospheric-tropospheric folding events leading to increased background levels of O3 at the surface. 7Be can be used as a tracer of upper atmospheric air parcels and the O3 associated with them. Aerosol samples with a 2.5-microm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August-September of 2000, and at Waddell, AZ, near Phoenix, in June-July of 2001. A comparison of 7Be levels with 12-hr O3 averages and maxima shows little correlation. Comparison of nighttime and daytime O3 levels indicate that during the day, when mixing is anticipated to be higher, the correlation of 7Be with O3 in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O3 by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O3 variance can be explained by the correlation with 7Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for 7Be correlations with either O3 24-hr averages or O3 12-hr maxima and is also in the range of the low O3 levels (25 ppb) observed at Deer Park during a tropical storm event where the O3 is attributable primarily to background air masses. That is, maximum background O3 level contributions from stratospheric sources aloft are estimated to be in the range of 15-30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

A direct passive method for measuring water and contaminant fluxes in porous media

This paper introduces a new direct method for measuring water and contaminant fluxes in porous media. The method uses a passive flux meter (PFM), which is essentially a self-contained permeable unit properly sized to fit tightly in a screened well or boring. The meter is designed to accommodate a mixed medium of hydrophobic and/or hydrophilic permeable sorbents, which retain dissolved organic/inorganic contaminants present in the groundwater flowing passively through the meter. The contaminant mass intercepted and retained on the sorbent is used to quantify cumulative contaminant mass flux. The sorptive matrix is also impregnated with known amounts of one or more water soluble 'resident tracers'. These tracers are displaced from the sorbent at rates proportional to the groundwater flux; hence, in the current meter design, the resident tracers are used to quantify cumulative groundwater flux. Theory is presented and quantitative tools are developed to interpret the water flux from tracers possessing linear and nonlinear elution profiles. The same theory is extended to derive functional relationships useful for quantifying cumulative contaminant mass flux. To validate theory and demonstrate the passive flux meter, results of multiple box-aquifer experiments are presented and discussed. From these experiments, it is seen that accurate water flux measurements are obtained when the tracer used in calculations resides in the meter at levels representing 20 to 70 percent of the initial condition. 2,4-Dimethyl-3-pentanol (DMP) is used as a surrogate groundwater contaminant in the box aquifer experiments. Cumulative DMP fluxes are measured within 5% of known fluxes. The accuracy of these estimates generally increases with the total volume of water intercepted.     

Adsorption studies and the removal of dissolved metals using pyrolusite as adsorbent

The adsorption of metals from aqueous solutions of Pb²⁺, Zn²⁺ and Mg²⁺ on naturally occurring pyrolusite have been studied. The chemical stability of the pyrolusite has been determined in NaOH, H₂SO₄, HNO₃, HCl, NaCl and NK₄Cl solutions of various concentrations. Adsorption of the metal ions followed the order Pb²⁺>Zn²⁺>Cd²⁺.The maximum adsorption of Pb²⁺ (100%) occurred at pH 7. the relation between the amount of Pb²⁺ adsorbed per unit weight of pyrolusite and the concentration of Pb²⁺ at equilibrium follows the Freundlich adsorption isotherm.The efficiency of pyrolusite has been demonstrated by removing lead from synthetic waste water. 100% and 96% removal of lead have been achieved from synthetic waste water containing 5 mg l^–1 and 120 mg l^–1 of Pb²⁺ respectively at pH 7. The results of these studies suggest that pyrolusite might provide an economical method for the removal of lead from industrial waste water.     

Monitoring of Hydrocarbon Emissions in a Petroleum Refinery

In a petroleum refinery the hydrocarbon emissions which are mostly fugitive in nature are emitted from process, offsites and periodic accidental releases such as: materials storage & handling, process, equipment leaks, solvent evaporation, combustion sources, waste treatment etc. In India, the monitoring of such emissions in a refinery are limited as also the standards are not set for its limit in ambient air. Hence there is an urgent need for generating a database for such emissions. Recently in India, MoEF/CPCB has set some guidelines under CREP rules for monitoring such emissions in a refinery. A detailed monitoring of the hydrocarbon emissions from different sources in a typical 10.5 MMTPA Indian refinery is undertaken during 1999–2001 and the results are presented. It is observed that the storage tank emissions alongwith process leaks form the major contributor towards fugitive hydrocarbon emissions.     

Ozone air quality over north america: part II--an analysis of trend detection and attribution techniques

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 climatological 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.     

Design of aquifer remediation systems: (2) estimating site-specific performance and benefits of partial source removal

A Lagrangian stochastic model is proposed as a tool that can be utilized in forecasting remedial performance and estimating the benefits (in terms of flux and mass reduction) derived from a source zone remedial effort. The stochastic functional relationships that describe the hydraulic "structure" and non-aqueous phase liquid (NAPL) "architecture" have been described in a companion paper (Enfield, C.G., Wood, A.L., Espinoza, F.P., Brooks, M.C., Annable, M., Rao, P.S.C., this issue. Design of aquifer remediation systems: (1) describing hydraulic structure and NAPL architecture using tracers. J. Contam. Hydrol.). The previously defined functions were used along with the properties of the remedial fluids to describe remedial performance. There are two objectives for this paper. First, is to show that a simple analytic element model can be used to give a reasonable estimate of system performance. This is accomplished by comparing forecast performance to observed performance. The second objective is to display the model output in terms of change in mass flux and mass removal as a function of pore volumes of remedial fluid injected. The modelling results suggest that short term benefits are obtained and related to mass reduction at the sites where the model was tested.     

Analysis of ambient,precipitation-weighted,and lake sulfate concentrations in the Adirondack region of New York

AbstractIt is well known that many ecosystems in the eastern United States, including the Adirondack Mountain region of New York, are particularly sensitive to acidic deposition because the soils and lakes in the region tend to have low values of base saturation and acid neutralizing capacity, respectively [e.g. Environ Sci Policy, 1 (1998), 185]. To facilitate tracking the impacts of anthropogenic emissions on air quality, acidic deposition, and surface water quality, the National Atmospheric Deposition Program, New York State Department of Environmental Conservation, and Adirondack Lake Survey Corporation have been monitoring ambient sulfur dioxide and aerosol sulfate levels, and anion and cation concentrations in wet deposition and lake water over the past few decades. In this paper, we discuss the seasonality and year-to-year variability, and illustrate some of the complexities in estimating temporal trends in these data. The periods of analysis extended through 2000, beginning in 1991 for the ambient air quality data, 1978 for the wet deposition data, and 1982 for the lake water quality data. While the lake water SO4(2-) concentrations appear to be decreasing gradually, the air concentration data appear to have changed abruptly in the 1990s and the precipitation-weighted concentrations exhibited both gradual and sharp decreases during the same period.