An Operational Assessment of the Application of the Relative Reduction Factors in the Demonstration of Attainment of the 8-Hr Ozone National Ambient Air Quality Standard

Abstract

The U.S. Environmental Protection Agency in 1997 revised the 1-hr ozone (O₃) National Ambient Air Quality Standard (NAAQS) to one based on an 8-hr average, resulting in potential nonattainment status for substantial portions of the eastern United States. The regulatory process provides for the development of a state implementation plan that includes a demonstration that the projected future O₃ concentrations will be at or below the NAAQS based on photochemical modeling and analytical techniques.

In this study, four photochemical modeling systems, based on two photochemical models, Community Model for Air Quality and the Comprehensive Air Quality Model with extensions, and two emissions processing models, Sparse Matrix Optimization Kernel for Emissions and Emissions Modeling System, were applied to the eastern United States, with emphasis on the northeastern Ozone Transport Region in terms of their response to oxides of nitrogen and volatile organic carbon-focused controls on the estimated design values. With the 8-hr O₃ NAAQS set as a bright-line test, it was found that a given area could be termed as being in or out of attainment of the NAAQS depending upon the modeling system. This suggests the need to provide an estimate of model-to-model uncertainty in the relative reduction factor (RRF) for a better understanding of the uncertainty in projecting the status of an area's attainment. Results indicate that the model-to-model differences considered in this study introduce an uncertainty of the future estimated design value of ～3–5 ppb.     

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.     

Rethinking the assessment of photochemical modelin systems in air quality planning applications

The U.S. Environmental Protection Agency provides guidelines for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards on the basis of the application of photochemical modeling systems to simulate the effect of emission reductions. These guidelines also require assessment of the model simulation against observations. In this study, we examined the link between the simulated relative responses to emission reductions and model performance as measured by operational evaluation metrics, a part of the model evaluation required by the guidance, which often is the cornerstone of model evaluation in many practical applications. To this end, summertime O3 concentrations were simulated with two modeling systems for both 2002 and 2009 emission conditions. One of these two modeling systems was applied with two different parameterizations for vertical mixing. Comparison of the simulated base-case 8-hr daily maximum O3 concentrations showed marked model-to-model differences of up to 20 ppb, resulting in significant differences in operational model performance measures. In contrast, only relatively minor differences were detected in the relative response of O3 concentrations to emission reductions, resulting in differences of a few ppb or less in estimated future year design values. These findings imply that operational model evaluation metrics provide little insight into the reliability of the actual model application in the regulatory setting (i.e., the estimation of relative changes). In agreement with the guidance, it is argued that more emphasis should be placed on the diagnostic evaluation of O3-precursor relationships and on the development and application of dynamic and retrospective evaluation approaches in which the response of the model to changes in meteorology and emissions is compared with observed changes. As an example, simulated relative O3 changes between 1995 and 2007 are compared against observed changes. It is suggested that such retrospective studies can serve as the starting point for targeted diagnostic studies in which individual aspects of the modeling system are evaluated and refined to improve the characterization of observed changes.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

Assessing contamination of smoked sprats (Sprattus sprattus) with polycyclic aromatic hydrocarbons (PAHs) and changes in its level during storage in various types of packaging

The analysis of material used in this study demonstrated that the amount of polycyclic aromatic hydrocarbons (PAHs) in smoked sprats varies from the level below the lowest detection limit in muscles up to 9.99 µg kg^?1 of benzo[a]pyrene (BaP) in fish skin. Such a high level of PAHs in skin was reported only in one of six batches of sprats, while mean BaP level was at 1.69 µg kg^?1. Regardless such a high BaP level in skin, its concentration in muscles did not exceed the maximum acceptable level. The study objective was to assess to what extent packaging materials adsorb PAH compounds from food. Changes in the PAH levels were monitored in fish during their storage in packages made of various materials. The storage time was from 0 to 168 hours. The obtained results varied considerably, therefore their scatter did not allow to confirm unequivocally the preliminary hypothesis about the reduction of PAHs due to their migration to packaging material. However, analysis of the packaging used in this study demonstrated a significant increase in the level of total 16 PAHs. When high-density polyethylene (HDPE) packaging was analysed, a six-fold increase in the total 16 PAHs was observed comparing to the blank sample.     

Rheological and sensory properties of hydrophilic skin protection gels based on polyacrylates

Introduction. With the current increases in occupational skin diseases, literature data attesting the decreasing efficiency of barrier creams with respect to the manufacturer’s declarations and legal regulations granting skin protection gels for employees, research is required to analyse and evaluate the recipes used for hydrophilic skin protection gels based on polyacrylates. Methods. This study investigated the rheological properties, pH and sensory perception of hydrophilic barrier gels based on polyacrylates. Results. The acrylic acid derivatives used were good thickeners, and helped to form transparent gels of adequate durability. They could be used to create hydrophilic films on the surface of the skin to protect it against hydrophobic substances. A correlation was shown between the results of the rheological properties and the barrier properties of the gels. This confirms the possibility of monitoring the quality of the gels at the stage of recipe development. Conclusions. Polyacrylates are viable for use in industry to produce hydrophilic barrier creams suitable for skin protection.     

Evaluation of laboratory-scale in-vessel co-composting of tobacco and apple waste

Efficient composting process requires set of adequate parameters among which physical–chemical properties of the composting substrate play the key-role. Combining different types of biodegradable solid waste it is possible to obtain a substrate eligible to microorganisms in the composting process. In this work the composting of apple and tobacco solid waste mixture (1:7, dry weight) was explored. The aim of the work was to investigate an efficiency of biodegradation of the given mixture and to characterize incurred raw compost. Composting was conducted in 24 L thermally insulated column reactor at airflow rate of 1.1 L min^?1. During 22 days several parameters were closely monitored: temperature and mass of the substrate, volatile solids content, C/N ratio and pH-value of the mixture and oxygen consumption. The composting of the apple and tobacco waste resulted with high degradation of the volatile solids (53.1%). During the experiment 1.76 kg of oxygen was consumed and the C/N ratio of the product was 11.6. The obtained temperature curve was almost a “mirror image” of the oxygen concentration curve while the peak values of the temperature were occurred 9.5 h after the peak oxygen consumption.     

Numerical modeling of aquaculture dissolved waste transport in a coastal embayment

Marine aquaculture is expanding rapidly without reliable quantification of effluents. The present study focuses on understanding the transport of dissolved wastes from aquaculture pens in near-coastal environments using the hydrodynamics code SUNTANS (Stanford Unstructured Nonhydrostatic Terrain-following Adaptive Navier–Stokes Simulator), which employs unstructured grids to compute flows in the coastal ocean at very high resolution. Simulations of a pollutant concentration field (in time and space) as a function of the local environment (bathymetry), flow conditions (tides and wind-induced currents), and the location of the pens were performed to study their effects on the evolution of the waste plume. The presence of the fish farm pens cause partial blockage of the flow, leading to the deceleration of the approaching flow and formation of downstream wakes. Results of both the near-field area (area within 10 to 20 pen diameters of the fish-pen site) as well as far-field behavior of the pollutant field are presented. These detailed results highlight for the first time the importance of the wake vortex dynamics on the evolution of the near-field plume as well as the rotation of the earth on the far-field plume. The results provide an understanding of the impact of aquaculture fish-pens on coastal water quality.     

Analysis of Toxic Air Contaminant Data Containing Concentrations Below the Limit of Detection

Air quality data often contain several observations reported only as below the analytical limit of detection (LOD), resulting in “censored” data sets. Such censored and/or truncated data sets tend to complicate statistical analysis. This paper discusses various procedures for estimating mean concentration and Its 95 percent confidence bounds from air contaminant data sets which contain values that are reported as below the LOD, A quantitative approach for assessing the uncertainty Inherent In the estimated mean concentration due to (a) presence of values below the LOD In the data set, and (b) natural variability of atmospheric concentration data, is described. The utility of this approach In the analysis and interpretation of ambient pollutant concentration data Is demonstrated for both hypothetical and observed singly-censored data sets, and for a multiply-censored, multi-pollutant observed concentration data set. The methodologies discussed here should be particularly useful In verifying compliance with environmental regulations, and In estimating the risks associated with long-term exposure of populations to toxic air contaminants and assessing the uncertainty associated with these estimates.