Issues with ozone attainment methodology for Houston, TX

To comply with the federal 8-hr ozone standard, the state of Texas is creating a plan for Houston that strictly follows the U.S. Environmental Protection Agency's (EPA) guidance for demonstrating attainment. EPA's attainment guidance methodology has several key assumptions that are demonstrated to not be completely appropriate for the unique observed ozone conditions found in Houston. Houston's ozone violations at monitoring sites are realized as gradual hour-to-hour increases in ozone concentrations, or by large hourly ozone increases that exceed up to 100 parts per billion/hr. Given the time profiles at the violating monitors and those of nearby monitors, these large increases appear to be associated with small parcels of spatially limited plumes of high ozone in a lower background of urban ozone. Some of these high ozone parcels and plumes have been linked to a combination of unique wind conditions and episodic hydrocarbon emission events from the Houston Ship Channel. However, the regulatory air quality model (AQM) does not predict these sharp ozone gradients. Instead, the AQM predicts gradual hourly increases with broad regions of high ozone covering the entire Houston urban core. The AQM model performance can be partly attributed to EPA attainment guidance that prescribes the removal in the baseline model simulation of any episodic hydrocarbon emissions, thereby potentially removing any nontypical causes of ozone exceedances. This paper shows that attainment of all monitors is achieved when days with observed large hourly variability in ozone concentrations are filtered from attainment metrics. Thus, the modeling and observational data support a second unique cause for how ozone is formed in Houston, and the current EPA methodology addresses only one of these two causes.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston, Texas

In Houston, some of the highest measured 8-hr ozone (O3) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O3 concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O3 changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O3 concentrations, the AQM predicted high O3 over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O3, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O3 concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O3 concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O3 standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O3, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.     

Modeled response of ozone to electricity generation emissions in the northeastern United States using three sensitivity techniques

Electrical generation units (EGUs) are important sources of nitrogen oxides (NO_x) that contribute to ozone air pollution. A dynamic management system can anticipate high ozone and dispatch EGU generation on a daily basis to attempt to avoid violations, temporarily scaling back or shutting down EGUs that most influence the high ozone while compensating for that generation elsewhere. Here we investigate the contributions of NO_x from individual EGUs to high daily ozone, with the goal of informing the design of a dynamic management system. In particular, we illustrate the use of three sensitivity techniques in air quality models—brute force, decoupled direct method (DDM), and higher-order DDM—to quantify the sensitivity of high ozone to NO_x emissions from 80 individual EGUs. We model two episodes with high ozone in the region around Pittsburgh, PA, on August 4 and 13, 2005, showing that the contribution of 80 EGUs to 8-hr daily maximum ozone ranges from 1 to >5 ppb at particular locations. At these locations and on the two high ozone days, shutting down power plants roughly 1.5 days before the 8-hr ozone violation causes greater ozone reductions than 1 full day before; however, the benefits of shutting down roughly 2 days before the high ozone are modest compared with 1.5 days. Using DDM, we find that six EGUs are responsible for >65% of the total EGU ozone contribution at locations of interest; in some locations, a single EGU is responsible for most of the contribution. Considering ozone sensitivities for all 80 EGUs, DDM performs well compared with a brute-force simulation with a small normalized mean bias (–0.20), while this bias is reduced when using the higher-order DDM (–0.10).

Implications: Dynamic management of electrical generation has the potential to meet daily ozone air quality standards at low cost. We show that dynamic management can be effective at reducing ozone, as EGU contributions are important and as the number of EGUs that contribute to high ozone in a given location is small (<6). For two high ozone days and seven geographic regions, EGUs would best be shut down or their production scaled back roughly 1.5 days before the forecasted exceedance. Including online sensitivity techniques in an air quality forecasting model can provide timely and useful information on which EGUs would be most beneficial to shut down or scale back temporarily.     

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO_x, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km², but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.     

Heavy metals and metalloid levels in the tissues of yellow-legged gulls (Larus michahellis) from Spain: sex,age, and geographical location differences

Environmental Science and Pollution Research - In the present study, mercury (Hg), cadmium (Cd), lead (Pb), selenium (Se), and arsenic (As) were measured in liver, kidney, and feathers of adult,...