Boundary Layer Evolution and its Influence on Ground-Level Ozone Concentrations

Accurate determination of the planetary boundary layer (PBL) height (i.e., mixing height (MH)) is critical to properly simulating pollutant levels with the grid-based photochemical models. In this study, the daytime mixing heights based on the parcel and bulk Richardson number methods are compared with those obtained directly from a numerical mesoscale meteorological model in an effort to evaluate the uncertainties in the estimation of the PBL evolution. Mixing heights are estimated from hourly outputs of meteorological variables of the Penn State/NCAR Mesoscale Model Version 3.3 (MM5V3) with two PBL schemes (Blackadar and Gayno-Seaman) during July 1999 over Philadelphia, PA. An analysis of the diurnal variation in the urban PBL and its influence on ground-level ozone (O₃) levels is presented in this paper. The results indicate that on average, the MHs determined from the bulk Richardson number were larger than those estimated from the parcel method. The MHs from the MM5V3 output were much smaller than those derived from the parcel and bulk Richardson number methods, especially for the Gayno-Seaman scheme that is based on turbulent kinetic energy. The MH and ground-level O₃ concentration have been found to be twice as much on episode days than on non-episode days. The average hourly MH growth rate and O₃ tendency (i.e. rate of change in O₃) were largest during the morning hours (0700 to 1000 eastern standard time (EST)), suggesting that vertical mixing contributes significantly to the accumulation of ground-level O₃ in urban areas in the morning hours.     

Aquatic toxicity of two Corexit dispersants

The oil spill dispersants, Corexit 9500 and Corexit 9527 have low to moderate toxicity to most aquatic species in laboratory tests. Toxicity estimates are significantly affected by test variables such as species, lifestage, exposure duration, and temperature. Aquatic toxicity data generated from spiked, declining exposures (107 min half-life) are more reflective of actual dispersant use conditions. Decisions to use oil spill response chemicals should not be based solely on aquatic toxicity. Factors to consider include product effectiveness, toxicity of dispersed oil, species/habitats requiring priority protection, and recovery potential of sensitive habitats and populations. An environmental risk assessment approach is recommended where dispersant toxicity data generated under environmentally relevant exposures are compared to estimated environmental concentrations of dispersants.     

Photolysis of diclobutrazol in methanol

The fungicide diclobutrazol (2RS,3RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol was irradiated by ultra-violet light in methanol solution using (1) borosilicate glass apparatus and (2) quartz apparatus. The major differences observed were that photodegradation occurred more rapidly in (2) than (1) and more breakdown products were found in the former. Using g.c.-m.s. ten compounds were detected in (1) of which five were identified. In (2) twelve of the eighteen compounds observed were identified and the major component was 1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-one. The compounds reported were formed by oxidation, loss of chlorine or by cyclisation. This previously unreported cyclisation gave the s-triazolo-(5,1a)isoquinoline ring system.     

A chassis test procedure to mimic the heavy-duty engine transient emissions certification test

In-use emissions from vehicles using heavy-duty diesel engines can be significantly higher than the levels obtained during engine certification. These higher levels may be caused by a combination of degradation of engine components, poor engine maintenance, degradation or failure of emissions after-treatment devices, and engine and emissions system tampering. A direct comparison of in-use vehicle emissions with engine certification levels, however, is not possible without removing an engine from the vehicle in order to perform engine dynamometer emissions testing. The goal of this research was to develop a chassis test procedure that mimics the engine performance, and as such the expected emissions levels, from the engine certification emissions test prescribed in the U.S. Code of Federal Regulations. Emissions measurements were taken from two engines during testing on an engine dynamometer using the transient heavy-duty Federal Test Procedure (FTP). Additionally, each engine was installed in an appropriate vehicle, and emissions measurements were taken using a chassis dynamometer while employing a vehicle driving schedule intended to match closely the instantaneous torque and speed schedule of the engine FTP. Engine and chassis testing was performed with the engines in stock (unmodified) condition as well as in several modes to simulate either tampered or poorly maintained conditions. The use of a chassis test as a predictive tool for determining whether an engine in a vehicle would pass the engine certification test has proven to be worthwhile. Analysis of the data shows that identification of chassis-mounted engines with NOx emissions above certification levels is possible by employing engine-specific correction factors. In the case of PM emissions, significant data scatter allowed only the identification of gross PM emitters. Engine tampering and poor maintenance can raise PM and NOx emissions, and these increases can be correctly identified by a chassis test. Analysis of chassis and engine CO and HC emissions did not reveal a strong enough correlation to warrant the use of the chassis test for emissions screening of these two pollutants.     

Beech (Fagus sylvatica) response to ozone exposure assessed with a chlorophyll a fluorescence performance index

This paper describes a relationship between ozone exposure, biomass, visual symptoms and a chlorophyll a fluorescence performance index for young beech trees (Fagus sylvatica). The plants were exposed to four levels of ozone in open-top fumigation chambers (50, 85, 100% of ambient, and 50% of ambient+30 nl l(-1) ozone) that fluctuated in parallel with ambient ozone during a single growing season. The trees were fumigated in the four treatments with ozone levels corresponding to an AOT40 (accumulated exposure above a threshold of 40 nl l(-1)) of 0.01, 3.35, 7.06 and 19.70 microl l(-1) h, respectively. Highly significant differences were found between the 50% of ambient+30 nl l(-1) ozone treatment and all other treatments, with a 70.5% reduction in primary photosynthetic performance, as measured with the PI index. The reduction of the PI values demonstrated a high correlation with visual symptom development (r(2)=0.98), and by the end of September with biomass loss (r(2)=0.99). A significant ozone exposure-response relationship was found between AOT40 and primary photochemistry (r(2)=0.97). Thus, analysis of PI provides an alternative method for regional monitoring of tree health within the context of the currently employed AOT40.     

Sources of variability in plant toxicity testing

Published literature is investigated regarding the response of plants to various substances to determine the sensitivity of agricultural plants versus other species, the similarity of effects seen at different taxonomic levels, sensitivity of plants growing outdoors versus in a greenhouse, and the sensitivity of different measurement endpoints. We find that agricultural species are not consistently more or less sensitive to the herbicides tested than non-crop species. Genus and family taxonomic groupings may show similar responses among species, but this similarity quickly decreases as the comparison progress between orders and classes. Results from field and greenhouse studies are less in agreement between studies than data from the other topics. Shoot length will be affected at concentrations lower than for other vegetative endpoints for most species tested for inorganic substances, but for organic substances root and shoot mass were more sensitive. Overall, there is no one species or endpoint that is consistently the most sensitive for all species or all chemicals in all soils, and differences in bioavailability among compounds may confound comparison of test results. Therefore, species sensitivity distributions, adjusted for bioavailability when possible, should be considered in order to better evaluate effects to non-target terrestrial plants.