Photochemical Reactivities of Paraffinic Hydrocarbon-Nitrogen Oxide Mixtures Upon Addition of Propylene or Toluene

Effects associated with photochemical air pollution were measured during irradiation of n-butane-nitrogen oxide or n-butane-ethane-nitrogen oxide mixtures, with small amounts of propylene or toluene added. The effects measured including nitrogen dioxide and oxidant dosages, yields of formaldehyde and peroxy-acetyl nitrate, and eye irritation response. The results obtained clearly show that beneficial effects result from selective changes in hydrocarbon composition as well as from reduction of total hydrocarbon concenfration. Exclusion of olefins and alkylbenzenes was highly effective in reducing oxidant dosage, formaldehyde and peroxyacetyl nitrate concentrations, and eye irritation response. The only penalty was a modest increase in nitrogen dioxide dosage. A large reduction in nitrogen oxide concentration reduced nitrogen dioxide dosage and eye irritation response, but with the penalty of a large increase in oxidant dosage. The desirability of preferentially reducing olefins and alkylbenzenes rather than paraffinic hydrocarbons, acetylene, and benzene is strongly supported by this study. Research and development efforts should be directed toward preferential hydrocarbon control by mechanical or catalytic control     

Nonmethane Organic Compound to Nitrogen Oxide Ratios and Organic Composition in Cities and Rural Areas

The observed ranges in nonmethane organic compound (NMOC) concentrations, NMOC composition and nitrogen oxides (NO_X) concentrations have been evaluated for urban and nonurban areas at ground level and aloft of the contiguous United States. The ranges in NMOC to NO_X ratios also are considered. The NMOC composition consistently shifts towards less reactive compounds, especially the alkanes, in air parcels over nonurban areas compared to the NMOC composition near ground level within urban areas. The values for the NMOC to NO_X ratios, 1.2 to 4.2, in air aloft over nonurban areas are lower than in air at ground level urban sites, ≥8, and much lower than in air at ground level nonurban sites, ≥20.

The layers of air aloft over a number of nonurban areas of the United States tend to accumulate NO_X emissions from the tall stacks of large fossil fuel power plants located at nonurban sites. During the night into the morning hours, the air aloft is isolated from any fresh NMOC emissions predominately coming from near surface sources. Conversely, during this extended period of restricted vertical mixing, air near the surface accumulates NMOC emissions while this air is isolated from the major NO_X sources emitting aloft. These differences in the distribution of NMOC and NO_X sources appear to account for the much larger NMOC to NO_X ratios reported near ground level compared to aloft over nonurban areas.

Two types of experimental results are consistent with these conclusions: (1) observed increases in surface rural NO_X concentrations during the morning hours during which the mixing depth increases to reach the altitude at which NO_X from the stacks of fossil fuel power plants is being transported downwind; (2) high correlations of total nitrate at rural locations with Se, which is a tracer for coal-fired power plant NO_X emissions.

The implications of these conclusions from the standpoint of air quality strategies are suggested by use of appropriate scenarios applied to both urban and regional scale photochemical air quality models. The predictions from urban model scenarios with NMOC to NO_X ratios up to 20 are that NO_X control will result in the need for the control of more NMOC emissions than necessary in the absence of NO_X control, in order to meet the O₃ standard. On a regional scale, control of NO_X emissions from fossil fuel power plants has little overall effect regionally but does result on a more local scale in both small decreases and increases in O₃ concentrations compared to the baseline scenario without NO_X control. The regional modeling results obtained to date suggest that NO_X control may be effective in reducing O₃ concentrations only for a very limited set of conditions in rural areas.     

An assessment of the risks associated with PCDDs and PCDFs following the application of sewage sludge to agricultural land in the UK

A model has been developed to describe the transfer of PCDDs and PCDFs from sludge-amended soils to the human foodchain. The model is conservative and assumes that all foods consumed by an individual are derived from sludge-amended soils. Predicted concentrations of PCDDs and PCDFs in potatoes, cereals, root vegetables and leafy vegetables were in close agreement with mean concentrations reported in the food survey conducted by MAFF in the UK. Predicted concentrations in milk were well below the Maximum Tolerable Concentration adopted by MAFF. Assuming a half-life of ten years in sludge-amended soils, the maximum estimated incremental daily intake (IDI) predicted by the model following ten applications of sludge to agricultural land was 0.80 pg I-TEQ kg⁻¹ day⁻¹, representing an increase of approximately 45% on current levels of background exposure. For an individual whose diet is solely derived from sludge-amended soils, the total exposure is predicted to be approximately 181 pg I-TEQ day⁻¹ or 2.6 pg I-TEQ kg⁻¹ day⁻¹. This compares with an average background exposure of approximately 2 pg I-TEQ kg⁻¹ day⁻¹, well within the TDI of 10 pg I-TEQ kg⁻¹ day⁻¹ and indicates that the application of sewage sludge to agricultural land under the conditions assumed would not appear to present a significant health risk under the conservative scenarios considered in this assessment.     

Relationship of Hydrocarbons to Oxidants in Ambient Atmospheres

The relation of ambient levels of hydrocarbons to the products of atmospheric photochemistry has proved to be an elusive problem. Models to account for the photochemical processes are available based on laboratory examination of simulated atmospheres. Likewise, dispersion models are available which, for nonreacting species, can predict air quality given knowledge of emission rates and meteorological variables. However, integration of the dispersion model with the photochemical model is as yet an unsolved problem. In this study an empirical approach was applied in which the only assumption made was that there exists a relationship between early morning average hydrocarbon concentrations and subsequent maximum hourly average oxidant concentrations. A direct examination of all available days in several cities shows that, at any given hydrocarbon level, there exists a limit on the amount of oxidant which can be generated. Specifically it shows that the average 6:00–9:00 A.M. concentration of 0.3 ppm C nonmethane hydrocarbon can be expected to produce a maximum hourly average oxidant concentration of up to 0.1 ppm.     

Estimation of the Natural Background of Ozone Present at Surface Rural Locations

The natural background in the ozone concentration at rural locations in the United States and western Europe has been estimated by use of several approaches. The approaches utilized include the following: (1) historical trends in ozone concentration measurements, (2) recent ozone measurements at remote sites, (3) use of tracers of air originating in the stratosphere or upper troposphere and (4) results from applications of tropospheric photochemical models. While each of these approaches has its own limitations it appears that the natural background of ozone during the warmer months of the year is in the range of 10 to 20 ppb. Most of the ozone originating in the lower stratosphere or upper troposphere is lost by chemical or physical removal processes as well as undergoing dilution by air in the lower troposphere before reaching ground level rural locations. Lower tropospheric photochemical processes, those below 5 km, are likely to account for most of the ozone measured at rural locations during the warmer months of the year.

A key aspect to improved quantitation of the contributions from lower tropospheric photochemical processes to ozone concentrations continues to be more extensive atmospheric measurements of the distribution of reactive species of nitrogen. The emission densities of anthropogenic sources of NO_x are known to be highly variable over populated areas of continents as well as between continental areas and the oceans. The emission densities of biogenic sources of NO_x are small, likely to be highly variable, but poorly quantitated. These wide variations indicate the need for use of three dimensional tropospheric photochemical models over large continental regions.

Available results do indicate higher efficiencies for ozone formation at lower NO_x concentrations, especially below 1 ppb.