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.     

Observations on the particulate chlorine distribution in the Houston-Galveston area

The chlorine component of total suspended paniculate (TSP) measured in the Houston-Galveston area during 10 days in June and September, 1975 has been examined for spatial variation and correlation with wind speed. The background concentrations of chlorine vary over an order of magnitude (from 0.2 to 6.6 μg m⁻³), and are found to depend on wind speed and direction. Higher background concentrations are associated with inland penetration of fresh marine air from the Gulf of Mexico. These background [Cl] variations are taken into account in order to identify anthropogenic [Cl] sources. Significant non-marine sources of [Cl], located in the industrialized Pasadena-Houston Ship Channel area, are evident in our data.     

Real-time control of sulphur dioxide emissions from an industrial area

Real-time emission control is an air quality policy which is alternative to permanent emission reduction. In general terms, it consists of controlling emission only when a forthcoming episode is forecast. Thus, control costs are lower than costs due to permanent abatement. The natural application is a case characterized by a limited number of polluting sources. In more specific terms, a real-time emission control scheme consists of the following operations at the beginning of each time interval (hour, say).

• 1.(i) Collect current concentration and meteorological measures by a monitoring network.
• 2.(ii) Forecast future values of relevant local meteorological variables.
• 3.(iii) On the basis of information about current concentration values, forecast meteorology and scheduled emissions predict future concentrations.
• 4.(iv) If future concentrations exceed some reference level, reduce the scheduled emissions.

The paper describes a case study [application of scheme (i)–(iv)] to SO₂ pollution from the industrial area in the Venetian lagoon region). The general characteristics are the following:The meteorological predictors [step (ii)] are simple stochastic methematical predictors.The concentration predictor [step (iii)] is based on a complex forecast algorithm (Kalman predictor). It is derived from the “stochastic version” of the numerical solution of the advection-diffusion partial differential equation.The control policy [step (iv)] is assumed to consist of mixing with cleaner fuel under the constraint of maintaining the production scheduled by each polluting plant. The results of the case study are supplied as cost-effectiveness curves (cost versus effectiveness of the control action).     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels

The impact of biogenic volatile organic compound (BVOC) emissions on European ozone distributions has not yet been evaluated in a comprehensive way. Using the CHIMERE chemistry-transport model the variability of surface ozone levels from April to September for 4 years (1997, 2000, 2001, 2003) resulting from biogenic emissions is investigated. It is shown that BVOC emissions increased on average summer daily ozone maxima over Europe by 2.5 ppbv (5%). The impact is most significant in Portugal (up to 15 ppbv) and in the Mediterranean region (about 5 ppbv), being smaller in the northern part of Europe (1.3 ppbv north of 47.5°N). The average impact is rather similar for the three summers (1997, 2000, 2001), but is much larger during the extraordinarily hot summer of 2003. Here, the biogenic contribution to surface ozone doubles compared to other years at some locations. Interaction with anthropogenic NO_x emissions is found to be a key process for ozone production of biogenic precursors. Comparing the impact of the state-of-the-art BVOC emission inventory compiled within the NatAir project and an earlier, widely used BVOC inventory derived from Simpson et al. [1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research 104(D7), 8113–8152] on surface ozone shows that ozone produced from biogenic precursors is less in central and northern Europe but in certain southern areas much higher e.g. Iberian Peninsula and the Mediterranean Sea. The uncertainty in the regionally averaged impact of BVOC on ozone build-up in Europe is estimated to be ±50%.     

Vegetation fire emissions and their impact on air pollution and climate

Gaseous and particulate emissions from vegetation fires substantially modify the atmospheric chemical composition, degrade air quality and can alter weather and climate. The impact of vegetation fire emissions on air pollution and climate has been recognised in the late 1970s. The application of satellite data for fire-related studies in the beginning of the 21th century represented a major break through in our understanding of the global importance of fires. Today the location and extent of vegetation fires, burned area and emissions released from fires are determined from satellite products even though many uncertainties persist. Numerous dedicated experimental and modeling studies contributed to improve the current knowledge of the atmospheric impact of vegetation fires. The motivation of this paper is to give an overview of vegetation fire emissions, their environmental and climate impact, and what improvements can be expected in the near future.     

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

The impact of motor vehicle control technologies on future photochemical ozone formation in the United Kingdom

Legislation to control motor vehicle exhaust emissions has been introduced in the United Kingdom in stages since the early 1970s. Recently, a further step has been taken towards reducing future exhaust emissions of carbon monoxide, unburnt hydrocarbons and oxides of nitrogen in the 'Luxembourg agreement' (Lubinska, 1985). In this paper, the possible impact of these proposed controls on photochemical air pollution formation in the United Kingdom is investigated, including an evaluation of the relative merits of the two principal emission control options for petrol-driven cars: 'Lean Burn' engines and 'Catalyst' exhaust gas treatment.     

Assessment of total concentrations of heavy metals in industrial sludges from the North of Vietnam and their potential impact on the ecosystem

Environmental Science and Pollution Research - Industrial sludges from wastewater treatment plants of industrial parks and a drinking water treatment plant in northern Vietnam were investigated in...     

Evaluating recycling fertilizers for tomato cultivation in hydroponics,and their impact on greenhouse gas emissions

Soilless culture systems offer an environmentally friendly and resource-efficient alternative to traditional cultivation systems fitting within the scheme of a circular economy. The objective of this research was to examine the sustainable integration of recycling fertilizers in hydroponic cultivation—creating a nutrient cycling concept for horticultural cultivation. Using the nutrient film technique (NFT), three recycling-based fertilizer variants were tested against standard synthetic mineral fertilization as the control, with 11 tomato plants (Solanum lycopersicum L. cv. Pannovy) per replicate (n = 4) and treatment: two nitrified urine-based fertilizers differing in ammonium/nitrate ratio (NH₄⁺:NO₃^?), namely (1) “Aurin” (AUR) and (2) “Crop” (CRO); as well as (3) an organo-mineral mixture of struvite and vinasse (S+V); and (4) a control (NPK). The closed chamber method was adapted for gas fluxes (N₂O, CH₄, and CO₂) from the root zone. There was no indication in differences of the total shoot biomass fresh matter and uptake of N, P and K between recycling fertilizers and the control. Marketable fruit yield was comparable between NPK, CRO and S+V, whereas lower yields occurred in AUR. The higher NH₄⁺:NO₃^? of AUR was associated with an increased susceptibility of blossom-end-rot, likely due to reduced uptake and translocation of Ca. Highest sugar concentration was found in S+V, which may have been influenced by the presence of organic acids in vinasse. N₂O emissions were highest in S+V, which corresponded to our hypothesis that N₂O emissions positively correlate with organic-C input by the fertilizer amendments. Remaining treatments showed barely detectable GHG emissions. A nitrified urine with a low NH₄⁺:NO₃^– (e.g., CRO) has a high potential as recycling fertilizer in NFT systems for tomato cultivation, and S+V proved to supply sufficient P and K for adequate growth and yield. Alternative cultivation strategies may complement the composition of AUR.

     

The impact trilemma of energy prices,taxation, and population on industrial and residential greenhouse gas emissions in Europe

Environmental Science and Pollution Research - As a major source of pollution and the cause of climate change, greenhouse gas emissions are attracting the attention of scholars, policymakers, and...     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.     

Influence of storage and release on particle emissions from new and used CRTs

This paper describes the results of three experiments performed with Continuously Regenerating Traps (CRTs^®) in a controlled laboratory setting to elucidate the effects of fuel sulfur content, filter age, and storage and release effects on particle concentration. In the first experiment, a new CRT was tested using near zero sulfur Fischer-Tropsch fuel and low sulfur lubricating oil (420 ppm). The objective was to measure particle emissions from an emission control device that had not previously been exposed to sulfur under a variety of operating and dilution conditions. Next, a used CRT was evaluated using the same fuel and lubricating oil. Finally, the used uncatalyzed Diesel particulate filter (DPF) from the used CRT was replaced with a new, uncatalyzed DPF. The emissions from the used Diesel oxidation catalyst (DOC) + new DPF were evaluated and compared to those of the used CRT.Our laboratory results show that particle number emissions from the new CRTs are 99.9% lower than equivalent used CRT data collected on-road at an exhaust temperature of 370 °C. Even as the new CRT temperature was increased to almost 400 °C, emission levels were still at background levels for roadway aerosol and no nucleation mode was observed. With the used CRT, the nucleation mode particle number concentration increased sharply at an exhaust temperature of about 380 °C and remained high for the duration of the test. Mass emissions were estimated and found to exceed US EPA on-road standards. The used DOC + new DPF led to essentially the same number emissions as the used CRT, suggesting that these emissions arise mainly from release of sulfates stored by the DOC and not the uncatalyzed DPF.     

Photochemical ozone formation in the Sydney airshed

The theoretical photostationary state relationship, k₃[O₃][NO]/k₁[NO₂] = 1, was tested in the free atmosphere using data obtained from a series of air mass trajectory experiments which were performed as part of the Sydney Oxidant Study. These data show that in general, the relationship was valid to within a factor of two for the Sydney airshed when three minute averaged concentration measurements were used. The effects of various averaging times upon the experimental photostationary state relationship arc discussed.     

On springtime high ozone events in the lower troposphere from Southeast Asian biomass burning

Ozone peaks with mixing ratios as high as 138 ppbv were observed in the lower troposphere (2.5–4.5 km) over Hong Kong in spring. Simultaneously observed high humidity suggests that this enhanced ozone was not the result of transport from the upper troposphere. Back trajectory analysis suggests that these enhancements resulted from lateral transport. Air masses arriving at the altitude of the ozone peaks appear to have passed over continental Southeast Asia where the bulk of biomass burning occurs at this time of the year (February–April). We hypothesize that biomass burning in this region provided the necessary precursors for the observed ozone enhancement. As far as we know this is the first observation of highly enhanced ozone layers associated with biomass burning in continental Southeast Asia.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

Atmospheric ozone: formation and effects on vegetation

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.     

Correlating emissions with time and temperature to predict worst-case emissions from open liquid area sources

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry's law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H2S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H2S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85-90 degrees F), the constant emission rate underestimated odor impact significantly (by 73%).     

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada)

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.