Comparisons of EPA Rollback,Empirical/Kinetic,and Physicochemical Oxidant Prediction Relationships in the San Francisco Bay Area

This paper describes, compares and evaluates selected Oxidant Prediction Relationships {OPRs) in terms of projections of hydrocarbon emission reductions required for attainment of the former 0.08 ppm standard and the new 0.12 ppm standard in the San Francisco Bay Area in 1985. The OPRs analyzed are the LIRAQ physicochemical model, EPA’s Empirical Kinetic Modeling Approach (EKMA), linear and Appendix J rollback, and an empirical OPR based on local observations.

LIRAQ simulations indicated that to achieve the 0.12 ppm ozone standard, 1985 hydrocarbon emissions must be reduced by 27% from projected levels. The equivalent reductions derived from simple linear rollback, linear rollback with 0.04 ppm background, and the local empirical OPR were 32%, 45% and 37%, respectively. The LIRAQ simulations also showed that reduction of both hydrocarbon and NO_x emissions is less effective than reduction of hydrocarbons only. The attempt to apply EKMA failed because the Bay Area’s low hydrocarbon/NO_x ratios and observed ozone levels are not consistent with the standard EKMA isopleth curves.

For planning, proper OPR selection is important because the wide range in the projections of various OPRs translates into a correspondingly wide range in control costs. Physicochemical OPRs are preferred because they are verifiable; they account for complex topography, meteorology, and source distributions; and because they can treat a variety of control strategies. In the future, the uncertainties associated with the projections can be resolved by assessing trends in air quality on a regular basis and by upgrading and reapplying the prediction methodologies as new information becomes available.     

NOX Levels in the Caracas Valley

An analysis of air quality data from 1970-1975 in the Los Angeles (LA) Basin has been made with emphasis on factors relevant to high hourly NO₂ concentrations, (NO₂). Detailed analysis of CO and SO₂ air quality and the (NO _x )/(CO) and (CO)/(SO₂) ratios reveals that high (NO₂) result mainly from vehicular sources; contributions from stationary sources to these high (NO₂) of greater than 10% occur rarely. Meteorological conditions (very low early-morning inversion base height and low wind speed) favoring the formation of high (NO₂) restrict the impact of elevated point NO _x sources on the ground level (NO₂) during the early to mid-morning hours. The overnight leftover NO _x during high NO₂ days is shown to originate largely from local sources near the monitoring sites. A regression analysis using NO₂, NO _x and HC data from downtown LA shows that a 50% reduction in (NO _x ) reduces high (NO₂) by 40-45%; a 50% reduction in (HC) reduces high (NO₂) by 5-10%. The present analysis supports assumptions used in an earlier generalized rollback model that related NO _x emissions to high 1-h average (NO₂) observed at downtown LA.     

Generalized Rollback Modeling for Urban Air Pollution Control

A general formula is derived that can be used to calculate the reductions in emissions of inert pollutants required to achieve National Ambient Air Quality Standards (NAAQS) and to predict future urban atmospheric concentrations. The derivation incorporates the main features of atmospheric diffusion modeling and takes account of all categories of sources and their spatial distribution. In our previous paper, carbon monoxide (CO) emissions from light duty vehicles were considered separately with the approximation that emissions from other sources of CO would grow and be controlled proportionately to that of light duty vehicles.

The new general formula is applied to Phoenix-Tucson using EPA data. It Is found that Phoenix-Tucson will meet the NAAQS for CO by 1985 if a 12 g/mi light duty vehicle emission standard is adopted. The EPA, using the same data in a modified rollback analysis, had predicted that Phoenix-Tucson, as well as a number of other localities, would not achieve the NAAQS even if the 3.4 g/mi statutory standard went into effect on schedule.

The underlying reasons for these very different predictions can be readily identified by means of the general formula. It is essential that the data and parameters used in these predictions be internally consistent. It is also noted that the current Federal Test Procedure (CVS-CH) for vehicle emissions gives data inconsistent with that needed to predict CO air quality with a correct methodology.     

A Comparative Assessment of Flue Gas Treatment Processes Part I—Status and Design Basis

The developmental status, projected costs, and environmental effects of 14 flue gas treatment processes are compared on a common basis in two consecutive issues of JAPCA. Part I summarizes the background and study basis and Part II compares environmental impact and relative costs. Each process is assumed to be associated with a grass roots installation that includes a modern 800 MW power plant burning Illinois No. 6 coal. Also considered is the effectiveness of these processes to control particulate matter, NO _x , trace inorganics, and polyorganic matter.

The processes are divided into those operating once-through (Limestone, Lime, Limestone and Lime, Dual-Alkali), and with regeneration (Magnesia, Wellman-Lord, Citrate, Aqueous Carbonate, IFP-Catalytic Inc., Copper-Dry Bed, and Carbon-Dry Bed). Also analyzed are NO _x control processes that are compatible with scrubbers or dry processes, and include the Exxon Thermal DeNO _x , Ozone NO Oxidation, and Copper and Carbon-Dry Bed.     

Relationships between Aerosol Extinction Coefficients Derived from Airport Visual Range Observations and Alternative Measures of Airborne Particle Mass

Epidemiological assessments of population exposures to airborne particles are often hampered by the scarcity of available fine particle mass measurements. In an attempt to overcome this serious problem, we analyze In this paper methods for predicting fine particle (M ₁) and Inhalable particle (IP) mass concentrations using relative humidity corrected light extinction coefficient (b _ext) estimated from airport visual range (V _r) observations. The analyses presented are based on theoretical determinations as well as statistical investigations utilizing EPA's NASN and Inhalable Particle Monitoring Network (IPMN) data bases and routine airport visual range observations In twelve large U.S. cities. Our results Indicate that, after controlling for certain limitations of airport visual range data, most of the regression models developed in this paper can be applied satisfactorily to predict M _t and IP. Furthermore, our findings Indicate that a more representative formula than the commonly used meteorological range formula to predict atmospheric b _ext values in urban areas may be b _ext = (1.8 ± 0.04)/V _r. Because of known local or regional influences, however, we do suggest calibration of any predictive model which utilizes airport visibility data against site-specific aerometric data on particle mass concentrations or scattering coefficient measurements.     

Analysis of metabolic changes in Trichoderma asperellum TJ01 at different fermentation time-points by LC-QQQ-MS

Trichoderma spp. are among the most widely recognized biocontrol fungi used to inhibit pathogens and promote plant growth. These functions are related to primary and secondary metabolites. This study investigated the different metabolites in Trichoderma asperellum TJ01 cultured for 24 and 72?h using liquid chromatography with triple-quadrupole mass spectrometry. Compared to the 24?h culture of T. asperellum TJ01, the 72?h culture with amino acid metabolism tended to decrease while sugar and lipid metabolisms tended to increase. Furthermore, the 72?h culture had a higher proportion of upregulated flavonoids, in combination with a higher proportion of downregulated alkaloids, and equal proportions of upregulated and downregulated polyphenols and hormones. This study also identified a few valuable medicinal substances such as trigonelline and 5-hydroxytryptophan in T. asperellum TJ01 fermentation cultures.     

Review of Recent Ecotoxicological Studies on Cladocerans

Cladocerans have been widely used as the bioassay organisms in evaluating the impact of different toxic substances. Literature survey during the last 10 years revealed that cladoceran ecotoxicological research has been in an exponential phase constituting nearly 10% of publications on this group. Many studies have considered typically planktonic taxa such as Daphnia magna, D. pulex, Moina macrocopa, M. micrura and Ceriodaphania dubia. Experimental data on toxicity tests, to a lesser extent, are also available for littoral-benthic genera such as Simocephalus, Macrothrix and Alona. Most toxicity tests are limited to the derivation of median lethal concentrations of various durations but mostly at 24 or 48 h. Studies related to the evaluation of changes in the life history variables of cladocerans as a result of sublethal exposure to toxic substances are not many, but gaining importance. The common toxic substances used in the cladoceran toxicity tests appear to be heavy metals, pesticides and a few natural toxins such as cyanotoxins. We review here the effect of different toxic substances on cladocerans based on both the field and the laboratory studies from an ecotoxicology point of view. Suggestions for the future cladoceran ecotoxicology are also commented on.     

Comparison of Hydrogen Sulfide Analysis Techniques

A summary and critique of common methods of analysis for H₂S is presented. The procedures described are: reflectance from silver plates and lead acetate-coated tiles, lead acetate and mercuric chloride paper tape, sodium nitroprusside and methylene blue wet chemical methods, infrared spectrophotometry, and gas chromatography. Pertinent details included for each method are type (continuous, semicontinuous, averaging), lower detection limit, range, known interferences and suggestions for their elimination, and appropriate instrument parameters as wavelength, flow rates, temperature, and sample size. The limitations of each technique are clearly described, as are the advantages, in such a manner as to aid the user to select proper instrumentation for his analytical requirements.     

Sorption of 1,2,4-trichlorobenzene and tetrachloroethene within an authigenic soil profile: Changes in Koc with soil depth

The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (K_d) found to decrease roughly 100-fold down the soil profile. K_d decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower K_d of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall K_d by more than 4-fold was observed on solids treated by either base extraction or H₂O₂ treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in K_oc among surface soil and deeper horizons.     

Ambient Air Hydroxyl Radical Concentrations: Measurements and Model Predictions

This review critically examines the limited number of recent near surface measurements of hydroxyl radicals in urban and rural areas. Predictions of average tropospheric, hemispheric and/or zonal concentrations of hydroxyl radicals derived from methylchloroform and carbon monoxide concentrations and models are discussed. The limitations of one- and two-dimensional model predictions of zonal and seasonal hydroxyl concentrations receive detailed consideration. Of especial concern on a regional scale are cloud cover effects on the penetration of ultraviolet radiation below 320 μm which is critical to the subsequent reactions forming hydroxyl radicals.     

Study on the denitrification performance of FexLayOz/activated coke for NH3-SCR and the effect of CO escaped from activated coke at mid-high temperature on catalytic activity

Currently, activated coke is widely used in the removal of multiple pollutants from industrial flue gas. In this paper, a series of novel Fe_xLa_yO_z/AC catalysts was prepared by the incipient wetness impregnation for NH₃-SCR denitrification reaction. The introduction of Fe-La bimetal oxides significantly improved the denitrification performance of activated coke at mid-high temperature, and 4% Fe_0.3La_0.7O_1.5/AC exhibited a superior NO_x conversion efficiency of 90.1% at 400 °C. The catalysts were further characterized by BET, SEM, XRD, Raman, EPR, XPS, FTIR, NH₃-TPD, H₂-TPR, et al., whose results showed that the perovskite-type oxide of LaFeO₃ and oxygen vacancies were produced on the catalysts’ surfaces during roasting. Fe-La doping enhanced the amount of acid sites (mainly Lewis and other stronger acid sites) and the content of multifarious oxygen species, which were beneficial for NO_x removal at mid-high temperature. Moreover, it was investigated that the effect of released CO from activated coke at mid-high temperature on the NO_x removal through the lifetime test, in which it was found that a large amount of CO produced by pyrolysis of activated coke could promote the NO_x removal, and long-term escaping of CO on the activated coke carrier did not have a significant negative impact on catalytic performance. The results of the TG-IR test showed that volatile matter is released from the activated coke while TG results showed that the weight loss rate of 4% Fe_0.3La_0.7O_1.5/AC only was 0.0015~0.007%/min at 300–400 °C. Hence, 4% Fe_0.3La_0.7O_1.5/AC had excellent thermal stability and denitrification performance to be continuously used at mid-high temperature. Finally, the mechanisms were proposed on the basis of experiments and characterization results.

     

The organic contamination level based on the total soil mass is not a proper index of the soil contamination intensity

Concentrations of organic contaminants in common productive soils based on the total soil mass give a misleading account of actual contamination effects. This is attributed to the fact that productive soils are essentially water-saturated, with the result that the soil uptake of organic compounds occurs principally by partition into the soil organic matter (SOM). This report illustrates that the soil contamination intensity of a compound is governed by the concentration in the SOM (C_om) rather than by the concentration in whole soil (C_s). Supporting data consist of the measured levels and toxicities of many pesticides in soils of widely differing SOM contents and the related levels in in-situ crops that defy explanation by the C_s values. This SOM-based index is timely needed for evaluating the contamination effects of food crops grown in different soils and for establishing a dependable priority ranking for intended remediation of numerous contamination sites.     

Screening of a potential leafhopper attractants and their applications in tea plantations

Abstract

Pheromones can be used as leafhopper attractants. However, commercial pheromone products, such as the Ingle lure, have certain limitations, including poor persistence in the field. In this study, (E)-2-hexenal, (Z)-3-hexen-1-ol, (Z)-3-hexenyl acetate, (E)-ocimene, linalool, and geraniol were selected and behaviorally tested as potential leafhopper attractants. Y-tube olfactometer tests showed that the C2 formulation was more effective than other formulations. In tea field trials, the number of leafhoppers caught by sticky board traps baited with C2 lures was greater than that caught by treatment. The number of leafhoppers attracted by the C2 lures was greater than that attracted by the commercial Ingle lures. Additionally, the total amount of active C2 components on lures was greater than that of the active components on the lure after 14 days. Thus, the results indicated that the C2 formulation may attract leafhoppers and have a greater persistence than other formulations in tea field.     

Smog Chamber Simulation of Los Angeles Pollutant Transport

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. In the absence of any evidence, it has been widely assumed that increasing NO _x emissions have caused oxidant levels to increase downwind of Los Angeles, i.e., Riverside and San Bernardino. This smog chamber study simulated pollutant transport from Los Angeles to the downwind areas by irradiating a typical Los Angeles hydrocarbon/NO _x mixture for extended periods of time. The smog chamber experiments were extended to 22 hours to obtain an integrated light intensity equal to that which occurs in the Los Angeles area. The effects of variations of nitrogen oxide emissions on an aged air mass were examined. The results show that downwind oxidant levels are only slightly affected by large changes in NO _x emissions. However, it is clear that reduced nitrogen oxide emissions will lead to an increase in oxidant in downtown Los Angeles.     

固体超强酸和金属氧化物类催化剂上CH4-SCR还原NOx研究进展

由于还原剂甲烷价廉易得,甲烷选择性催化还原NO_x（简称CH₄-SCR）被认为是最有潜力替代NH₃-SCR的催化还原技术。现有的CH₄-SCR催化剂中,分子筛类催化剂因催化活性高而被广泛研究,但由于其水热稳定性不好,使得非分子筛负载的催化剂成为近年来的研究热点,其中主要包括固体超强酸和氧化物两大类。综述了这两类催化体系在催化活性、反应机理及掺杂改性等方面的研究现状,比较了各种催化剂的优缺点,并对CH₄-SCR的发展前景进行了展望。     

Fungicide sensitivity of Trichoderma spp. from Agaricus bisporus farms in Serbia

Trichoderma species, the causal agents of green mould disease, induce great losses in Agaricus bisporus farms. Fungicides are widely used to control mushroom diseases although green mould control is encumbered with difficulties. The aims of this study were, therefore, to research in vitro toxicity of several commercial fungicides to Trichoderma isolates originating from Serbian and Bosnia-Herzegovina farms, and to evaluate the effects of pH and light on their growth. The majority of isolates demonstrated optimal growth at pH 5.0, and the rest at pH 6.0. A few isolates also grew well at pH 7. The weakest mycelial growth was noted at pH 8.0–9.0. Generally, light had an inhibitory effect on the growth of tested isolates. The isolates showed the highest susceptibility to chlorothalonil and carbendazim (ED₅₀ less than 1 mg L^?1), and were less sensitive to iprodione (ED₅₀ ranged 0.84–6.72 mg L^?1), weakly resistant to thiophanate-methyl (ED₅₀ = 3.75–24.13 mg L^?1), and resistant to trifloxystrobin (ED₅₀ = 10.25–178.23 mg L^?1). Considering the toxicity of fungicides to A. bisporus, carbendazim showed the best selective toxicity (0.02), iprodione and chlorothalonil moderate (0.16), and thiophanate-methyl the lowest (1.24), while trifloxystrobin toxicity to A. bisporus was not tested because of its inefficiency against Trichoderma isolates.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Alternative low-cost process for large-scale production of Bacillus thuringiensis in a simple and novel culture system

Abstract

An industrial-scale, profitable method for production of the most widely used bioinsecticide, Bacillus thuringiensis (Bt), is challenging because of its widespread application. The aim of this study is to present a strategy to develop a low-cost, large-scale bioprocess to produce Bt H14.

This study was first focused on the design of a culture medium composed of economical and available components, such as glycerol and lysed Saccharomyces cerevisiae. The production goal of 1200 ITU was achieved using a medium composed of 20:20 g L^?1of glycerol:lysed yeast in batch cultures. Efforts were subsequently focused on the design of an appropriate culture system, and an original two-stage culture system was proposed. First, yeast (the primary component of the culture medium) are cultivated using a minimal mineral medium and lysed, and in the second stage, Bt is cultivated in the same bioreactor using the lysed yeasts as culture medium (supplemented with a feeding pulse of 10 g L^?1 glycerol). This system was called fed batch one pot (FOP). A new inoculation strategy is also presented in this study, since these Bt cultures were inoculated directly with heat pre-treated spores instead of vegetative bacteria to facilitate the bioprocess. This study was developed from the laboratory to production-scale bioreactors (measuring from 500 mL to 2500 L), and the efficiency of the proposed strategy was evident in LD₅₀ tests results, achieving 1796 ITU in large-scale processes. Both the use of non-conventional sources and the process development for biomass production are important for cost-effective production of Bt-based insecticides in mosquito control projects.     

A Qualitative Approach to Evaluating the Anticipated Reliability of a Photochemical Air Quality Simulation Model for a Selected Application

ABSTRACT

Photochemical air quality simulation models are now used widely in evaluating the merits of alternative emissions control strategies on spatial scales from metropolitan to sub-continental. Greatly varying levels of resources have been available to support modeling, from relatively comprehensive databases and evaluation of performance to a paucity of aerometric data for developing model inputs. Where data are sparse, many alternative outcomes are consistent with the knowledge at hand. Where performance evaluation is inadequately supported, the probability of error may be high. In each instance, uncertainties may be large when compared with the signal of interest, and thus confidence in the reliability of the model as an estimator of future air quality may come into question.

This paper proposes a qualitative procedure for assessing whether a particular application of a modeling system is likely to be potentially unreliable, suggesting that either (1) modification and further evaluation is needed, if supportable, prior to adoption for regulatory application; or (2) the model should not be used if improvement is not supportable. The procedure is proposed for use by policy-makers, staffs of public agencies, air quality managers, environmental staffs of industrial organizations, and other interested parties. The proposed use of the procedure is (1) to assess, a priori, whether a proposed application is likely to be judged questionable or unacceptably uncertain in outcome; and (2) to provide, a posteriori, a basis for judging quickly the likely quality of model performance. The procedure is presented with tropospheric ozone as the pollutant of concern. With adjustments, however, the procedure should be applicable for particu-late matter and other pollutants of interest.     

The dissolution of benzene, toluene, m-xylene and naphthalene from a residually trapped non-aqueous phase liquid under mass transfer limited conditions

The results of dissolution experiments for benzene, toluene, m-xylene and naphthalene (BTXN) from a relatively insoluble oil phase (tridecane), residually trapped in a non-sorbing porous medium, are described. This mixture was chosen to simulate dissolution of soluble aromatic compounds from a petroleum hydrocarbon mixture, e.g., crude oil, for which a large fraction of the mixture is relatively insoluble. The experiments were carried out at a small source length to interstitial velocity ratio, L/v, so that dissolution would be mass transfer limited (MTL). When fitted to data for toluene, a multiregion mass transfer model was found to predict the experimental data satisfactorily for the other components without adjustment of the mass transfer rate parameters. These results indicate that the dissolution process can be generalized for various hydrophobic organic compounds present in a multicomponent non-aqueous phase liquid (NAPL) when mass transfer limitations are present. This also suggests that dissolution data obtained for one compound can be useful for predicting the dissolution histories for other compounds from petroleum hydrocarbon mixtures.