Reverse phase high performance liquid chromatographic determination of Baygon in water

A simple analytical procedure for determination of Baygon in water is described. The Baygon residues are extracted on a C18 SEP-PAK cartridge and subsequently analyzed by reverse phase high performance liquid chromatography using ultraviolet detection at 272 nm. Water samples spiked with Baygon are found to give greater than 90 percent recoveries. Concentration levels as low as 20 ppb can be easily detected by this method.     

Size Distribution of Particles That May Contribute to Soiling of Material Surfaces

ABSTRACT

This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH₃) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH₃ oxidation at high temperatures. From the NH₃ temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature

IMPLICATIONS Recently, NMO and manganese oxide have been reported as SCR catalysts. They usually have only reported the reaction characteristics and catalytic activity on the NH₃ SCR over NMO or manganese/metal oxide catalysts. There are no studies about the effect of addition of V to NMO. Therefore, this study investigates the catalytic activity and reaction characteristics on the NH₃ SCR over NMO and V/NMO, and a new application is proposed based on the conclusions of this study.     

Spatial Factors Influencing Winter Primary Particle Sampling and Interpretation

ABSTRACT

Aerosol samplers collect material that is locally generated as well as that transported from upwind; knowing the extent of the area from which the sample is drawn is necessary for proper interpretation of sampler data. The U.S. Environmental Protection Agency (EPA) PM_2.5 monitoring guidelines recognize a conceptual hierarchy of sampler spatial representation, but provide no objective measures of a site’s spatial representativeness. A case study of a sampler tributary area in central California provides insights into the factors that determine a sampler’s spatial representation. Winter diurnal cycles of fine particle concentrations at places of habitation ranging from urban cores to small farm towns show a marked cycle that can be linked to local human activity. Assessment of the possible causes of the observed cycles leads to the hypothesis that local sources dominate primary particle mass in winter samples. The hypothesis was tested using a simple model to relate routine 24-hr PM₁₀ and PM_2.5 samples to a sampler’s surroundings. Model results indicate that even minor sources very close to a sampler will overwhelm any regional component in a sample. The results for the cases studied also demonstrate that, in winter, most coarse (PM_10-2.5) particles collected are less than 2 hr old, and most primary fine (PM_2.5) particles are less than 4 hr old. Even on days that are not truly “stagnant,” samplers are very strongly influenced by their immediate surroundings (distances less than 10 km), and only weakly influenced by regional emissions.

The implications for interpretation of sample analyses are as follows: 1. Typical PM sampling networks are unlikely to represent regional conditions;

2. Similarity of samples in time and space between widely separated samplers probably arises from sampling analogous local environments rather than a uniformly mixed regional air mass;

3. Even weak sources near a sampler will prevent regionally representative samples, so that “background” specification in models can be strongly skewed by misapplication of sampler data;

4. Source-receptor relationships within a single modeling grid cell can cause measured and modeled source impacts at a sampler to diverge by orders of magnitude, even for grid cells as small as 1 km; and

5. Differential deposition of coarse and fine particles will skew source apportionment by chemical tracers unless the tracers and the source emissions have the same size distribution.

     

Factors Influencing the Variability of SO2 Concentrations in Istanbul

ABSTRACT

The correlation between sulfur dioxide (SO₂) concentrations measured at the European and Asian sides of Istanbul and meteorological parameters is investigated using principal component analysis (PCA) and multiple regression analysis techniques. Several meteorological parameters are selected to represent the atmospheric conditions during two winter periods: 1993–1994 and 1994–1995. Six principal components are found to explain the majority of the observed meteorological variability. Surface pressure, 850-mb temperature, and surface zonal (east-west) and meridional (north-south) winds show high loadings on separate factors identified by PCA. We seek dominant meteorological parameters that control the SO₂ levels at each monitoring station. Several multiple regression analysis models are fitted to the data from each monitoring station using six principal components and previous day SO₂ concentrations as independent variables.

Results suggest that the most important parameters, highly correlated with SO₂ concentrations in the Istanbul metropolitan area, are atmospheric pressure and surface zonal and meridional winds. These components have more influence on the determination of the air pollution levels at the Asian side than at the European side.     

Methane Emissions from Domestic Waste Management Facilities in Jordan—Applicability of IPCC Methodology

ABSTRACT

In this paper, methane emissions from municipal wastewater treatment plants and municipal solid waste (MSW) landfills in Jordan for 1994 have been estimated using the methodology developed by the Intergovernmental Panel on Climate Change (IPCC). For this purpose, the 14 domestic wastewater treatment plants in the country were surveyed. Generation rates and characterization of MSW components as well as dumping and landfilling practices were surveyed in order to estimate 1994 CH₄ emissions from these sites. Locally available waste statistics were used in cases where those of the IPCC guidelines were not representative of Jordan's statistics.

Methane emissions from domestic wastewater in Jordan were estimated at 4.66 gigagrams (Gg). Total 1994 CH₄ emissions from MSW management facilities in Jordan are estimated at 371.76 Gg—351.12 Gg (94.45%) from sanitary landfills, 19.83 Gg (5.33%) from MSW open dumps, and 0.81 Gg (0.22%) from raw sewage-water dumping ponds. Uncertainties associated with these estimations are presented.     

An Alternative Approach to Photochemical Ozone Creation Potentials Applied under European Conditions

ABSTRACT

Photochemical ozone creation potential (POCP) values for 83 different volatile organic compounds (VOCs), including CO and CH₄, were calculated under different environmental conditions representative for Europe. These calculations show that variations in POCP values are large between different types of chemical environments and that POCP values for VOCs should be presented as ranges instead of single values. POCP ranges are based on the extremes of the POCP values and are defined with the intention to include all POCP values an individual VOC will obtain in any European environment where O₃ formation is of environmental concern. The POCP ranges indicate large differences in O₃ production between individual VOCs, which justifies the use of this ranking scale instead of treating all VOCs as a homogeneous group of species in abatement strategies.

Both the average O₃ production over 96 hr and the maximum contribution to the O₃ concentration were studied. The most efficient O₃ producers were found to be iso-prene, 2-methyl-2-butene, and acrolein. As a group, the alkenes are the most potent O₃ producers, followed by higher alkanes and then the aromatics. The calculated values show a good agreement with previously calculated POCP values under northern European conditions.     

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl^?, SO₄^2?, and PO₄^3?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO₄^3?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO₄·^? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO₄^3?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO₄·^?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO₂, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD₅₀ and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.

     

Removal of Chromium from Abrasive Blast Media by Leaching and Electrochemical Precipitation

ABSTRACT

Water is effective in leaching out Cr⁶⁺ from a mixture of paint powders and abrasive blast media. However, acids such as HNO₃, HCl, and H₂SO₄ significantly enhance the leaching procedure. Cr ions in the leaching solutions are successfully removed by electrochemical precipitation. The consumable Fe electrodes generate ferrous ions to cause the reduction of Cr⁶+ to Cr³+. Cr³+ ions along with Fe²+ and Fe³+ are then removed mainly by precipitation as Cr(OH)₃, Fe(OH)₂, and Fe(OH)₃ near the cathode where OH^- ions are generated by water electrolysis. The electrochemical process is capable of discharging low levels of Cr⁶+, less than 1 mg/L, without pH adjustment.     

Temporal Variations of PM2.5, PM10, and Gaseous Precursors during the 1995 Integrated Monitoring Study in Central California

ABSTRACT

The spatial and temporal distributions of particle mass and its chemical constituents are essential for understanding the source-receptor relationships as well as the chemical, physical, and meteorological processes that result in elevated particulate concentrations in California’s San Joaquin Valley (SJV). Fine particulate matter ₍PM_2.5), coarse particulate matter (PM₁₀), and aerosol precursor gases were sampled on a 3-hr time base at two urban (Bakersfield and Fresno) and two non-urban (Kern Wildlife Refuge and Chowchilla) core sites in the SJV during the winter of 1995–1996.

Day-to-day variations of PM_2.5 and PM₁₀ and their chemical constituents were influenced by the synoptic-scale meteorology and were coherent among the four core sites. Under non-rainy conditions, similar diurnal variations of PM_2.5 and coarse aerosol were found at the two urban sites, with concentrations peaking during the nighttime hours. Conversely, PM_2.5 and coarse aerosol peaked during the morning and afternoon hours at the two non-urban sites. Under rainy and foggy conditions, these diurnal patterns were absent or greatly suppressed.

In the urban areas, elevated concentrations of primary pollutants (e.g., organic and elemental carbons) during the late afternoon and nighttime hours reflected the impact from residential wood combustion and motor vehicle exhaust. During the daytime, these concentrations decreased as the mixed layer deepened. Increases of secondary nitrate and sulfate concentrations were found during the daylight hours as a result of photochemical reactions. At the non-urban sites, the same increases in secondary aerosol concentrations occurred during the daylight hours but with a discernable lag time. Concentrations of the primary pollutants also increased at the non-urban sites during the daytime. These observations are attributed to mixing aloft of primary aerosols and secondary precursor gases in urban areas followed by rapid transport aloft to non-urban areas coupled with photochemical conversion.     

Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

The removal system for the absorption of CO₂ with amines and NH₃ is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO₂ by amines and NH₃ solutions was performed in this study to derive the reaction kinetics. The absorption of CO₂ as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH₃ was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O₂ concentration and pH value. The absorption efficiency of MEA is better than that of NH₃ and DEA, but the absorption capacity of NH₃ is the best. The active energies of the MEA and NH₃ with CO₂ are 33.19 and 40.09 kJ/mol, respectively.     

Particulate Emission Rates for Unpaved Shoulders along a Paved Road

ABSTRACT

This paper reports the first empirical estimate of particle emissions from unpaved shoulders along paved roads.¹ Its objectives are to develop and demonstrate an emission rate measurement methodology that can be applied in different areas; identify the mechanisms that suspend dust from unpaved shoulders and the observables related to this suspension process; and quantify PM₁₀ mass emissions in the form of an emission rate. To achieve these objectives, fast-response observations from nephelometers and a sonic anemometer were used to characterize shortlived dust plumes generated by passing vehicles. In addition, detailed soil surface measurements determined the mechanical properties of the shoulder surfaces.

Large traffic-induced turbulence events that led to significant dust entrainment were almost exclusively caused by “large” vehicles such as trucks, semis, and vehicles pulling trailers, all traveling 50-65 mph. PM₁₀ emission rates for these large, fast-traveling vehicles were determined to be 8 ± 4 grams per vehicle kilometer traveled under dry conditions. Emissions due to smaller vehicles such as cars, vans, and sport utility vehicles were negligible for normal on-road driving. These results indicate that the majority of PM₁₀ emissions from unpaved shoulders is caused by relatively few vehicles.     

A Life-Cycle Inventory Model of Municipal Solid Waste Combustion

ABSTRACT

Evaluation of alternate strategies for municipal solid waste (MSW) management requires models to calculate environmental emissions as a function of both waste quantity and composition. A methodology to calculate waste component-specific emissions associated with MSW combustion is presented here. The methodology considers emissions at a combustion facility as well as those avoided at an electrical energy facility because of energy recovered from waste combustion. Emission factors, in units of kg pollutant per metric ton MSW entering the combustion facility, are calculated for CO₂-biomass, CO₂-fossil, SO_x , HCl, NO_x , dioxins/furans, PM, CO, and 11 metals. Water emissions associated with electrical energy offsets are also considered. Reductions in environmental emissions for a 500-metric-ton-per-day combustion facility that recovers energy are calculated.     

Ozone Injection into an Activated Carbon Bed to Remove Hydrogen Sulfide in the Presence of Concurrent Substances

ABSTRACT

Adsorption using activated carbon is one of the most reliable techniques for preventing odor by substances such as H₂S. Concurrent substances in effluent gas often reduce the removal capacity of activated carbon for H₂S. As a means of restoring capacity under such conditions, ozone injection into an activated carbon column was examined. When activated carbon was saturated with substances such as toluene, ethanol, n-butanol, or iso-butanol, its capacity to remove H₂S decreased in proportion to the amount of the saturating substance. Under such conditions, ozone injection greatly increased capacity. Toluene, which is not easily decomposed by ozone, was displaced by ozone and by oxidized products of H₂S. Ethanol, which is adsorbed in small amounts by activated carbon and easily decomposed by ozone, was removed by ozone injection. Butanols, which are also decomposed by ozone and adsorbed in large quantities by activated carbon, showed intermediate behavior between that of toluene and ethanol.     

Measurement of photosynthesis as a way to assess phytotoxicity

Abstract

Toxic agents may affect photosynthesis either by altering the diffusion of CO₂ to the photosynthesizing cells or by altering the chloroplast activity for CO₂ fixation. Therefore, the effect of toxic chemicals can be assessed by measurement of the rate of CO₂ fixation. The effects on photosynthesis caused by altered CO₂ diffusion can be distinguished from those caused at the chloroplast level by evaluating the CO₂ concentration inside the leaf. If CO₂ concentrations remain constant or rise as photosynthesis declines, the inhibition must act on chloroplast activity. If the CO₂ concentrations decrease as photosynthesis declines, the inhibition may be caused by slower diffusion of CO₂into the leaf. The latter possibility would suggest a stomatal closure to be the most probable cause of the decline of photosynthesis.     

Effect of NOx Control Processes on Mercury Speciation in Utility Flue Gas

Abstract

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NO_x control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NO_x control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH₃, has been evaluated. The influence of NH₃ on fly ash Hg reactions also is being investigated.     

Source Apportionment of Fine Particulate Matter in the Southeastern United States

Abstract

Particulate matter (PM) less than 2.5 μm in size (PM_2.5)source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH₄HSO₄, (NH₄)₂SO₄,NH₄NO₃, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (<50%) of ambient PM_2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

A Study on the Treatment of CO2, SO2, Nox,and Fly Ash by Pulse Activation

ABSTRACT

This paper presents a technique for the complete, simultaneous decomposition of CO₂, SO₂, and NO_x, as well as the simultaneous removal of fly ash by ultra-high voltage pulse activation. Ultra-high voltage narrow pulse is used to make the gases in the reactor become active molecules, which are then dissociated into nonpoisonous gas molecules and solid particles under the control of a directional reaction model. By using a sufficient charge and a strong electric field, the fly ash can be removed. It becomes the carrier of C and S, and its efficiency is 99.5%. Owing to the action of catalyst B (using Ni as the mother's body), the activation energy of CO₂, SO₂, and NO_x gases is reduced in great magnitude, and their removal efficiency can reach 75~90% at normal pressure and 180 °C.     

Wintertime PM2.5 and PM10 Source Apportionment at Sacramento,California

ABSTRACT

The chemical mass balance (CMB) model was applied to winter (November through January) 1991–1996 PM2.5 and PM10 data from the Sacramento 13th and T Streets site in order to identify the contributions from major source categories to peak 24-hr ambient PM_2.5 and PM₁₀ levels. The average monthly PM₁₀ monitoring data for the nine-year period in Sacramento County indicate that elevated concentrations are typical in the winter months. Concentrations on days of highest PM₁₀ are dominated by the PM2.5 fraction. One factor contributing to increased PM_2.5 concentrations in the winter is meteorology (cool temperatures, low wind speeds, low inversion layers, and more humid conditions) that favors the formation of secondary nitrate and sulfate aerosols. Residential wood burning also elevates fine particulate concentrations in the Sacramento area.

The results of the CMB analysis highlight three key points. First, the source apportionment results indicate that primary motor vehicle exhaust and wood smoke are significant sources of both PM_2.5 and PM₁₀ in winter. Second, nitrates, secondarily formed as a result of motor-vehicle and other sources of nitrogen oxide (NO_x), are another principal cause of the high PM_2.5 and PM₁₀ levels during the winter months. Third, fugitive dust, whether it is resuspended soil and dust or agricultural tillage, is not the major contributor to peak winter PM_2.5 and PM10 levels in the Sacramento area.     

Nonthermal Plasma Chemical Processing of Bromomethane

ABSTRACT

Nonthermal plasma chemical decomposition of bromomethane (CH₃Br) was investigated with a coaxial type packed-bed plasma reactor. It has been demonstrated that plasma chemical processing is an effective approach to decompose CH₃Br in a wide concentration range. It has been shown that CH₃Br decomposition reactivity depends on reactor operating factors such as background gas, O₂ concentration, and humidification. Higher decomposition efficiencies can be obtained in dry N₂. However, organic byproducts such as BrCN are concurrently produced under deaerated conditions. Water suppresses CH₃Br decomposition and also affects the yields of CO_x (CO and CO₂) and organic byproducts due to the involvement of some active species generated from water. The presence of O₂ retards CH₃Br decomposition by quenching high-energy electrons, while it suppresses organic byproducts and improves CO_x yield. The reacted carbons in CH₃Br are recovered as CO_x almost quantitatively in air. Higher CO₂ selectivities cannot be achieved by increasing O₂ concentration. NO_x formation, which is accompanied by CH₃Br decomposition, can be effectively suppressed by decreasing O₂ concentration down to 2%. Furthermore, reaction mechanisms are discussed by comparing the reactivities of CH₃Br and its congeners.