Potential Interference Bias in Ozone Standard Compliance Monitoring

Abstract

The U.S. Environmental Protection Agency has established a federal reference method (FRM) for ozone (O₃) and allowed for designation of federal equivalent methods (FEMs). However, the ethylene‐chemiluminescence FRM for O₃ has been replaced by the UV photometric FEM by most state and local monitoring agencies because of its relative ease of operation. Accumulating evidence indicates that the FEM is prone to bias under the hot, humid, and stagnant conditions conducive to high O₃ formation. This bias may lead to overreporting hourly O₃ concentrations by as much as 20–40 ppb. Measurement bias is caused by contamination of the O₃ scrubber, a problem that is not detected by dry air calibration. An adequate wet test has not been codified, although a procedure has been proposed for agency consideration. This paper includes documentation of laboratory tests quantifying specific interferant responses, collocated ambient FRM/FEM monitoring results, and smog chamber comparisons of the FRM and FEMs with alternative scrubber designs. As the numbers of reports on monitor interferences have grown, interested parties have called for agency recognition and correction of these biases.     

Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Manure placement depth impacts on crop yields and N retained in soil

The objective of this study was to determine the impact of manure placement depth on crop yield and N retention in soil. Experimental treatments were deep manure injection (45 cm), shallow manure injection (15 cm), and conventional fertilizer-based management with at least three replications per site. Water infiltration, and changes in soil N and P amounts were measured for up to 30 months and crop yield monitored for three seasons following initial treatment. Deep and shallow manure injections differed in soil inorganic N distributions. For example, in the manure slot the spring following application, NO₃-N in the surface 60 cm was higher (p < .01) when injected 15 cm (21.4 μ g/g) into the soil than 45 cm (11.7 μ g/g), whereas NH₄-N had opposite results with shallow injection having less (p = 0.045) NH₄-N (102 μ g/g) than deep (133 μ g/g) injection. In the fall one year after the manure was applied, NO₃-N and NH₄-N were lower (p = 0.001) in the shallow injection than the deep injection. The net impact of manure placement on total N was that deep injection had 31, 59, and 44 more kg N ha^{? 1} than the shallow injection treatment 12, 18, and 30 months after application, respectively. Deep manure injection did not impact soybean (Glycine max L.) yield, however corn (Zea mays L.) yield increased if N was limiting. The higher corn yield in the deep injected treatment was attributed to increased N use efficiency. Higher inorganic N amounts in the deep injection treatment were attributed to reduced N losses through ammonia volatilization, leaching, or denitrification. Results suggest that deep manure placement in glacial till soil may be considered a technique to increase energy, N use efficiency, and maintain surface and ground water quality. However, this technique may not work in glacial outwash soils due to the inability to inject into a rocky subsurface.     

Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H₂O₂ addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H₂O₂ and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

1987 Joint EPRI/EPA Symposium on Stationary Combustion NOX Control

From March 23rd to 26th, 1987, the city of New Orleans hosted 350 attendees, including representatives from 15 foreign countries, at the 1987 Joint Symposium on Stationary Combustion NO_x Control. Cosponsored by the Electric Power Research Institute (EPRI) and the U.S. Environmental Protection Agency (EPA), the symposium provided attendees the opportunity to hear 49 papers in nine sessions covering technological and regulatory developments on NO_x control in the United States and abroad since the May 1985 symposium in Boston. Session topics included general environmental issues, low-NO_x combustion equipment (i.e., low-NO_x burners, reburning, etc.), flue gas treatment, fundamental combustion research, and special issues for cyclone coal-fueled boilers, oil- and gas-fired boilers, and industrial combustion applications.

Advances to the state-of-the-art presented at this symposium include: improved and/or newly applied combustion modifications for pulverized coal-fired boilers; further analyses of reburning, the leading combustion modification option for cyclone-equipped boilers; initial experiences with catalytic flue gas treatment in Europe; studies of NO_x control retrofit options for oil- and gas-fired utility systems; and new technology developments for coal, oil, and gas fueled utility and industrial combustors.

This paper summarizes those presentations that discussed significant changes since May 1985 in areas of potential interest to EPRI and its utility members. Where appropriate, they include our perspectives on the applicability of these newly disclosed findings to utility systems.     

Predicting and Managing the Health Risks of Sour-Gas Wells

The development of sour-gas resources in Canada and the United States has prompted concerns about the public health risks of accidental releases of gas contaminated with hydrogen sulfide (H₂S) from wells. This paper focuses on methods for improving the prediction and management of those risks. Data associated with the health effects of hydrogen sulfide are examined, and it is suggested that sublethal effects should be addressed in risk assessments of sour-gas wells along with the life-threatening effects normally considered. The demarcation of hazard zones around wells can be improved by using a statistical approach for estimating an upper-bound H₂S release rate; this rate can then be used in an atmospheric dispersion model to estimate maximum distances to downwind concentrations for lethal (300 ppmv) and sublethal (50 ppmv) effects resulting from an accidental release. A vertical release is found to have little impact, especially under stable atmospheric conditions; horizontal releases, on the other hand, result in the greatest downwind distances for health impacts. Management of health risks depends on a mix of safety technologies and contingency actions, such as well-ignition options and provision for post-release monitoring and assessment of ambient H₂S concentrations.     

Removal of Volatile Aliphatic Hydrocarbons in a Soil Bioreactor

Soil removal of propane, isobutane and n-butane from a waste air stream was evaluated in the laboratory and in a prototype soil bioreactor. Laboratory investigations indicated first-order kinetics and the potential to degrade light aliphatic hydrocarbons and trichlorethylene, a compound ordinarily resistant to aerobic biological treatment. The predicted behavior of the bioreactor, based on laboratory studies, agreed closely with the actual behavior of the Reid system. The prototype bioreactor reduced the hydrocarbon concentrations in the air by at least 90percent with a residence time of 15 minutes and a pressure drop of 85 cm of water. The bioreactor functioned well through a range of temperatures, 12°C to 24°C.     

Water Content of Collected Aerosols in the South Coast and Southeast Desert Air Basins

Pollution prevention/waste minimization is a win-win-win situation for government, industry, and the public, which offers more than just protection of the environment for all. Industry gains from reduced capital and operating costs, reduced liabilities, cleaner and safer working conditions, conservation of energy and material resources, and the opportunity for government and industry to work together in a cooperative manner. However, a number of regulatory barriers exist which discourage pollution prevention/waste minimization. This paper provides examples from the aluminum, chemical, petroleum, and wood treating industries of how these regulatory barriers become disincentives. To promote pollution prevention/waste minimization, Congress and the U.S. EPA need to reexamine those RCRA provisions which support a command and control strategy that creates the barriers. The barriers include the distinction between value and valueless materials, offsite storage requirements prior to reuse/recycle, the “Derived from Rule”, the “Burning for Fuel Rule”, land ban technology standards, and RD&;D restrictions. A new RCRA Pollution Prevention/Waste Minimization subtitle is proposed to eliminate or minimize these barriers.