Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine

For the first time, regulatory protocols defined in the OECD guidelines were applied to determine the fate properties of a nanopesticide in two agricultural soils with contrasting characteristics. The nanoformulation studied had no effect on the degradation kinetics of atrazine indicating that (1) the release of atrazine from the polymer nanocarriers occurred rapidly relative to the degradation kinetics (half-lives 36–53 days) and/or that (2) atrazine associated with the nanocarriers was subject to biotic or abiotic degradation. Sorption coefficients, derived from a batch and a centrifugation technique at a realistic soil-to-solution ratio, were higher for the nanoformulated atrazine than for the pure active ingredient. Results indicate that the nanoformulation had an effect on the fate of atrazine. However, since the protocols applied were designed to assess solutes, conclusions about the transport of atrazine loaded onto the nanocarriers should be made extremely cautiously. The centrifugation method applied over time (here over 7 days) appears to be a useful tool to indirectly assess the durability of nanopesticides under realistic soil-to-solution ratios and estimate the period of time during which an influence on the fate of the active ingredient may be expected. More detailed investigations into the bioavailability and durability of nanopesticides are necessary and will require the development of novel methods suitable to address both the “nano” and “organic” characteristics of polymer-based nanopesticides.     

Audience Response to Values-based Marketplace Advocacy by the Fossil Fuel Industries

A form of issue advocacy, marketplace advocacy campaigns often arise in response to burgeoning societal concerns, especially those faced by energy industries. Although these campaigns may include brief and selective references to corporate activities, most campaigns place a much stronger emphasis on commonly shared societal values. This study examines audience response to values-based environmental marketplace advocacy messages by the fossil fuel industries through a series of focus groups. Four instrumental values were identified in campaign videos (innovation, community, resilience, and patriotism), and the terminal value of pragmatism, especially as it relates to environmental issues, was identified as a result of identification with one or more of the instrumental values. The findings are discussed through the lens of extant research on marketplace advocacy and organizational values as well as Habermas's theory of refuedalization, shedding light on the ways corporations appeal to commonly held societal values in an effort to generate support for a given industry.     

Effects of Constant versus Diurnally-Varying Light Intensity on Ozone Formation

Abstract

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photo-chemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

Comparison of Observed and Predicted Sector-Averaged Air Concentrations for Elevated Releases of Fluorescein Particles

The DWNWND gaussian plume computer code was used to calculate normalized 22.5° sector-averaged dispersant concentrations at distances from 400 to 7000 meters downwind from a 56 m high release point. These results were compared to sector average values obtained in fluorescein release experiments performed at Hanford, WA between 1967 and 1973. Pasquill-Gifford (PG) and Brookhaven National Laboratory (BNL) dispersion parameterization schemes were used, and atmospheric stability classes were determined from temperature gradient (Δr/ΔZ) and wind direction standard deviation (σ_θ) measurements. Comparisons between calculated values and experimental results were made as functions of changes in dispersion parameterization, stability class determination method, deposition velocity v _d , and gravitational fall velocity v _g . Values of the correlation coefficient ranged from significant (p < 0.01) to insignificant (p > 0.05). Best agreement between comparisons was found with v _g = v _d = 1.8 cm/s and Pasquill-Gifford parameters based on stability classes determined using wind direction standard deviation, σ_θ, rather than temperature gradient, ΔT/ΔZ. The best agreement gave a Pearson’s correlation coefficient r = 0.41 (significant at p < 0.01).     

Remedial Options for Leaking Underground Storage Tanks

Remedial options for leaking underground storage tanks were investigated in a joint project of the Electric Power Research Institute and the Underground Storage Tank Committee of the Utility Solid Waste Activities Group. Both existing and emerging technologies were examined. Thirteen remedial techniques were identified and initially characterized as in situ or non-in situ. In situ methods include volatilization, biodegradation, leaching and chemical reaction, vitrification, passive remediation, and isolation or containment. Non-in situ techniques include land treatment, thermal treatment, asphalt incorporation, solidification and stabilization, groundwater extraction and treatment, chemical extraction, and excavation. Soil and groundwater remediation problems have many site-specific considerations which must be considered in choosing an appropriate remedial option; these include cleanup goals, site and contaminant characteristics, cost, exposure pathways, and others. Appropriate remedial techniques are chosen by assessing technical, implementational, environmental and economic considerations of each available option to achieve the desired cleanup goal at the specified site.     

Development and Evaluation of a Method to Determine Indicator Microorganisms in Air Emissions and Residue from Medical Waste Incinerators

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80°C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

Canister-Based Method for Monitoring Toxic VOCs in Ambient Air

The availability of reliable, accurate and precise monitoring methods for toxic volatile organic compounds (VOCs) is a primary need for state and local agencies addressing daily monitoring requirements related to odor complaints, fugitive emissions, and trend monitoring. The canister-based monitoring method for VOCs is a viable and widely used approach that is based on research and evaluation performed over the past several years. This activity has involved the testing of sample stability of VOCs in canisters and the design of time-integrative samplers. The development of procedures for analysis of samples in canisters, including the procedure for VOC preconcentration from whole air, the treatment of water vapor in the sample, and the selection of an appropriate analytical finish has been accomplished. The canister-based method was initially summarized in the EPA Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air as Method TO-14. Modifications and refinements are being added to Method TO-14 in order to obtain a Statement of Work for the Superfund Contract Laboratory Program for Air. This paper discusses the developments leading to the current status of the canisterbased method and provides a critique of the method using results obtained in EPA monitoring networks.     

Comparison of Particle Size Distributions and Elemental Partitioning from the Combustion of Pulverized Coal and Residual Fuel Oil

ABSTRACT

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impac-tion as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments.

Experimental results on the mass and compositions of particles between 0.03 and >20 μm in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-μm aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large.

Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM <2.5 μm without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (~0.1 μm). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM <2.5 μm and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.     

PM10 Dispersion Modeling for Treasure Valley,Idaho

ABSTRACT

The recorded exceedances of the 24-hr PM₁₀ National Ambient Air Quality Standard (NAAQS) in Treasure Valley, Idaho, have been associated with prolonged stagnation periods during the winter. A comprehensive modeling study of PM₁₀ impact in Treasure Valley was performed to support the State Implementation Plan (SIP). The study included base-year and short-term episodic conditions. The ISCST3 (Industrial Source Complex Short Term 3) model, using the base-year meteorology and gridded emissions of mobile sources, point sources, and wood burning as input, generally agreed well with measurements in both temporal patterns and annual averages. The WYNDvalley model was evaluated using monitoring data and was used to simulate the PM₁₀ impact for episodic exceedances during stagnant winter conditions. An emission inventory was prepared for a base year (1995) and then extrapolated to the years 2000, 2005, 2010, and 2015 in order to determine air quality planning requirements. According to the simulations using base-year emissions and meteorology, exceedances are not expected. However, exceedances at some stations could be expected using projected emissions and episodic meteorology. Results from emission control strategies we developed indicate that mobile-source emissions have the most significant impact; reduction of 25% would be needed to eliminate the simulated exceedances in all projected years.