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.     

Analysis of extinction in ultraviolet and visible spectra of water bodies of the Paraguay and Brazil wetlands

The extinction spectra in ultraviolet and visible radiation were analyzed using filtered and unfiltered water samples obtained in 11 open water bodies in the Neembucù (Paraguay) and Pantanal (Brazil) wetlands. The role of dissolved and suspended matter in the total extinction was analyzed between 260 nm and 700 nm. The chromophoric dissolved organic matter (CDOM) was the major component in extinction of considered ultraviolet radiation (260-400 nm). The differences in CDOM concentrations explained the main pattern of extinction of the ultraviolet radiation in the samples. Nevertheless, differences between the studied water bodies were found also to depend on the rate of photodegradation and photobleaching. The methodology developed in the present study was to distinguish "humic optic waters" according to quantity and quality of dissolved and suspended matter present. In the "humic optic water", the penetration of 10% of incident UV radiation and the photoactive layer are estimated. The influence of particulate matter increases in the total extinction of the wavelengths higher than 400 nm. The integral of the extinction curve of suspended matter in the visible wavelengths (400-700 nm) was found to relate with the total suspended solids and chlorophyll concentrations.     

Development of a regenerable system employing silica-titania composites for the recovery of mercury from end-box exhaust at a chlor-alkali facility

The release of mercury to the environment is of particular concern because of its volatility, persistence, and tendency to bioaccumulate. The recovery of mercury from end-box exhaust at chlor-alkali facilities is important to prevent release into the environment and reduce emissions as required by NESHAP (National Emission Standards for Hazardous Air Pollutants). A pilot-scale photocatalytic reactor packed with silica-titania composite (STC) pellets was tested at a chloralkali facility over a 3-month period. This pilot reactor treated up to 10 ft3/min (ACFM) of end-box exhaust and achieved 95% removal. The pilot reactor was able to maintain excellent removal efficiency even with large fluctuations in influent mercury concentration (400-1600 microg/ft3). The STC pellets were regenerated ex situ by regeneration with hydrochloric acid and performed similarly to virgin STC pellets when returned to service. On the basis of these promising results, two full-scale reactors with in situ regeneration capabilities were installed and operated. After optimization, these reactors performed similarly to the pilot reactor. A cost analysis was performed comparing the treatment costs (i.e., cost per pound of mercury removed) for sulfur-impregnated activated carbon and the STC system. The STC proved to be both technologically and economically feasible for this installation.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

The effect of cyclic aerobic-anoxic conditions on biodegradation of benzoate.

The response of a mixed microbial culture to cyclic aerobic and anoxic (denitrifying) conditions was studied in a chemostat with a 48-hour hydraulic residence time receiving a feed containing benzoate and pyruvate. When the cyclic conditions were 3-hour aerobic and 9-hour anoxic, the bacteria-degraded benzoate aerobically via the catechol 2,3-dioxygenase (C23DO) pathway. The quantity of C23DO remained constant throughout the anoxic period but decreased during the initial portion of the aerobic period before returning to the level present in the anoxic period. Anoxic biodegradation of benzoate was via benzoyl-CoA reductase, which remained constant regardless of the redox condition. The aerobic benzoate uptake capability (AeBUC) of the culture increased during the aerobic period but decreased during the anoxic period. The anoxic benzoate uptake capability (AnBUC) exhibited the opposite response. When the cycle was 6-hour aerobic and 6-hour anoxic, aerobic biodegradation of benzoate proceeded via the protocatechuate 4,5-dioxygenase (P45DO) pathway. The P45DO activity decreased early in the aerobic period, but then increased to the level present during the anoxic period. The level of benzoyl-CoA reductase was constant throughout the cycle. Furthermore, AeBUC and AnBUC responded in much the same way as in the 3/9-hour chemostat. During a 9-hour aerobic and 3-hour anoxic cycle, the culture synthesized both P45DO and C23DO, with the former having significantly higher activity. Unlike the other two cycles, AeBUC changed little during the aerobic period, although AnBUC decreased. The culture was well-adapted to the cyclic conditions as evidenced by the lack of accumulation of either substrate during any cycle tested. This suggests that cyclic aerobic-anoxic processes can be used in industrial wastewater-treatment facilities receiving significant quantities of simple aromatic compounds like benzoate. However, the results showed that the kinetics of benzoate degradation were different under aerobic and anoxic conditions, a situation that must be considered when modeling cyclic bioreactors receiving aromatic compounds.     

Treatment of carbofuran-bearing synthetic wastewater using UASB process

In the present study, fate of carbofuran in anaerobic environments and the adverse effects of carbofuran on conventional anaerobic systems were evaluated. Carbofuran degradation studies were carried out in batch reactors with varying carbofuran concentrations of 0 to 270.73 mg/L corresponding to a sludge-loading rate (SLR) of 2.12 x 10(-6) to 3.83 x 10(-3) g of carbofuran/g of volatile suspended solids (VSS)/d. Carbofuran concentration was reduced to undetectable levels at the end of 8 and 13 days in the batch reactors operated with a SLR of 2.12 x 10(-6) and 3.33 x 10(-5) g of carbofuran/g of VSS/d, respectively. Performances of two anaerobic reactors i.e. upflow anaerobic sludge blanket (UASB) and modified UASB (with tube settlers) were evaluated in the presence and absence of carbofuran using synthetic wastewater. In the absence of carbofuran, the soluble chemical oxygen demand (COD) removal efficiency in the conventional UASB reactor at 8 h and 6 h hydraulic retention time (HRT) was nearly 88% and 76%, respectively, whereas in modified UASB reactor it was increased to 90% at 8 h HRT and 78% at 6 h HRT. When 28 mg/L (SLR of 1.19 x 10(-2) g of carbofuran/g of VSS/d) of carbofuran was introduced in the reactors, the COD removal efficiency was reduced to 41% and 44% in conventional and modified UASB reactors respectively. However, the reactor could maintain around 80% COD removal efficiency at a carbofuran concentration of 7.84 mg/L (SLR of 3.64 x 10(-3) g of carbofuran/g of VSS/d). The reactor efficiency was also measured in terms of specific acetoclastic methanogenic activity (SMA). The toxic effect of carbofuran was reversible to a certain extent. Carbofuran removal efficiency in the conventional UASB reactor at carbofuran concentrations of 7, 13 and 28 mg/L were 40 +/- 3%, 27 +/- 3%, and 11 +/- 3%, respectively. In modified UASB reactor, carbofuran removal efficiency was almost uniform at 7 and 13 mg/L but it was reduced nearly by 56% at 28 mg/L. The major metabolite of carbofuran i.e. 3-keto carbofuran was found in all the reactors.     

Field dissipation of oxyfluorfen in onion and its dynamics in soil under Indian tropical conditions

Oxyfluorfen, a diphenyl-ether herbicide is being used to control annual and perennial broad-leaved weeds and sedges in a variety of field crops including onion. The present study was aimed to investigate the dynamics and field persistence of oxyfluorfen in onion plant, bulb and soil under Indian tropical conditions. Application of four rates of oxyfluorfen viz., 200, 250, 300 and 400 g AI ha^?1 as pre-emergence gave good weed control in field experiment with onion. The oxyfluorfen residue dissipated faster in plant than in soil respectively, with a mean half-life of 6.1 and 11.2 days. Dissipation followed first-order kinetics. In laboratory column leaching experiments, 17 percent of the applied oxyfluorfen was recovered from the soil and indicates its solubility in water and mobility in sandy clay loam soil was low. A sorption study revealed that the adsorption of oxyfluorfen to the soil was highly influenced by the soil organic carbon with the K_oc value of 5450. The study concludes that the dissipation of oxyfluorfen in soil and onion was dependent on the physico-chemical properties of the soil and environmental conditions.     

Diflubenzuron residue and persistence on an oak forest after aerial application

Abstract

A twenty hectare forest block in central Pennsylvania was aerially sprayed with diflubenzuron (Dimilin 25W®) at the dose of 33.23g A.I./ha in 9.4 litres/ha. Leaf samples were collected from the upper and lower canopies of 27 oaks and understory within this block on the day of spray, May 29, 1991. Canopy leaves were also collected on May 31, June 10, July 29 and September 26, 1991.

Recovery of diflubenzuron residues on fortified canopy‐leaf and litter‐leaf samples using analytical techniques employed in this study averaged 87.4% (SE = 7.5%) and 66.2% (SE = 8.2%), respectively.

On the day of spray, diflubenzuron residues on the upper canopy, lower canopy and understory averaged 81.18, 39.65 and 8.35 ng/cm², respectively. Diflubenzuron residues on canopy‐leaf samples collected 2, 12, 61 and 120 days post‐spray averaged 14.83 (SE = 10.19), 16.75 (SE = 9.95), 12.84 (SE = 8.25) and 11.20 (SE = 7.52) ng/cm², respectively. Diflubenzuron residues on litter‐leaf samples collected after leaf senescence ‐ 169 and 323 days post spray contained measurable amounts of diflubenzuron in 51 and 59% of the samples, respectively. Of the samples with measurable amounts of diflubenzuron, residues averaged 1.36 (SE = 2.44) and 0.65 ng/cm² (SE = 0.73) respectively.     

Improved computational model (AQUIFAS) for activated sludge, integrated fixed-film activated sludge, and moving-bed biofilm reactor systems, Part I: Semi-empirical model development

Research was undertaken to develop a model for activated sludge, integrated fixed-film activated sludge (IFAS), and moving-bed biofilm reactor (MBBR) systems. The model can operate with up to 12 cells (reactors) in series, with biofilm media incorporated to one or more cells, except the anaerobic cells. The process configuration can be any combination of anaerobic, anoxic, aerobic, post-anoxic with or without supplemental carbon, and reaeration; it can also include any combination of step feed and recycles, including recycles for mixed liquor, return activated sludge, nitrates, and membrane bioreactors. This paper presents the structure of the model. The model embeds a biofilm model into a multicell activated sludge model. The biofilm flux rates for organics, nutrients, and biomass can be computed by two methods--a semi-empirical model of the biofilm that is relatively simpler, or a diffusional model that is computationally intensive. The values of the kinetic parameters for the model were measured using pilot-scale activated sludge, IFAS, and MBBR systems. For the semiempirical version, a series of Monod equations were developed for chemical oxygen demand, ammonium-nitrogen, and oxidized-nitrogen fluxes to the biofilm. Within the equations, a second Monod expression is used to simulate the effect of changes in biofilm thickness and fraction nitrifiers in the biofilm. The biofilm flux model is then linked to the activated sludge model. The diffusional model and the verification of the models are presented in subsequent papers (Sen and Randall, 2008a, 2008b). The model can be used to quantify the amount of media and surface area required to achieve nitrification, identify the best locations for the media, and optimize the dissolved oxygen levels and nitrate recycle rates. Some of the advanced features include the ability to apply different media types and fill fractions in cells; quantify nitrification, denitrification, and biomass production in the biofilm and mixed liquor suspended solids; and perform dynamic simulations.