Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Yield response of potato to spatially patterned nitrogen application

Although crop response to nitrogen fertilization has long been studied, classical experimental designs have led to inadequate accounting of spatial variability in field properties and yield response. Analytical methods to explicitly account for spatial variability now exist but the complementary modification of experimental design is still developing. There is a need to combine these analytical methods with non-traditional experimental design. A 2-year study was implemented to assess the response of potato (Solanum tuberosum cv. Kennebec) yield to nitrogen fertilizer rate. We used a transect-type plot design where four nitrogen treatments (0, 56, 112, and 280 kg N ha^?1) were applied systematically in a continuous sinusoidal pattern along longitudinal transects. Measured field properties included topography, soil texture, pre-application soil nitrate levels, and plant available soil water content. A random field linear model was used to simultaneously account for treatment effects and soil properties. The results showed that treatment effects were significantly different from each other; however, if spatially correlated errors were accounted for, these differences were smaller and significance levels lower. Nitrogen response functions varied widely throughout the field. Of the covariates, only clay content proved important in explaining spatial differences in response to N. The sinusoidal response pattern of N was similar over the 2 years but the amplitudes varied due to differences in weather. Interactions between uncharacteristically high rainfall and a sandy field soil may have minimized discernable effects of the other covariates. The results demonstrated how the statistical analysis of potato response to a patterned application of nitrogen fertilizer can take advantage of spatial correlations to understand the response of potato to nitrogen application over larger areas.     

Influence of x-ray diffraction sample preparation on quantitative mineralogy: implications for chromate waste treatment

Powders of chromite ore processing residue (COPR) were mineralogically evaluated using quantitative X-ray powder diffraction (XRPD) to illustrate the impacts of sample preparation procedures. Chromite ore processing residue is strongly alkaline, reactive, contains minerals of varying hardness and absorption coefficients, and exhibits significant amorphicity. This poses a challenge to produce powders for XRPD analysis that are sufficiently fine and of uniform particle size while avoiding mineral reactions and overgrinding effects. Dry, hand pulverization to different grain sizes, and wet, mechanical pulverization (micromilling) using four milling liquids (cyclohexane, isopropanol, ethanol, and water), and variable milling durations (up to 15 min) were evaluated. Micromilling with a light, nonpolar, highly evaporative liquid such as cyclohexane with a milling time of 5 min mitigated systematic errors such as microabsorption and preferred orientation as it produced finer and more uniform particle size distributions than the hand-pulverized powders, while simultaneously affording the least time for sample preparation. Conversely, the use of water as milling liquid resulted in extensive hydration reactions during sample preparation, causing mischaracterization and significant underestimation of its reactive brownmillerite content, which can complicate the remediation design process for COPR. Hand pulverization emerged as a necessary complement to quantify Cr(VI)-containing, softer minerals destroyed during mechanical milling, the quantification of which has also important implications for COPR treatment design. The findings of this study may be applicable in a variety of geochemically complicated and reactive environmental media (metal-contaminated soils, stabilized/solidified media, inorganic waste), and points to the importance of the sample preparation method to obtain reliable quantitative XRPD results.     

Novel Concepts,Methods and Advanced Technology in Particulate/Gas Separation

Particulate/gas separation techniques have been the subject of much research in recent years. From this research have come new concepts and methods, such as the use of acoustics, high gradient magnetic fields, and electrostatic filtration in particulate/gas separation. Some of the results of the work in the field were discussed by scientists in a workshop held at the University of Notre Dame in April 1977. The highlights of the discussions at that workshop are presented here.     

A Method of Predicting Point and Path- Averaged Ambient Air VOC Concentrations,Using Meteorological Data

A method of predicting point and path-averaged ambient air VOC concentrations is described. This method was developed for the case of a plume generated from a single point source, and is based on the relationship between wind directional frequency and concentration. One-minute means of wind direction and wind speed were used as inputs to a Gaussian dispersion model to develop this relationship.

Both FTIR spectrometry and a whole-air sampling method were used to monitor VOC plumes during simulated field tests. One test set was also conducted using only whole-air samplers deployed in a closely-spaced network, thus providing an evaluation of the prediction technique free of any bias that might exist between the two analytical methods.

Correlations between observed point concentrations and wind directional frequencies were significant at the 0.05 level in most cases. Predicted path-integrated concentrations, based on observed point concentrations and meteorological data, were strongly correlated with observed values. Predicted point concentrations, based on observed path-integrated concentrations and meteorological data, accurately reflected the location and magnitude of the highest concentrations from each test, as well as the shape of the concentration-versus-crosswind distance curve.     

Weekday/Weekend Ozone Differences: What Can We Learn from Them?

Abstract

A national analysis of weekday/weekend ozone (O₃) differences demonstrates significant variation across the country. Weekend 1-hr or 8-hr maximum O₃ varies from 15% lower than weekday levels to 30% higher. The weekend O₃ increases are primarily found in and around large coastal cities in California and large cities in the Midwest and Northeast Corridor. Both the average and the 95th percentile of the daily 1-hr and 8-hr maxima exhibit the same general pattern. Many sites that have elevated O₃ also have higher O₃ on weekends even though traffic and O₃ precursor levels are substantially reduced on weekends. Detailed studies of this phenomenon indicate that the primary cause of the higher O₃ on weekends is the reduction in oxides of nitrogen (NO_x) emissions on weekends in a volatile organic compound (VOC)-limited chemical regime. In contrast, the lower O₃ on weekends in other locations is probably a result of NO_x reductions in a NO_x-limited regime. The NO_x reduction explanation is supported by a wide range of ambient analyses and several photochemical modeling studies. Changes in the timing and location of emissions and meteorological factors play smaller roles in weekend O₃ behavior. Weekday/weekend temperature differences do not explain the weekend effect but may modify it.     

The potential inhalation hazard posed by dioxin-contaminated soil

Conservative models were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates originating from soil containing 100 ppb TCDD. The upper-bound estimates were 3.25 pg/m³ of airborne TCDD vapor on-site and 0.51 pg/m³ for TCDD vapor 100 meters downwind. The TCDD air concentration on-site due to suspended particulate is estimated to be 1.4 pg/m³, based on a TSP level of 0.07 mg/m³. Assuming 70 years of continuous exposure to these concentrations, the upper-bound cancer risks determined from the Jury model were estimated to be 9.4 × 10⁻⁶ to 1.1 × 10⁻⁴ and 1.5 × 10⁻⁶ to 1.7 × 10⁻⁵ for inhalation of on- and off-site vapor, respectively, and 4.1 × 10⁻⁶ to 4.6 × 10⁻⁵ for dust inhalation. Since few sites have average soil concentrations as high as 100 ppb TCDD, this worst-case analysis indicates that inhalation will rarely, if ever, be a significant route of exposure to TCDD-contaminated soil. Experimental results support this claim and point to much lower risk estimates (8.4 × 10⁻⁹ to 9.9 × 10⁻⁸), suggesting that the parameters used in the Jury model are likely to overestimate the actual airborne levels of TCDD at contaminated sites.     

Environmental Technology Verification (ETV) test of dioxin emission monitors

The performance of four dioxin emission monitors, including two long-term sampling devices, the Dioxin-MonitoringSystem (DMS) and AMESA (the adsorption method for sampling dioxins and furans), and two semireal-time continuous monitors, the resonance ionization with multimirror photon accumulation time-of-flight mass spectrometer (RIMMPA-TOFMS) and the jet resonance-enhanced multiphoton ionization (jet-REMPI) system were tested. A package boiler burning a simulated chlorinated hazardous waste was used for a total of nine tests. Reference samples were collected during each test and analyzed for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs) using gas chromatography mass spectrometry. The PCDD/F concentrations of the reference samples measured by EPA Method 23 ranged from 0.9 to 6.0 ng toxic equivalence (TEQ)/dry standard cubic meter. The relative accuracies achieved by DMS, AMESA, and jet-REMPI varied from 22.6% to 78.2%, with 100% data completeness. The RIMMPA-TOFMS produced no quantifiable results due to various difficulties associated with the instrument during the testing. The two long-term samplers were easy to install and operate and provided a cumulative, averaged emission for the sampling period. The operations of the two semi-real-time continuous monitors were relatively complex, but one of them provided on-site, real-time data for PCDD/F emissions from measurement of a TEQ correlative indicator compound. This article summarizes results from the individual Environmental Technology Verification reports for the four dioxin monitors. This work was presented, in part, at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)