Effect of pH and Temperature on the Kinetics of Odor Oxidation Using Chlorine Dioxide

Abstract

Increasing public concerns over odors and air regulations in nonattainment zones necessitate the remediation of a wide range of volatile organic compounds (VOCs) generated in the poultry-rendering industry. Currently, wet scrubbers using oxidizing chemicals such as chlorine dioxide (ClO₂) are utilized to treat VOCs. However, little information is available on the kinetics of ClO₂ reaction with rendering air pollutants, limiting wet scrubber design and optimization. Kinetic analysis indicated that ClO₂ does not react with hexanal and 2-methylbutanal regardless of pH and temperature and implied that alde-hyde removal occurs primarily via mass transfer. Contrary to the aldehydes, ethanethiol or ethyl mercaptan (a model compound for methanethiol or methyl mercaptan) and dimethyl disulfide (DMDS) rapidly reacted with ClO₂. The overall reaction was found to be second and third order for ethanethiol and DMDS, respectively. Moreover, an increase in pH from 3.6 to 5.1 exponentially increased the reaction rate of ethanethiol (e.g., k ₂ = 25– 4200 L/mol/sec from pH 3.6 to 5.1) and significantly increased the reaction rate of DMDS if increased to pH 9 (k ₃ = 1.4 × 10⁶ L²/mol²/sec). Thus, a small increase in pH could significantly improve wet scrubber operations for removal of odor-causing compounds. However, an increase in pH did not improve aldehyde removal. The results explain why aldehyde removal efficiencies are much lower than methanethiol and DMDS in wet scrub-bers using ClO₂.     

Effectiveness of urea in enhancing the extractability of 2,4,6-trinitrotoluene from chemically variant soils

One of the major challenges in developing an effective phytoremediation technology for 2,4,6-trinitrotoluene (TNT) contaminated soils is limited plant uptake resulting from low solubility of TNT. The effectiveness of urea as a solubilizing agent in increasing plant uptake of TNT in hydroponic systems has been documented. Our preliminary greenhouse experiments using urea were also very promising, but further characterization of the performance of urea in highly-complex soil-solution was necessary. The present study investigated the natural retention capacity of four chemically variant soils and optimized the factors influencing the effectiveness of urea in enhancing TNT solubility in the soil solutions. Results show that the extent of TNT sorption and desorption varies with the soil properties, and is mainly dependent on soil organic matter (SOM) content. Hysteretic desorption of TNT in all tested soils suggests irreversible sorption of TNT and indicates the need of using an extractant to increase the release of TNT in soil solutions. Urea significantly (p < 0.0001) enhanced TNT extraction from all soils, by increasing its solubility at the solid/liquid interface. Soil organic matter content and urea application rates showed significant effects, whereas pH did not exert any significant effect on urea catalysis of TNT extraction from soil. The optimum urea application rates (125 or 350 mg kg⁻¹) for maximizing TNT extraction were within the limits set by the agronomic fertilizer-N rates used for major agricultural crops. The data obtained from this batch study will facilitate the optimization of a chemically-catalyzed phytoremediation model for cleaning up TNT-contaminated soils.     

Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Co-composting of alkaline tissue digester effluent with yard trimmings

Alkaline digestion of animal carcasses is gaining popularity as a method of disposing of animals because of its very effective pathogen control and general ease of operation. Once completed, the resulting high-strength effluent can be released into the municipal sewer systems. In some cases where the municipal system is unable to handle this high-strength wastewater, alternate methods of treatment are required. Co-composting with a low-moisture substrate such as yard trimmings can be an effective option. This paper reports the results of absorption tests to determine the amount of digester effluent (from the Tissue Digestortrade mark process) that can be added to yard waste before leachate production begins. In addition, a low dosage of liquid effluent was added to yard trimmings and composted in laboratory bioreactors. Results show that leachate production begins when 0.6L-effluent is added per kg-unamended yard waste at an original moisture content of 55.6%. The amount of leachate produced increases exponentially following the empirical equation: leachate in mL/kg=0.145 e(6.007Effluent dosage in L/kg) (valid in the effluent addition range of 0-1.2L/kg). Composting of yard waste with effluent showed that the initial pH did not inhibit microbial activity up to 9.39 pH. Variability was high and there was no statistically significant difference in dry matter degradation between treatments (measured range was 1.3-6.0% of initial dry matter). Final compost had nitrogen and phosphorus concentrations of approximately 1% and 0.1%, respectively. The potassium concentration increased with increasing effluent addition and was 1.84% in the 0.2-L/kg treatment. All regulated heavy metals were several-fold below US EPA limits.     

Studies on the Uptake of Heavy Metals by Various Plant Species on Chromite Minespoils in Sub-tropical Regions of India

The presence of heavy metals (Cr, Ni and Fe) in soil and accumulated by herbs, shrubs and trees regenerated naturally on the minewaste-dumps of Sukinda chromite mines (TISCO sector) were investigated. There was significant correlationship between Cr and Fe in the soil where a tree species (Catunaregam spinosa) occurred. Guazuma ulmifolia and Diospyros montana also did show significant correlation between leaf, stem and soil for Cr, Ni and Fe. Among the shrubs (Calotropis gigantea, Chromolaena odorata, Phyllanthus reticulatus and Woodfordia fruticosa) significant and positive correlations were obtained for Cr and Ni in soil and iron and nickel in leaf and chromium and nickel in stem. Among the annual herbs, whole plant of tephrosia purpurea and Borrevia articularis showed significant and positive correlation with chromium and nickel with the maximum correlation coefficient value. It was concluded that the above information would be useful in revegetation programmes in subtropical regions having seasonal rainfall.     

Diclofenac disposition in Indian cow and goat with reference to Gyps vulture population declines

Gyps vultures across India are declining rapidly and the NSAID diclofenac has been shown to be the major cause. Vultures scavenge livestock carcasses that have been treated with diclofenac within the days preceding death. We present data on diclofenac disposition in Indian cow and goat, and field data on the prevalence of diclofenac in carcases in the environment. In the disposition experiment, animals were treated with a single intramuscular injection of diclofenac at 1000 microg kg-1 bw. In cow, diclofenac was detectable in liver, kidney and intestine up to 71 h post-treatment; in plasma, half-life was 12.2 h. In goat, tissue residues were undetectable after 26 h. Prevalence of diclofenac in liver from 36 dead livestock collected in the field was 13.9%. Data suggest that diclofenac residues in Indian cow and goat are short-lived, but diclofenac prevalence in carcasses available to vultures may still be very high.     

Chlorine emission during the chlorination of water – case study

This paper deals with the incident of the excessive use of chlorine and leakage of unused chlorine from an industrial chlorination cistern and the lesson learned.     

Additional danger of arsenic exposure through inhalation from burning of cow dung cakes laced with arsenic as a fuel in arsenic affected villages in Ganga-Meghna-Brahmaputra plain

In arsenic contaminated areas of the Ganga-Meghna-Brahmaputra (GMB) plain (area 569,749 sq. km; population over 500 million) where traditionally cow dung cake is used as a fuel in unventilated ovens for cooking purposes, people are simply exposed to 1859.2 ng arsenic per day through direct inhalation, of which 464.8 ng could be absorbed in respiratory tract.     

Assessment of heavy metal status and identification of source in soils under intensive vegetable growing areas of Brahmaputra valley,North East India

Environmental Monitoring and Assessment - Evaporation is an important meteorological variable that has a great impact on water resources. In the current research, climatology data, and seasonal...