In Situ Determination of the Rate of Unassisted Degradation of Saturated-Zone Hydrocarbon Contamination

Abstract

A method to measure the in situ degradation rate of dissolved hydrocarbon contamination has been developed and applied at two locations at a field site. The method uses the rates of downward diffusion of oxygen and upward diffusion of carbon dioxide through the unsaturated zone, as calculated from vertical soil-gas concentration gradients, combined with stoichiometry to obtain two degradation rates in hydrocarbon mass per water table surface area per time. Values of 0.385 gram per m² per day and 0.52 gram per m² per day (based upon oxygen data) and 0.056 gram per m² per day and 0.12 gram per m² per day (based upon carbon dioxide data) were calculated at a field site with dissolved fuel contamination. This result of lower values from ground-air carbon dioxide concentrations is consistent with a significant fraction of the carbon dioxide produced being lost to the aqueous phase. Based upon a single-stage equilibrium phase-transfer model, gas/water volume ratios of 0.02 and 0.2 for the capillary fringe were calculated. Groundwater carbon dioxide fugacities and soil-gas carbon dioxide concentrations were used at the two locations and a third to determine whether the source of elevated soil carbon dioxide concentrations were unsaturated-zone hydrocarbon degradation or a saturated-zone process. This technique has potential applicability in setting risk-based remedial criteria and in allowing inclusion of the contribution of in situ degradation in remedial design. This can result in major remedial cost savings.     

Electro-Deposited Lead Dioxide Plates: A New Technique for Sulfation Rate Studies

Sulfation rates have long been used to estimate roughly atmospheric SO2 content on a monthly basis. Either lead dioxide coated candles or petri dishes (Huey plates) have so far been used.^1-6 Although in many advanced countries there are now commercially available duly coated petri dishes which are relatively rugged and can stand moderately rough handling during routine operations, small working groups, particularly in developing countries have to be content with “homemade” plates. In tropical climate we find the Huey plates prone to peeling and damage under adverse climatic conditions or routine operations. Besides, the Pb02 slurry deposition technique demands uniformity and submicron size of deposited PbC>2 which is hard to obtain particularly in “homemade” plates.     

The Plume Volume Molar Ratio Method for Determining NO2/NOx Ratios in Modeling—Part I: Methodology

ABSTRACT

During New Source Review modeling of proposed major sources of oxides of nitrogen (NO_x), maximum impacts are often predicted to occur very close to the source. At the same time, current modeling guidance recommends techniques that may be overly conservative in estimating the fraction of nitrogen dioxide (NO₂) in these plumes. A new technique called the Plume Volume Molar Ratio Method (PVMRM) is being proposed that simulates both chemistry and dispersion to better estimate the fraction of NO₂. This paper documents the methodology behind the technique. A follow-up pa-per¹ will evaluate its performance against a number of databases. This method is designed to realistically predict NO₂ fraction at close-in receptors yet still provide conservative estimates so that the air quality standards can be protected.     

Evaluation of the Sodium Arsenite Method for Measurement of NO2 in Ambient Air

The sodium arsenite method for measurement of nitrogen dioxide in ambient air was evaluated. The method has a constant-high collection efficiency (82%) for nitrogen dioxide, and is insensitive to normal variations in operating parameters. Nitric oxide and carbon dioxide are positive and negative interferents, respectively. The combined average effect of these interferents, over ambient levels, is a positive bias of 9.9 µg/m³. This bias, although statistically significant, is minor ( 10 % ) in relation to the ambient air standard of 100 µg NO₂/m³ and does not warrant modification of the method to remove the interference.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

The C02 Pulse Technique for Determining the Condition of Adsorbent Charcoal Beds

Activated charcoal is widely used for the purification of air. Charcoal has a large surface area (ca. 1000 square meters per gram) and acts to purify air by adsorbing gaseous pollutants on its surface. When the capacity of the surface is exhausted, the charcoal is no longer effective and must be replaced.

The carbon dioxide (CO₂) pulse technique, developed at NRL, is a non-destructive method by which one can determine the remaining capacity, or the residual life of a charcoal bed before it has become exhausted. A dose of CO₂ is injected into the air stream ahead of the charcoal bed and is eluted through the bed. The shape of the emerging CO₂ elution peak is determined by the condition of the charcoal bed. For a new, unused charcoal bed the CO₂ elution peak is considerably dispersed (flattened and broadened) due to adsorption and desorption at the charcoal surface. For a partially spent bed the elution peak is dispersed to a degree proportional to the remaining capacity of the bed. For a fully spent bed the CO₂ elution peak is little affected by passage through the bed.

The carbon dioxide puise technique has been shown to be indicative of charcoal capacity for a wide range of non-polar materials (such as hydrocarbons, alcohols, etc.), which are taken up primarily by physical adsorption. The method is essentially insensitive to relative humidity in the range between 10 and 70%. An adaptation of the method has been used for detection of leaks in a charcoal bed, such as those caused by channeling, faulty packing, etc.     

Inactivation of LPS and RNase A on photocatalytically active surfaces

TiO₂ coated surfaces are able to generate highly reactive oxidizing species under mild UV-A light exposure in the presence of water and oxygen. We have demonstrated that these radicals are sufficient to eliminate different pathogenic bacteria, by breaking their cell walls. The photocatalytic activity of surfaces coated with titanium dioxide offers therefore an alternative possibility of disinfection. However, restriction of bacterial growth does not protect surfaces from bacterial derived contaminations, such as endotoxins. Lipopolysaccharides (LPS) and Ribonuclease A (RNAse A) represent the two most abundant contaminations, causing severe problems in biomedical and immunological research as well as in the pharmaceutical industry. Due to their high stability, complete removal of these contaminants is technically challenging. Using irradiated TiO₂ coated glass plates, RNAse A and LPS containing contaminations could be completely inactivated. By establishing highly sensitive immuno-based assays, destruction of the contaminants was quantified and shown to be independent of the initial concentrations, following a zero-order reaction. Exposure for 96 h resulted in a reduction of 11 ng of LPS and 7 units of RNase A cm⁻² surface. These amounts are comparable to contamination levels found under standard working conditions. Titanium dioxide coatings provide therefore a powerful tool for auto-disinfection and self-cleaning of surfaces.     

The Plume Volume Molar Ratio Method for Determining NO2/NOx Ratios in Modeling—Part II: Evaluation Studies

ABSTRACT

A previous paper¹ discusses the methodology for a new method for deriving the nitrogen dioxide/nitrogen oxide (NO₂/NO_x) ratio in plumes that originally are composed mainly of (NO_x). It is called the Plume Volume Molar Ratio Method (PVMRM). This paper documents its performance against six different data sets. These performance evaluations show that the PVMRM can realistically predict the NO₂ fraction at close-in receptors yet still provide conservative estimates so that the air quality standards can be protected.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Synthesis of [14C]biphenyl and of some chlorinated [14C]biphenyls containing 4-chloro-, 2,4-dichloro- and 2,3,6-trichlorophenyl nuclei from the corresponding labelled anilines

The preparation of ¹⁴C-labelled biphenyl, 2,5-dichlorobiphenyl, 2,4′,5-trichlorobiphenyl, 2,2′,4,5′-tetrachlorobiphenyl, 2′,3,4,4′,5-pentachlorobiphenyl, 2,2′,3,4,4′-pentachlorobiphenyl, 2,3,3′,4′,6-pentachlorobiphenyl and 2,2′,3,3′,6-pentachlorobiphenyl is described [¹⁴C]Aniline hydrogen sulfate used as a starting material was acetylated, chlorinated and deacetylated followed by coupling to benzene or an appropriate chlorobenzene to give the biphenyls labelled in the phenyl nuclei having chlorine atoms at the 4-, 2,4- or 2,3,6-positions, respectively. The structures of the labelled compounds were established by comparison with authentic samples among which 2′,3,4,4′,5- and 2,2′,3,4,4′-pentachlorobiphenyl were not earlier described.A simple method for the preparation of 2,3,6-trichloroacetanilide, unlabelled and labelled, was worked out. 2,6-Dichloroacetanilide in concentrated hydrochloric acid gave the $\text{meta}$ substituted product when treated with chlorine.An improved thin layer chromatographic technique utilizing plates impregnated with certain tetraalkylammonium salts was used for separation of some of the labelled compounds prepared.     

Developing a High-Resolution Vehicular Emission Inventory by Integrating an Emission Model and a Traffic Model: Part 2—A Case Study in Beijing

Abstract

A grid-based, bottom-up method has been proposed by combining a vehicle emission model and a travel demand model to develop a high-resolution vehicular emission inventory for Chinese cities. Beijing is used as a case study in which the focus is on fuel consumption and emissions from hot-stabilized activities of light-duty gasoline vehicles (LGVs) in 2005. The total quantity of emissions, emission intensity, and spatial distribution of emissions at 1- by 1-km resolution are presented and compared with results from other inventory methods commonly used in China. The results show that the total daily fuel consumption and vehicular emissions of carbon dioxide, carbon monoxide, hydrocarbons, and oxides of nitrogen from LGVs in the Beijing urban area in 2005 were 1.95 × 10⁷ L, 4.28 × 10⁴ t, 1.97 × 10³ t, 0.28 × 10³ t, and 0.14 × 10³ t, respectively. Vehicular fuel consumption and emissions show spatial variations that are consistent with the traffic characteristics. The grid-based inventory developed in this study reflects the influence of traffic conditions on vehicle emissions at the microscale and may be applied to evaluate the effectiveness of traffic-related measures on emission control in China.     

Extraction of Sudan dyes from environmental water by hemimicelles-based magnetic titanium dioxide nanoparticles

A novel method for the extraction of Sudan dyes including Sudan I, II, III, and IV from environmental water by magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) coated with sodium dodecylsulfate (SDS) as adsorbent was reported. Fe₃O₄@TiO₂ was synthesized by a simple method and was characterized by transmission electron microscopy, Fourier-transform infrared spectrometry, and vibrating sample magnetometer. The magnetic separation was quite efficient for the adsorption and desorption of Sudan dyes. The effect of the amount of SDS, extraction time, pH, desorption condition, maximal extraction volume, and humic acid on the extraction process were investigated. This method was employed to analyze three environmental water samples. The results demonstrated that our proposed method had wide linear range (25–5,000 ng L^?1) with a good linearity (R ²?>?0.999) and low detection limits (2.9–7.3 ng L^?1). An enrichment factor of 1,000 was achieved. In all three spiked levels (25, 250, and 2,500 ng L^?1), the recoveries of Sudan dyes were in the range of 86.9–93.6 %. The relative standard deviations obtained were ranging from 2.5 to 9.3 %. That is to say, the new method was fast and effective for the extraction of Sudan dye from environmental water.     

A new look at atmospheric carbon dioxide

Carbon dioxide is increasing in the atmosphere and is of considerable concern in global climate change because of its greenhouse gas warming potential. The rate of increase has accelerated since measurements began at Mauna Loa Observatory in 1958 where carbon dioxide increased from less than 1 part per million per year (ppm yr^?1) prior to 1970 to more than 2 ppm yr^?1 in recent years. Here we show that the anthropogenic component (atmospheric value reduced by the pre-industrial value of 280 ppm) of atmospheric carbon dioxide has been increasing exponentially with a doubling time of about 30 years since the beginning of the industrial revolution (～1800). Even during the 1970s, when fossil fuel emissions dropped sharply in response to the “oil crisis” of 1973, the anthropogenic atmospheric carbon dioxide level continued increasing exponentially at Mauna Loa Observatory. Since the growth rate (time derivative) of an exponential has the same characteristic lifetime as the function itself, the carbon dioxide growth rate is also doubling at the same rate. This explains the observation that the linear growth rate of carbon dioxide has more than doubled in the past 40 years. The accelerating growth rate is simply the outcome of exponential growth in carbon dioxide with a nearly constant doubling time of about 30 years (about 2%/yr) and appears to have tracked human population since the pre-industrial era.     

Public Relations Handbook

A major difficulty encountered in laboratory research on the atmospheric interaction of an aerosol-gas system is the unstable nature of the aerosol phase. Previously reported aerosol stabilizing techniques often severely alter the aerosol so that laboratory results cannot be validly extrapolated to the atmospheric environment. A new technique which does not alter the nature of the aerosol is described in this paper.

Aerosol particles are deposited on an inert substrate such as Teflon beads. The deposition is carried out in a fluidized-bed to ensure discrete aerosol deposition and to achieve a uniform distribution of aerosol concentration on the supporting beads. Aerosol-gas interactions can be investigated conveniently by exposing these stabilized aerosols to the reacting gases in dynamic or static systems. Laboratory results obtained by using stabilized aerosols may be extrapolated to the atmospheric environment.

This aerosol stabilizing technique was incorporated into an investigation of the particulate-catalyzed atmospheric oxidation of sulfur dioxide. Teflon beads with deposited aerosol particles of CuCl₂, MnCl₂, and NaCI were exposed to 4–42 ppm of sulfur dioxide in a plug flow reactor. The rate of oxidation of sulfur dioxide was found to be influenced by type of catalyst, concentration of catalyst, relative humidity and concentration of sulfur dioxide. The rate of oxidation by sodium chloride particulate was measurable at low to moderate relative humidities (45–60%), but the rate was several times higher when the sodium chloride catalyst particles change from solid form into droplet form at high relative humidities (>80%).     

Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.     

Studies on the Removal of Sulfur Dioxide from Hot Flue Gases to Prevent Air Pollution

The pollution of the atmosphere by sulfur dioxide is one of the gravest of all in public nuisance problems, especially in the industrial regions. A practically applicable method in industry for the removal of sulfur dioxide has been studied. The Kiyoura-T .I .T. process utilizes the oxidation method to convert S0₂ of the flue gas to S0₃ in the presence of vanadium oxide. A limited amount of water vapor present in the flue gas reacts with S0₃ to form H₂SO₄. Ammonia is then introduced to the gaseous mixture, which is now at the suitable temperature, to form ammonium sulfate. Conditions are controlled to produce ammonium sulfate of the right size to produce aggregate that may be removed by a dry cyclone separator.     

Acetaldehyde residue in polyethylene terephthalate (PET) bottles

A simple sample preparation technique was developed for rapid analysis of acetaldehyde residue in Polyethylene Terephthalate (PET) bottles. A laboratory-built heating system was used and coupled with gas chromatography-flame ionization detector (GC-FID) at optimized conditions. The results were a tremendous reduction of the sample preparation time from 24 hours, for the conventional method, to only one hour. The analysis took only 1.5 min with other good analytical performances i.e. a low detection limit, 0.3 ng mL^{? 1} and a wide linear dynamic range, 0.3 ng mL^{? 1} to 6.6 μ g mL^{? 1} with R² > 0.99.Acetaldehyde residue in freshly blown bottles were analyzed and found in the range of 0.4 to 1.1 ng mL^{? 1}. The results were good agreement with the conventional 24-hour airspace method (P < 0.01). The PET-bottle sampling technique was also developed to minimize the complication of sample transportation and pre-concentration. A purge and trap technique was found to be the most suitable. Then, it was implemented and compared, the results showed no significant difference (P < 0.01) with and without purge and trap.     

Rate Constant Ratios During Nitrogen Dioxide Photolysis

Nitrogen dioxide is the light absorber in the hydrocarbon system leading to production of photochemical air pollution. Studies of the reactions involved are based on the kinetics of nitrogen dioxide photolysis and the values of the rate constants derived therefrom. The photolysis of nitrogen dioxide was investigated in the 2-20 ppm concentration range. The value of the bimolecular rate constant of the reaction between oxygen atoms and nitrogen dioxide was calculated to be 5.26 × 10⁹1 mole^–1 sec^–1, and thetermolecular rate constant of the reaction between oxygen atoms and nitrogen dioxide in presence of a third body is 4.24 × 10^–10 1²mole^–2 sec^–1. The rate constant for the reaction between oxygen atoms and nitric oxide in the presence of a third body was calculated to be 2.31 × 10¹⁰ 1²mole^–2 sec^–1. Nitrogen was used as the third body. In terms of order of magnitude these calculated rate constants are similar to previously reported values. However, in certain cases their use leads to an oxygen atom concentration which is 100% greater than previously calculated.     

Quantification of ventilation on distribution of gaseous pollutants emitted from stored swine manure

Abstract

This paper describes the quantification of the effects of ventilation on distribution of gaseous pollutants as a result of mass transfer from stored manure to ventilation air in a swine confinement building. A multiple airflow regions model is developed and used to simulate the dynamics of gaseous pollutants in any airspace within a ventilated slotted‐inlet enclosure. The model predictions compared favorably with the measured results adapted from a literature research at ventilation rates between 443 and 932 m³/hr (deviations of 5.1 ‐ 14.68%) for carbon dioxide and ammonia concentrations. A comparison between predictions and measured carbon dioxide concentrations derived from an environmental chamber test found deviations ranged from 3.1 ‐ 5.6% at ventilation rates between 281 and 995 m³/hr. The results suggest that the model can be experimentally applied between ventilation rates of 443 and 995 m³/hr. The model also capable of predicting air exchange rate required to maintain acceptable levels of gaseous pollutants in swine confinement buildings based on gas emission rates.     

New Fe-immobilized natural bentonite plate used as photo-Fenton catalyst for organic pollutant degradation

Novel photo-Fenton catalysts were prepared by immobilizing iron species on commercial bentonite plates via two methods: (1) ion exchange reaction (Fe³⁺ vs. Na⁺) by aqueous suspension powder-clay/FeCl₃ followed by plate preparation, and (2) forced hydrolysis of Fe(NO₃)₃ onto a prefabricated clay plate. The last method led to a more photo-active Fe-oxide/bentonite plate. This material allowed, at a non-adjusted initial pH of 5.5 and in the presence of H₂O₂, the total degradation of resorcinol and 55% mineralization in 80 and 100 min of irradiation, respectively. The reached degradation percentages were correlated to the presence of dissolved iron, demonstrating that in these processes, the homogeneous photo-Fenton reactions were mainly responsible for the resorcinol elimination.Likewise, in slurry system, where clay has normally an increased surface area, there was no increase in activity because of a reduced leached iron probably due to the diminished light penetration in the suspension. Despite the lower surface area, in comparison to that of the slurry, the clay plates have the advantage, as heterogeneous photo-catalysts, that separation of the reaction media after treatment is not needed, and thus, a potential use for batch and continuous reaction systems is proposed.