Bacteria additives to the changes in gaseous mass transfer from stored swine manure

Abstract

A bacteria additives treatment experiment in assessing the changes in gaseous mass transfer from stored swine manure is presented. The experiment is tested for ammonia, methane, hydrogen sulfide, and carbon dioxide emission data sampled from pilot swine manure columns and analyzed by GC/MS. The result shows that bacteria additives slightly reduce the methane and carbon dioxide releases, while the same additives do not show any effect on the reduction of ammonia. The hydrogen sulfide contents of stored swine manure continued to be low. Gas concentrations emitted from treated and untreated stored swine manure were: 3.76 and 2.2 ppm for methane, 0.35 and 0.11 ppm for ammonia, and 1000 and 470 ppm for carbon dioxide, respectively. A simple model to estimate gas emission rates is also developed from the viewpoint of two‐film resistance theory. The average emission rates calculated from the model for methane, ammonia, and carbon dioxide are respectively: 0.01, 0.0005, and 13.98 g/min from untreated stored manure; while 0.07, 0.096, and 0.55 g/min from treated manure. The emission model also indicates that for most gaseous pollutants of environmental concern, liquid phase transfer coefficient controls the rate of volatile compounds emitted from stored swine manure and gas phase transfer coefficient has insignificant effect in the calculation of overall mass transfer coefficient.     

Closed-Loop Recovery of Site Remediation Gas Phase Contaminants

A novel gas phase treatment system (contaminant absorption and recovery [CAR]) for removal and subsequent recycling of gas phase VOCs from soil vapor extraction/gas stripping systems has been developed. Gas phase removal efficiencies using a packed column contactor exceed 99 percent The VOC-laden absorption fluid is subsequently vacuum-stripped of the VOCs, allowing potential condensation into liquid solvent concentrates. Partition coefficients for trichloroethylene (TCE) in triethylene glycol (TEG) ranged to ca. 5.0 mole fraction gas/mole fraction liquid, indicating a significant capacity for removal from the gas phase. Results of pilot-scale operation indicate favorable removal efficiencies and cost-effective performance in comparison to GAC or thermal destruction processes. System mass transfer coefficient predictions were done, using a variety of mathematical models and compared to experimental results. A modified Mangers and Ponten correlation was found to describe system mass transfer coefficients well. The impact of water carry-over on TCE/TEG partitioning was found to be significant. The standard change in entholpy (ΔH°) and the standard change in volume (ΔV°) values were also calculated, and predictions of temperature and pressure on system performance were evaluated.     

石灰石湿法脱硫过程中SO2吸收数学模型

为揭示石灰石湿法脱硫体系中喷淋塔内SO2的浓度和脱硫效率的变化情况,针对喷淋塔内石灰石在气膜控制、气液膜控制和固体溶解控制的3个不同阶段,以双膜理论为基础,以单个石灰石颗粒为研究对象,通过石灰石在不同阶段的转化率和粒径变化,得到SO2在不同阶段脱硫效率随时间的变化规律,建立SO2吸收的数学模型.模型计算结果表明,在烟气行程上,脱硫效率受SO2气膜传质阻力和石灰石溶解速率限制.在吸收塔底部和上端SO2吸收速率较低,在SO2和石灰石摩尔比在适宜条件下,有效吸收段高度为2 m左右.理论模型揭示的规律对喷淋塔的设计和运行参数选取有一定借鉴意义.     

Modeling the formation of PCDD/F in solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) appear in unacceptable amounts in the gaseous emissions during the incineration of wastes containing significant quantities of chlorine and metals, such as MSW and medical waste. They are formed both in the gas phase at temperatures above 600 degrees C and on the surface of the solid phase (flyash) in the temperature range 400-225 degrees C. Both the precursor (from existing smaller chlorinated molecules) and de novo (from elemental carbon) routes are involved. An empirically derived global model for their de novo formation on flyash in MSW and medical waste incinerators has now been extended to include the precursor mechanism, and a gas phase formation component, with separate rate expressions for PCDD and PCDF. Homogeneous PCDD formation is governed by the concentration of chlorophenols and PCDF by that of chlorophenols and chlorobenzenes. The result is more complete system which distinguishes between the gas and solid phase contributions to the I-TEQ. An additional step for the adsorption of gaseous PCDD/F back onto the solid phase during cooling suggests this should be minimal in the gas ducts of an incinerator. The extended model has been tested against experimental data collected from a well-controlled pilot incinerator and commercial incinerators, and found to adequately describe the measured outputs. With the model it should be possible to predict the PCDD/F emissions from commercial incinerators, provided that the ash properties and the overall temperature-time profiles are known.     

Mercury chemistry in the MBL: Mediterranean case and sensitivity studies using the AMCOTS (Atmospheric Mercury Chemistry over the Sea) model

The atmospheric oxidation of mercury in the Mediterranean marine boundary layer (MBL) has been studied using the Atmospheric Mercury Chemistry over the Sea (AMCOTS) model. The model results have been compared to measured data obtained during an oceanographic research campaign in 2000, with more success than previous modelling attempts. In light of the often high concentrations of ozone present in the Mediterranean boundary layer, seasonal case studies using typical meteorological conditions and average ozone concentrations have been performed to identify the main oxidants of elemental mercury. The sensitivity of the modelled reactive gaseous mercury (RGM) concentrations to the Hg+O₃ rate constant has been assessed using the two most recent rate determinations. The results using the higher of the two literature values gives results inconsistent with measured values of RGM when the reaction between Hg and O₃ is assumed to give a gas phase product. This does not necessarily indicate that the rate constant is incorrect but possibly that other rate constants in the model are overestimated or indeed that there may be reduction reactions occurring in the atmosphere which have yet to be identified. Alternatively, when the reaction product of Hg and O₃ is assumed to be a solid and therefore not contribute to RGM the modelled and measured results are comparable. The deposition rates calculated by the model when compared with calculated and measured sea surface emission fluxes available in the literature indicate that dry deposition flux of RGM is comparable to the sea surface emission flux. The calculated lifetime of Hg⁰ in the Mediterranean MBL is between one and two weeks.     

Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

Prediction of adsorption rate of phosphate removal from wastewater with gas concrete

Gas concrete, a conventional structural material, is used to remove phosphate from wastewater. A batch study of phosphate removal from wastewater with waste particles of gas concrete has been performed. The concentration-time graphs were plotted against pH, temperature, and agitation speed, and the reaction rate equation was adapted to adsorption. The differential method was used to define reaction rate. The adsorption rates, reaction rate constants, and reaction rates were determined by tangent lines of drawn curves at different concentrations, depending on pH, temperature, and agitation speed. The adsorption rate increased with pH and temperature. The maximum effect of agitation speed on the adsorption rate was observed at 150 rpm. The activation energy of reaction and the pre-exponential factor were calculated using the Arrhenius equilibrium equation. The zeta potentials of waste gas concrete were determined at various pH values. The surface area of gas concrete was obtained using BET apparatus as 22 m2/g. The composition of gas concrete was determined by X-ray diffractometry. The results indicate that gas concrete is an effective adsorbent to remove phosphate from wastewater.     

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~0.01 m/day, and a gas phase that covers greater than ~10% of the pool surface area and is located within ~0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.     

Chemical kinetic modeling of de novo synthesis of PCDD/F in municipal waste incinerators

A kinetic model is developed for de novo synthesis of PCDD/F from carbon in incinerator fly ash. The main mechanistic steps considered in the model are carbon gasification, PCDD/F formation, desorption and degradation. Rate equations are derived which can relate PCDD/F formation with process variables including carbon concentration of fly ash, partial pressure of oxygen, reaction temperature and time. The kinetic model has been verified using laboratory de novo synthesis data reported in the literature. When the model is applied to industrial incinerator conditions, PCDD/F formation levels of 0.1-0.5 microg/N m3 in the gas phase and 0.1-1.2 microg/g in the solid phase are calculated, and both are in good agreement with incinerator measurements.     

Enhanced naphthalene solubility in the presence of sodium dodecyl sulfate: effect of critical micelle concentration

Surfactants can increase the solubility of non-polar compounds, and have been applied in areas such as soil washing and treatment of non-aqueous phase liquids (NAPLs). This investigation explored the feasibility of removing vapor phase polycyclic aromatic hydrocarbon (PAH) from gases using an anionic surfactant. The solubility of vapor phase naphthalene was measured herein using gas chromatograph (GC) with a photon ionization detector (PID). The measurement results indicated that surfactant molecules were not favorable to micelle formation when temperatures increased from 25 degrees C to 50 degrees C. Regardless of whether solutions were quiescent or agitated, equilibrium naphthalene apparent solubility increased linearly with surfactant concentrations exceeding critical micelle concentration (CMC). The pH effects on naphthalene apparent solubility were small. Agitation increased naphthalene apparent solubility and lumped mass transfer coefficients. Furthermore, lumped mass transfer coefficients decreased with increasing surfactant concentration owing to increase in interfacial resistance and viscosity and decreased spherical micelle diffusion coefficients. Finally, the net absorption rate increased because the solubilization effects of micelles exceeded the reduction effects of mass transfer coefficient above the CMC. The enhanced naphthalene apparent solubility from the addition of surfactant can be expressed by an enrichment factor (EF). The EF value of naphthalene for the surfactant solution at 0.1 M with agitation at 270 rpm relative to quiescent water could reach 18.6. This work confirms that anionic surfactant can improve the removal efficiency of hydrophobic organic compound (HOC) from the gas phase.     

新型离心式脱硫塔气液两相流数值模拟

利用FLUENT软件和SIMPLE算法对新型旋流脱硫塔的气液两相流场进行了数值模拟。计算中气相采用了RSM湍流模型,颗粒相采用了Lagrange坐标系下的随机轨道模型。分析结果表明,气相流场具有强旋流特性;喷射液滴的直径、喷淋量和烟气流速影响其在塔内的分布:喷射液滴粒径越大、喷射量越小、烟气流速越大,入口段降温越少;塔体上方截面平均浓度随液滴粒径的增加而降低,随液气比的增加而增加,随烟气流速的增加会先增加至最高值然后降低。喷淋液滴在其他运行参数不变时,平均粒径范围为0.5～1 mm,会对进口烟气起到较好的净化与降温的作用,并使塔体上方喷淋液滴在截面z=4.15 m处浓度分布均匀且覆盖率高;在保证液滴粒径较小时,通过降低烟气流速或增加喷淋量可提高液滴喷淋覆盖率,使得烟气与喷淋充分接触。计算得到的气相流场分布与实测值吻合较好,证明了数学模型的合理性,为进一步优化分离器结构提供了可靠依据。     

Trichloroethylene degradation by photocatalysis in annular flow and annulus fluidized bed photoreactors

The effects of trichloroethylene (TCE) gas flow rate, relative humidity, TiO(2) film thickness, and UV light intensity on photodegradation of TCE have been determined in an annular flow type photoreactor. Phosgene and dichloroacetyl chloride formation could be controlled as a function of TCE gas flow rate and photodegradation of TCE decreased with increasing relative humidity. The optimum thickness of TiO(2) film was found to be approximately 5 mum and the photocatalytic reaction rate of TCE increased with square root of UV light intensity. In addition, the effects of the initial TCE concentration, phase holdup ratio of gas and solid phases (epsilon(g)/epsilon(s)), CuO loading on the photodegradation of TCE have been determined in an annulus fluidized bed photoreactor. The TCE photodegradation decreased with increasing the initial TCE concentration. The optimum conditions of the phase holdup ratio (epsilon(g)/epsilon(s)) and CuO wt.% for the maximum photodegradation of TCE was found to be 2.1 and 1.1 wt.%, respectively. Therefore, an annulus fluidized bed photoreactor is an effective tool for TCE degradation over TiO(2)/silica gel with efficient utilization of photon energy.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.     

生物化学法净化低浓度甲苯废气的传质研究

通过试验和理论分析,研究生物化学法净化低浓度甲苯废气这一传质一生化反应过程的控制因素,结果表明生物化学法净化低学本废气为传播控制过程,并以气膜控制为主,研究为工业化装置的设计和操作提供了理论依据。     

Simultaneous determination of chlorothalonil and its metabolite 4-hydroxychlorothalonil in greenhouse air: dissipation process of chlorothalonil

An analytical method was developed and tested for the simultaneous determination of chlorothalonil and its main metabolite 4-hydroxychlorothalonil, in airborne samples. High performance liquid chromatography equipped with Ultra-violet detector was used to separate and quantify the analytes. Glass microfibre filters for the collection of the analytes' particles were tested. Solid sorbents, such as Tenax, Florisil, XAD-2 and silica gel, were studied to find out the most suitable material for the collection of the analytes in the gas phase. The results have shown that only chlorothalonil was trapped in the vapor phase with highest results obtained when silica gel was the sorbent of choice. Linearity was demonstrated in a wide concentration range 0.01-10.00 mg L(-1). Recoveries from spiked glass microfibre filters and silica gel cartridges for chlorothalonil and 4-hydroxychlorothalonil were almost quantitative. The quantification limits were calculated to be 8.4 and 19.6 ng m(-3) in air for chlorothalonil and 4-hydroxychlorothalonil, respectively. The two analytes spiked on the GF/A filters and silica gel cartridges were proven to be stable for more than 15 days, at 4degrees C and ambient temperature. The applicability of the present method was demonstrated by the analysis of the chlorothalonil and its metabolite in greenhouse air.     

Control of Odors from a Continuous Soap Making Process

Innovations in the use of lung and myocardial tissue in vitro have permitted continuous morphological observation of cells treated with a controlled gaseous environment. The mammalian tissues are covered with a dialysis membrane and cultured in a Rose chamber containing a large gas phase. Test gases can be flushed continuously through two hypodermic needles in the culture chamber wall. Cell movement and morphology have been recorded with time lapse cinematography in chambers containing cells washed from lung airways or organotypic lung cultures. Myocardial cell morphology and beating rate have been analyzed with the aid of a remote TV monitoring system. Histochemical and ultrastructural techniques were also applied. The beating rate of myocardial cells was found to be an objective and convenient endpoint for testing the characteristics of the exposure system. A comparison of the response of cells in the gas phase with that of elements in the fluid phase within the same chamber suggested that this system can serve as a model for evaluating the effect of an increasing diffusion barrier.     

Investigation of hydrogeologic processes in a dipping layer structure: 2. Transport and biodegradation of organics

Numerical simulation tools have been used to study the dominating processes during transport of aromatic hydrocarbons in the unsaturated soil zone. Simulations were based on field observations at an experimental site located on a glacial delta plain with pronounced layered sedimentary structures. A numerical model for transport in the unsaturated zone, SWMS-3D, has been extended to incorporate coupled multispecies transport, microbial degradation following Monod kinetics and gas diffusive transport of oxygen and hydrocarbons. The flow field parameters were derived from previous work using nonreactive tracers. Breakthrough curves (BTC) from the hydrocarbon field experiment were used to determine sorption parameters and Monod kinetic parameters using a fitting procedure. The numerical simulations revealed that the assumption of homogeneous layers resulted in deviations from the field observations. The deviations were more pronounced with incorporation of reactive transport, compared with earlier work on nonreactive transport. To be able to model reasonable BTC, sorption had to be reduced compared to laboratory experiments. The initial biomass and the maximum utilisation rate could be adjusted to capture both the initial lag phase and the overall degradation rate. Nevertheless, local oxygen limitation is predicted by the model, which was not observed in the field experiment. Incorporation of evaporation and diffusive gas transport of the hydrocarbons did not significantly change the local oxygen demand. The main cause of the observed discrepancies between model and field are attributed to channelling as a result of small-scale heterogeneities such as biopores.     

Gas production and migration in landfills and geological materials.

Landfill gas, originating from the anaerobic biodegradation of the organic content of waste, consists mainly of methane and carbon dioxide, with traces of volatile organic compounds. Pressure, concentration and temperature gradients that develop within the landfill result in gas emissions to the atmosphere and in lateral migration through the surrounding soils. Environmental and safety issues associated with the landfill gas require control of off-site gas migration. The numerical model TOUGH2-LGM (Transport of Unsaturated Groundwater and Heat-Landfill Gas Migration) has been developed to simulate landfill gas production and migration processes within and beyond landfill boundaries. The model is derived from the general non-isothermal multiphase flow simulator TOUGH2, to which a new equation of state module is added. It simulates the migration of five components in partially saturated media: four fluid components (water, atmospheric air, methane and carbon dioxide) and one energy component (heat). The four fluid components are present in both the gas and liquid phases. The model incorporates gas-liquid partitioning of all fluid components by means of dissolution and volatilization. In addition to advection in the gas and liquid phase, multi-component diffusion is simulated in the gas phase. The landfill gas production rate is proportional to the organic substrate and is modeled as an exponentially decreasing function of time. The model is applied to the Montreal's CESM landfill site, which is located in a former limestone rock quarry. Existing data were used to characterize hydraulic properties of the waste and the limestone. Gas recovery data at the site were used to define the gas production model. Simulations in one and two dimensions are presented to investigate gas production and migration in the landfill, and in the surrounding limestone. The effects of a gas recovery well and landfill cover on gas migration are also discussed.     

Impacts of meteorological situations and chemical reactions on daily dry deposition of nitrogen into the southern North Sea

The impact of the meteorological situation and chemistry on dry deposition to the southern North Sea is investigated. The studies are performed using a high-resolution meteorology/chemistry model system of different complexity for a five-day period in June 1998. The simulations consider passive tracer transport (Case I), gas phase chemistry (Case II), gas phase plus simple aerosol chemistry (Case III), gas phase plus size dependent aerosol chemistry (Case IV). The results show a very good agreement of meteorology model results with measured data and a reasonable agreement for the concentrations. The dry deposition to the southern North Sea differs a factor of three to seven within the investigated five-day period. Differences are larger for a more complex chemistry. The average dry deposition increases by a factor of three when including gas phase reactions or adding a simple aerosol model and up to a factor of eleven when considering a sectional aerosol model. The input composition depends on the chemistry considered.     

Flamelet modeling of NO formation in laminar and turbulent diffusion flames

The applicability of the laminar flamelet concept for the formation and destruction of nitric oxides in laminar and turbulent diffusion flames has been studied. In a first step, temperatures and species concentrations in an axisymmetric laminar diffusion flame have been calculated (i) by solving the detailed conservation equations and (ii) by applying the laminar flamelet concept. The main purpose of this step was the identification of differences between results from both approaches. It turned out that for highly temperature sensitive or relatively slow chemical processes, the inclusion of the full range of the prevailing scalar dissipation rates plays a major role for the calculated species concentrations. This behavior is obvious from the concept of the laminar flamelet model, where the scalar dissipation rate can be discussed in terms of the reciprocal of a residence time for attaining chemical equilibrium. In a second step, flamelet modeling of NOx formation was extended to a turbulent hydrogen diffusion flame. In both the steps, the flow fields of the flames were calculated by solving the Navier-Stokes equations in axisymmetric formulation using the SIMPLER algorithm. For the turbulent flow, Favre-averaged equations have been used and turbulence was modeled with the standard k-epsilon model including a correction term for axisymmetric systems. The averaging of the species concentrations was accomplished with presumed shape probability density functions (pdfs). The pdf of the mixture fraction was described with a beta-function whereas that of the scalar dissipation rate was assumed to be log-normal. Buoyancy effects have been taken into account. The calculated temperatures and concentrations were compared with data from different experiments.