Manometric study of CO2 and H2S emission from aqueous solutions and wastewater

The emissions of CO₂ and H₂S from the aqueous solutions and wastewater were studied to determine and compare the times required to reach the equilibrium of H₂S and CO₂ between water and gas phases. The solutions of NaHCO₃ and NaHS were acidified and the change in the pressure of emitted gases was measured with a manometric OxiTop^® system. The average time required to achieve the equilibrium state of distribution of CO₂ between two phases was 16.7±1.5 min, and it did not depend on the initial amount of NaHCO₃ in the solution. The average time required to achieve the equilibrium of H₂S (sulfide) was 19.5±5.5 min, having the same value for solutions with different initial contents of sulfide ions. The average time required to achieve the equilibrium of H₂S in the wastewater was 16.2±3.6 min, and it showed the faster emission of gaseous H₂S to decrease the oversaturation of the solution. The ratio of measured values of pressure to the calculated values did not depend on the concentration of NaHS in the initial solution, and its average value was 0.86±0.14. The results showed that measured values of pressure of H₂S emitted from the wastewater were twice lower than the calculated values and it is necessary to take into account the catalyzed formation of polysulfide in the solution of sulfides.     

A Continuous Quantitative Detection Method for Total Mercaptans,Organic Sulphides,H2S,and CS2 for Odouriferous Emissions

A monitoring system enabling detection and determination of the nature of odour nuisance caused by industrial emissions of volatile organic sulphur compounds is presented. The system consists of two continuous, highly sensitive detectors for sulphur compounds at the ppb-level. One of the detectors is equipped with a SO_x-scrubber and measures the total amount of non-S0₂ sulphur compounds. By the use of a newly developed scrubber retaining S0₂, H₂S and CS₂ the second detector monitors the presence of odorous mercaptans and organic sulphides in ambient air. Both these continuous detection signals are fed to a data processor which triggers air collection for the determination of the individual compounds by gas chromatographic analysis in the laboratory. The concept and operation, as well as the practical possibilities and applications of the system are explained     

A Simple Technique for Measuring Mean H2S Concentration

Lead acetate impregnated ceramic tiles are useful devices for determining H₂S levels in the outdoor air. The exposure of tiles in simple shelters and for an overnight period is effective in an areawide sampling program to determine: (1) whether a significant H₂S source exists, (2) the source location, (3) the area affected, and (4) the relative intensity pattern.

On the basis of an overnight exposure, tiles can “see” a mean H₂S concentration range of 0.003 to 0.3 ppm. The lower level of sensitivity is near 0.03 ppm X hr. Hence, tiles offer a way to verify whether hourly air quality standards are being exceeded.

Tiles can be qualitatively evaluated against: experience, known effects, or by ranking against each other. Tiles can be semi-quantitatively evaluated by visual grading against painted standards developed by exposing tiles of particular manufacture to known H₂S dosages.     

Operational Characteristics of Effective Removal of H2S and NH3 Waste Gases by Activated Carbon Biofilter

Abstract

Simultaneous removal of hydrogen sulfide (H₂S) and am- gases. monia (NH₃) gases from gaseous streams was studied in a biofilter packed with granule activated carbon. Extensive studies, including the effects of carbon (C) source on the growth of inoculated microorganisms and gas removal efficiency, product analysis, bioaerosol emission, pressure drop, and cost evaluation, were conducted. The results indicated that molasses was a potential C source for inoculated cell growth that resulted in removal efficiencies of 99.5% for H₂S and 99.2% for NH₃. Microbial community observation by scanning electron microscopy indicated that granule activated carbon was an excellent support for microorganism attachment for long-term waste gas treatment. No disintegration or breakdown of biofilm was found when the system was operated for 140 days. The low bioaerosol concentration emitted from the biofilter showed that the system effectively avoided the environmental risk of bioaerosol emission. Also, the system is suitable to apply in the field because of its low pressure drop and treatment cost. Because NH₃ gas was mainly converted to organic nitrogen, and H₂S gas was converted to elemental sulfur, no acidification or alkalinity phenomena were found because of the metabolite products. Thus, the results of this study demonstrate that the biofilter is a feasible bioreactor in the removal of waste gases.     

Control of H2S Emissions During Slag Quenching

An analysis of slag pit variables has been made and correlations obtained between pit dimensions, time interval between pours, and the slag temperature when the pit is filled and ready for quenching. Field trials have demonstrated the effect of temperature on the level of emission and how the level varies during the quench period. Quantitative information has been obtained to show the effects of slag filling rates, air cooling prior to quenching, and the influence of oxidizing agents added to the quench water. A significant reduction in H₂S emission level can be attained by proper application of these results.     

Adsorption kinetics and modeling of H2S by treated waste oil fly ash

Waste oil fly ash (OFA) collected from disposal of power generation plants was treated by physicochemical activation technique to improve the surface properties of OFA. This synthesized material was further used for potential hydrogen sulfide (H₂S) adsorption from synthetic natural gas. The raw OFA was basically modified with a mixture of acids (20% nitric acid [HNO₃] and 80% phosphoric acid [H₃PO₄]), and it was further treated with 2 M potassium hydroxide (KOH) to enhance the surface affinity as well as surface area of synthesized activated carbon. Correspondingly, it enhanced the adsorption of H₂S. Crystallinity, surface morphology, and pore volume distribution of prepared activated carbon were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. Fourier transform infrared (FTIR) study was also performed to identify the functional groups during different synthesis stages of modified activated carbon. The Langmuir, Freundlich, Sips, and dual-site Langmuir (DSL) models were used to study the kinetic and breakthrough behavior of H₂S adsorption over alkali-modified activated carbon. Modeling results of isotherms indicated that OFA has dual sites with high and low affinity for H₂S adsorption. The Clark model, Thomas model, and Yoon-Nelson model were used to examine the effects of flow rate and inlet concentration on the adsorption of H₂S. Maximum uptake capacity of 8.5 mg/g was achieved at 100 ppm inlet concentration and flow rate of 0.2 L/min.

Implications: Utilization of worthless oil fly ash from power plant is important not only for cleaning the environment but also for solid waste minimization. This research scope is to eradicate one pollutant by using another pollutant (waste ash) as a raw material. Chemical functionalization of synthesized activated carbon from oil fly ash would lead to attachment of functional groups of basic nature to attract the acidic H₂S. Such type of treatment can enhance the uptake capacity of sorbent several times.     

Kinetics of Sulfur-Oxide Formation in Flames: II. Low Pressure H2S Flames

The microstructure of 1/10 and 1/20 atmosphere, lean H₂S—O₂—N₂ flames is developed using the mass-spectrometric flame-sampling technique. The flame mechanism developed is in agreement with that determined from an earlier study on 1-atm H₂S flames. The formation of SO₂ appears to be primarily related to the production of SH and the ensuing oxidation steps SH + O₂ = SO + OH and SO + O₂ = SO₂ + O. While there is some question whether SO₂ formation occurs via an SO or an S₂O intermediate, the present study does not give direct support to the role of S₂O in the oxidation mechanism. However, the presence of significant quantities of free sulfur in the pre-flame zone may be indicative of S₂O formation via SO + S → S₂O, and, possibly, via the disproportionation of SO, 3SO → S₂O + SO₂. Kinetic analyses of some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the decomposition of H₂S. The actual initiation process in the flame mechanism requires further examination. The specific rate for the reaction step H₂S + O = OH + SH is given by k ₆ = 1.45 × 10₁₅ exp ( – 6600/RT) cm³ mole^–1 sec^–1, and the specific rate for the oxidation of SO, SO + O₂ = SO₂ + O, is given by k ₅ = 5.2 × 10₁₄ exp (—19,300/RT) cm³ mole^–1 sec^–1.     

Determination of S02 Emission from Oil Combustion Sources by Fuel Analyses and S02/C02 Relations

The current S0₂ emission test methods, based on wet chemistry, are time consuming and costly. Final results depend on at least 10 separate measurements of quantities which may introduce significant errors due to human factors especially under unfavorable field environment. Performance evaluation of several promising S0₂ instrumental methods indicated that results were reliable and reproducible, but instrumental problems still exist. The problems were found to be calibration, mechanical and electronic components, and sample conditioning system. An alternative method proposed requires only two separate analyses: ultimate fuel analysis and stack gas analysis for C0₂. This method can be further simplified with reasonable accuracy by a single measurement of sulfur in the fuel if results are corrected to 12% C0₂. The method can be a useful addition to the current methods, especially if cost and manpower preclude actual stack tests. A test program was conducted at four industrial and utility power plants. Results are presented with discussion to show the application and validity of the simplified method.     

Long-Term Operation of a Biofilter for Simultaneous Removal of H2S and NH3

Abstract

Simultaneous removal of NH₃ and H₂S was investigated using two types of biofilters—one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH₃ and H₂S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH₃ and H₂S were decreased to 30–50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H₂S (over 200 ppm) but recovered gradually after H₂S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH₃ concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH₄)₂SO₄] ac-cumulating on the packing materials during the extended operation. The removal capacities for NH₃ and H₂S were 6.0–8.0 and 45–75 mg N, S/L/hr, respectively.     

Degradation of bisphenol A by the UV/H2O2 process: a kinetic study

A theoretical and experimental study of bisphenol A (BPA) degradation by the UV/H₂O₂ process in water is presented. The effects of the H₂O₂ concentration and the specific rate of photon emission (E_P,0) on BPA degradation were investigated. A kinetic model derived from a reaction sequence was employed to predict BPA and hydrogen peroxide concentrations over time using an annular photochemical reactor in batch recirculation mode. The local volumetric rate of photon absorption (LVRPA) inside the photoreactor was computed using a Line Source with Parallel Plane emission model (LSPP). From the proposed kinetic model and the experimental data, the second order rate constants of the reactions between hydroxyl radicals and the main reacting species (H₂O₂ and BPA) were estimated applying a nonlinear regression method. A good agreement between the kinetic model and experimental data, for a wide range of operating conditions, was obtained. For BPA, H₂O₂, and TOC concentrations, the calculated root means square errors (RMSE) were 2.3?×?10^??2, 9.8?×?10^??1, and 9.0?×?10^??2 mmol L^??1, respectively. The simplified kinetic model presented in this work can be directly applied to scaling-up and reactor design, since the estimated kinetic constants are independent of the reactor size, shape, and configuration. Further experiments were made by employing low BPA initial concentration (100 μg L^??1) in water and real wastewater. A lower degradation rate of BPA was observed in the real wastewater, although the UV/H₂O₂ process has also been able to completely degrade the target pollutant in less than 1 h.

     

Predictions of Maximum Ground-Level H2S Concentrations Resulting from Two Sour Gas Well Blowouts

Alberta has recently experienced two sour gas well blowouts: Lodgepole and Claresholm. Sulphur emissions associated with the blowouts were about 1400 and 2 tonnes per day, respectively. The Lodgepole blowout was not only of much greater magnitude but also lasted significantly longer than the Claresholm blowout (67 vs. 4 days). Special air quality monitoring with respect to H₂S was conducted to assess impacts of the blowouts. Monitoring was especially extensive for the Lodgepole incident. Maximum observed ground-level H₂S concentrations were compared to predictions obtained using a Gaussian model which makes allowance for the effects of sonic exit velocity on plume spread and the effects of wind shear on plume transport. There was appreciable agreement between predicted and observed values.     

Comparative study on the removal efficiency of hydrogen sulfide (H2S) using three different packings

To improve the removal efficiency on hydrogen sulfide (H₂S), a biofilter was developed and was made of polyvinyl chloride (PVC) pipes. The effects of three different packings (i.e., packing A, packing B, and packing C), containing different proportions of activated carbon, sawdust, wormcast, perlite, and pig manure compost, based on different biofilter parameters on H₂S removal efficiency, were investigated. With the extension of running time, the H₂S removal rate of packing A reached up to 90.12%, that of packing B reached a peak at 92.96%, and that of packing C was highest at 87.21%. The contribution rate of each packing at the bottom of the device was significantly greater (p < 0.01) than that of other parts, and those of the top of the devices were all greater than those of the middle of the devices. The H₂S removal rate increased with greater filler layer height. The removal rate of group B increased first with humidity, and then declined, with the optimal humidity level for the removal of H₂S 50–65% in this study. With the prolongation of the run, the pH of packing A was reduced from 7.1 to 5.91, while the pH of packing B and C remained within the range of 6.53–7.10. An increase was found in the number of bacteria and fungi over time. The count of bacteria in packing B and C and following a decreasing order was bottom > middle > top, whereas that for fungi was the opposite. In conclusion, it is thought that packing B (comprising wormcast + sawdust + activated carbon) is more efficient in the removal of H₂S than the other packings and may thus be utilized in biofilters. These results hope to provide useful information for future related research on the removal efficiency of H₂S using packings.

Implications: Wormcasts use as biological filter packing to remove H₂S is limited and needs yet to be explored. A comparative study on the removal efficiency of H₂S using three packings showed the packings that included wormcast were more efficient than others, and showed the combined features of physical absorption and biological removal with long sustainability and good efficiency, although these were largely influenced by environmental factors and nutrient content for the microorganisms. In summary, wormcast could be utilized in biological filters in the future in related research beacuse of its good efficiency and low cost.     

Performance Characterization and Optimization of the AgNO3-Filter/FMA Fluorimetric Method for Atmospheric H2S Measurements

This sensitive, albeit precarious, method for measuring ppb-ppt (V/V) concentrations of H₂S was examined for various sources of potential error within the procedure. Filter preparation, filter storage, filter extraction, fluorimetric reagent stabilities, matrix differences between standards and samples, and possible interferences from other sulfur-containing compounds were separately studied for their effects on the analytical performance of the method. The overall method showed no Interference from SO₂, CS₂, COS, CH₃SH, CH₃SCH₃, and SO₄ ^-2. To minimize bias and obtain a reliable estimate of precision, the method should be calibrated with H₂S standards rather than liquid bisulfide standards. The measurement precision is a function of the quantity of H₂S collected as Ag₂S and/or AgSH on the impregnated filters. Because of the method’s linear dynamic range, sufficient air should be sampled to achieve filter loadings of 15 to 35 ng S/filter. A quality control method based on fluorescein mercuric acetate (FMA) is presented that ensures data quality while reducing the otherwise frequent need for fluori-metric calibration.     

Performance of the Annular Denuder System with Different Arrangements for HNO3 and HNO2 Measurements in Taiwan

ABSTRACT

Experiments on different annular denuder system (ADS)arrangements for sampling nitrous acid (HNO₂) and ni-tric acid (HNO₃) gases were conducted in this study toevaluate their sampling artifacts. The evaluation basis isthe one that employed one sodium chloride denuder forsampling HNO₃ gas and two sodium carbonate (Na₂CO₃)denuders for sampling HNO₂ gas, which is a commonlyemployed ADS arrangement in many field applicationsin the United States. A field study was conducted inHsinchu, Taiwan, and the results indicated that this ADSarrangement may yield over 80% relative errors for HNO₃gas. It also showed that the relative errors for HNO₂ gascan be less than 10% as sampled with only one Na₂CO₃denuder. This is attributed to the fact that the ambientHNO₃ concentration measured in this study was relativelylow while the HNO₂ concentration was high, as comparedto typical concentrations of these two gases measured inthe United States.

The sampling error of HNO₃ gas may be due to highconcentrations of N-containing interfering speciespresent in Taiwan’s atmosphere. Because the relative sam-pling errors of HNO₃ and HNO₂ gases depend mainly ontheir concentrations in the atmosphere as well as con-centrations caused by interfering species, the risk for higherror while measuring low HNO₂ concentrations by onlyone Na₂CO₃ denuder is also possible. As a result, it is sug-gested that pretests are necessary to evaluate possiblesources and degrees of sampling errors before fieldsampling of HNO₂ and HNO₃ gases. The sampling errorsof these two gases can, therefore, be minimized with abetter arrangement of the ADS.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Sulfur Toxicity and Media Capacity for H2S Removal in Biofilters Packed with a Natural or a Commercial Granular Medium

Abstract

Two types of media, a natural medium (wood chips) and a commercially engineered medium, were evaluated for sulfur inhibition and capacity for removal of hydrogen sulfide (H₂S). Sulfate was added artificially (40, 65, and 100 mg of S/g of medium) to test its effect on removal efficiency and the media. A humidified gas stream of 50 ppm by volume H₂S was passed through the media-packed columns, and effluent readings for H₂S at the outlet were measured continuously. The overall H₂S baseline removal efficiencies of the column packed with natural medium remained >95% over a 2-day period even with the accumulated sulfur species. Added sulfate at a concentration high enough to saturate the biofilter moisture phase did not appear to affect the H₂S removal process efficiency. The results of additional experiments with a commercial granular medium also demonstrated that the accumulation of amounts of sulfate sufficient enough to saturate the moisture phase of the medium did not have a significant effect on H₂S removal.

When the pH of the biofilter medium was lowered to 4, H₂S removal efficiency did drop to 36%. This work suggests that sulfate mass transfer through the moisture phase to the biofilm phase does not appear to inhibit H₂S removal rates in biofilters. Thus, performance degradation for odor-removing biofilters or H₂S breakthrough in field applications is probably caused by other consequences of high H₂S loading, such as sulfur precipitation.     

Health Risks of Short-term S02 Exposure to Exercising Asthmatics

A method is described for quantifying health risks to asthmatics briefly exposed to elevated levels of SO₂. By combining symptomologlcal and physiological measurements, we have developed a dose-response surface that relates both severity and incidence of response to ambient air quality levels. The complete model to assess potentially avoidable risks includes power plant emission data; ambient SO₂ background levels; demographic and activity patterns of asthmatics, the identified population at risk; and the dose-response surface. The estimated annual risk to persons experiencing an SO₂-lnduced response due to a nearby power plant is quite small (response rates under 3 percent). Uncertainties due to modeling errors, variations in activity patterns, demographics and physiological response are discussed.     

络合铁法脱除垃圾填埋气中的H2S

建立了以EDTA和柠檬酸为铁盐络合剂的循环脱硫体系,采用络合铁法对垃圾填埋气中的H2S进行脱硫中试实验,结果表明实验所建立的络合铁脱硫体系运行稳定,脱硫效率高,适合应用于垃圾填埋气中硫化氢脱除。     

A theoretical estimate of O3 and H2O2 dry deposition over the northeast United States

Estimates of short-term, regional-scale spatial distributions of ozone (O₃) and hydrogen peroxide (H₂O₂) dry deposition over the northeast U.S. are presented. Dry deposition fluxes to surfaces are computed using a regional tropospheric chemistry model with deposition velocities which vary with local meteorology, land type, insolation, seasonal factors and surface wetness. A compilation of O₃ surface resistances is presented based on a survey of O₃ dry deposition measurements. The surface resistance for H₂O₂ is assumed to be small under most conditions, causing H₂O₂ to dry deposit at a rate which is frequently limited by surface-layer turbulence. Regional patterns of dry deposition velocities for these oxidants over the northeast U.S. are computed using landuse data and meteorological information predicted using a mesoscale meteorology model. Domain-averaged O₃ deposition velocities during a spring period reach a mid-day peak of 0.7–0.8 cm s⁻¹ and drop to 0.1–0.2 cm s⁻¹ at night. Domain-averaged H₂O₂ deposition velocities at a height of approximately 80 m are predicted to reach a mid-day peak of 1.6–2.0cm s⁻¹, and fall to 0.6–0.9 cm s⁻¹ at night. Time-averaged surface-layer H₂O₂ concentrations show a latitude dependence, with higher concentrations in the south. H₂O₂ concentrations are significantly reduced due to efficient wet removal and chemical destruction during the passage of a cyclonic frontal system. In contrast, O₃ concentrations are predicted to rise during the passage of a frontal system due to efficient vertical exchange of midtropospheric air into the boundary layer during convective conditions, followed by synoptic-scale subsidence occurring in the high pressure airmass following a cyclone. Maximum O₃ deposition during this 3-day springtime period occurs in polluted agricultural areas. In contrast, H₂O₂ dry deposition exhibits a latitude dependence with maximum 3-day accumulations occurring in the south. Domain-averaged mid-day deposition rates for O₃ and H₂O₂ were 45–50 μmol m⁻² h⁻¹ and 4–5 μmol m⁻² h⁻¹. At night, deposition rates were approximately 5–10 μmol m⁻² h⁻¹ and 1.5–2.5 μmol m⁻² h⁻¹ for O₃ and H₂O₂. These model results show that regional patterns of oxidant dry deposition are strongly influenced by oxidant concentrations, atmospheric stability, surface roughness and numerous other surface and meteorological factors. Each of these factors must be well-characterized before regional patterns of biological damage associated with oxidant dry deposition can be quantified.