The effect of ionic strength on the manganese catalyzed oxidation of sulfur(IV)

We have measured the effect of ionic strength on the rate of the manganese catalyzed oxidation of sulfur in both the high (10⁻³M) and low (10⁻⁶M) sulfur concentration regimes. The effect is an extreme inhibition of the reaction as the ionic strength increases. Ionic strength, not hydrogen ion, accounts for the pH dependence of the rate, and makes it possible (1) to explain some unusual behavior described in the literature on this reaction, and (2) to reconcile in part a number of the literature rates. The inhibition is the same in both concentration regimes. Because of the complexity of this reaction, we believe that it is still not clear which rate law is appropriate for use in atmospheric calculations, athough we suggest provisional use of the first order, low sulfur rate.     

The Compact Sequential Automatic Air Sampler

The body of information presented in this paper is directed to ecologists concerned with the effects and economic impact of sulfur dioxide on forest growth. Investigations were carried out over a ten-year period, 1953–1963, in the Sud-bury smelter district of Ontario, where three large smelters discharge annually approximately 2,000,000 tons of sulfur dioxide gas into the surrounding atmosphere. The study was designed to determine the long-term chronic effects of sulfur dioxide on yield, growth, and survival of plant life. Since eastern white pine is the most susceptible coniferous tree to sulfur dioxide injury, it was selected as the indicator tree to determine the degree and extent of injury in the Sudbury area. Tree data accumulated from the sample plots were correlated with records of atmospheric sulfur dioxide monitored continuously during the growing season by a network of ten strategically-located Thomas autometers. Based on the degree of injuries exhibited by the trees, and on air sampling records of sulfur dioxide, the Sudbury area was segregated into three fume zones: Inner, Intermediate, and Outer. An estimate was made of the loss in income suffered by the owners of wood or the producers of wood products in the Sudbury area as a result of sulfur dioxide air pollution, by utilizing the white pine volume growth loss data     

Catalytic reduction of sulfur dioxide with carbon monoxide over tin dioxide for direct sulfur recovery process

SO(2) reduction by CO over SnO(2) catalyst was studied in this work. The parameters were the reaction temperature, space velocity (GHSV) and [CO]/[SO(2)] molar ratio. The optimal temperature, GHSV and [CO]/[SO(2)] molar ratio were 550 degrees C, 8000 h(-1) and 2.0, respectively. Under these conditions, the SO(2) conversion and sulfur selectivity were about 78% and 68%, respectively. The following reaction pathway involving two mechanisms was proposed in SO(2) reduction by CO over SnO(2) catalyst: in the first step involving Redox mechanism, the elemental sulfur was produced by the mobility of the lattice oxygen between SO(2) and SnO(2) surface. In the second step, COS was formed by the side reaction between elemental sulfur and CO or metal sulfide and CO. In the third step involving COS intermediate mechanism, the abundant elemental sulfur was produced by the SO(2) reduction by COS which was produced in the second step and was more effective reducing agent than CO.     

Investigation of the reaction of hexabromocyclododecane with polysulfide and bisulfide in methanol/water solutions

Reactions of hexabromocyclododecane (HBCD), a widely used brominated flame retardant, with reduced sulfur species (e.g., polysulfide and bisulfide) were investigated in well-defined solutions under anoxic conditions. It is likely that reactions of HBCD with reduced sulfur species such as polysulfides and bisulfide present in anoxic subregions of coastal water bodies and sediments could have a significant impact on the fate of HBCD. The second-order reaction rate constant of HBCD with polysulfides in 80% methanol/20% water at 40°C is 2.2 (±0.3)×10(-2) M(-1) s(-1). The second-order reaction rate constant of HBCD with bisulfide is 8.9 (±2.8)×10(-4) M(-1) s(-1) under the same conditions. The formation of two products was observed with either of the two reduced sulfur species. The experiments also indicate that the γ-isomer of HBCD is reacting significantly faster with reduced sulfur species than the α-isomer.     

A System for Abatement Control Strategy Evaluation

The Air Quality Control Program of the Commonwealth of Massachusetts has developed an implementation plan for the Metropolitan Boston Intrastate Air Quality Control Region as required by PL 90-148. An essential part of the plan was a set of control regulations designed to achieve and maintain an air quality compatible with adopted standards. Control strategy modeling was used as a tool in selecting the most appropriate regulations to achieve this goal. The body of information presented in this paper is directed to those state and county air pollution control officials concerned with the formulation and evaluation of regulations.

The paper details the procedures developed and presents a case history of their use in the region. The system is a synthesis of generally-available software and newly-developed computer programs to provide ahighly automated computational structure. It permits rapid simulation of the emissions resulting from the application of various control regulations. Predictions on the changes expected in ambient air quality levels are then made by the use of the Air Quality Display Model (AQDM).

The initial step in the application was a calibration of the system using predicted and measured annual concentrations. This step yielded correlation coefficients of 0.92 for sulfur dioxide and 0.85 for particulates. Subsequently, the system was used to evaluate the baseline case of uncontrolled sulfur in fuel use. Alternative sulfur control strategies were tested for compatibility with air quality standards. The principal strategies tested were: (a) 1% sulfur uniformly throughout the region; (6) 1% sulfur in core area of region, 2.2% sulfur elsewhere; (c) 0.5% sulfur in core area of region, 2.2% sulfur elsewhere; (d) 0.5% sulfur in core area of region, 1.0% sulfur elsewhere.

Strategies (b) and (d) were implemented into a time phased set of control regulations for the region.

Experience with the system has shown it to be a convenient and rapid method for simulating the effects of control regulations. Furthermore, the utility of this initial model warrants expansion of its application to the other air quality control regions in the Commonwealth.     

Effect of different types of elemental sulfur on bioleaching of heavy metals from contaminated sediments

The application of two different types of elemental sulfur (S0) was studied to evaluate the efficiency on bioleaching of heavy metals from contaminated sediments. Bioleaching tests were performed in suspension and in the solid-bed with a heavy metal contaminated sediment using commercial sulfur powder (technical sulfur) or a microbially produced sulfur waste (biological sulfur) as substrate for the indigenous sulfur-oxidizing bacteria and thus as acid source. Generally, using biological sulfur during suspension leaching yielded in considerably better results than technical sulfur. The equilibrium in acidification, sulfur oxidation and metal solubilization was reached already after 10-14 d of leaching depending upon the amount of sulfur added. The metal removal after 28 d of leaching was higher when biological sulfur was used. The biological sulfur added was oxidized with high rate, and no residual S0 was detectable in the sediment samples after leaching. The observed effects are attributable to the hydrophilic properties of the biologically produced sulfur particles resulting in an increased bioavailability for the Acidithiobacilli. In column experiments only poor effects on the kinetics of the leaching parameters were observed replacing technical sulfur by biological sulfur, and the overall metal removal was almost the same for both types of S0. Therefore, under the conditions of solid-bed leaching the rate of sulfur oxidation and metal solubilization is more strongly affected by transport phenomena than by microbial conversion processes attributed to different physicochemical properties of the sulfur sources. The results indicate that the application of biological sulfur provides a suitable means for improving the efficiency of suspension leaching treatments by shortening the leaching time. Solid-bed leaching treatments may benefit from the reuse of biological sulfur by reducing the costs for material and operating.     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Toxicity evaluation of organic sediment extracts resolved by size exclusion chromatography using rainbow trout hepatocytes.

The (geno)toxicity of sediment dichloromethane extracts and fractions obtained by size exclusion chromatography were evaluated to investigate effects based on size fractionation. In this study, three sediments were selected according to their incremental contamination in PAHs and in PCBs: Hamilton harbour, Toronto bay and lake St. Clair sediments. Heavy metals, total sulfur and elemental sulfur (S8) were also determined in the (un)fractionated sediment extracts. The liver cells were exposed to concentrations of sediment extracts and fractionated samples for 24 h at 15 degrees C, afterwhich cell viability, cytochrome P4501A1 activity, available free Zn, DNA damage and oxidative stress were determined. The results showed that the sediment extracts contained high levels of sulfur most of which was found in the low molecular weight (LMW) region, i.e., the 2000-50 atomic mass unit (amu) fraction. Elemental sulfur (S8) accounted for 14-41% of extractable sulfur and were found to elute in the post-column volume (PCV) fraction despite its molecular weight of 256 amu. Heavy metals were found mainly in the HMW (i.e. the > 2000 amu) fraction and LMW fractions and very few or none were observed in the PCV fractions. In sediment extracts, sublethal effects were present principally by the HMW and LMW fractions suggesting that some chemicals were also associated with high molecular weight compounds of extractable organic matter. Less toxicity or effect was sometimes found in the extract indicating an antagonistic effect of the contaminants. We found that cell viability and genotoxicity evaluations could be performed on the unfractionated extracts while EROD, available Zn and oxidative stress measurements should be performed on the LMW fractions because of possible antagonist or shielding effects. Considering the cytotoxic responses, the best toxicity ranking in respect to contaminant levels in sediment extract was obtained with the LMW and PCV fractions which accounted for most of the toxic responses in the chromatographic fractions. Moreover, the shielding effect could be explained, in part, by the association of LMW contaminants to large macromolecules.     

PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters

Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry’s law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3–45 °C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H₂S, a higher enthalpy of air–liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that co-solute effects for sulfur compounds can be neglected in numerical biofilter models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength.     

On a Strategy for Reducing Short-range Daytime Ground Level Concentrations Due to Emissions from Very Tall Stacks

Abstract

Airborne fine particle sulfur data from the summer intensive of Project MOHAVE (Measurement of Haze and Visual Effects) was analyzed by the Receptor Model Applied to Patterns in Space (RMAPS) model, a novel multivariate receptor-oriented model that applies to secondary and primary species. The sulfur data from 17 sites were found to be well predicted by three spatial patterns interpreted as sources along the valley of the Colorado River; transport from sources located to the southwest; and transport from sources located to the southeast. The model was tested by using parameters derived from the 17-site data set to apportion sulfur for six sites that were not part of the original data set. The sulfur apportionment for these six sites was in agreement with the original apportionment and the physical interpretation of the spatial patterns given above. The effects of systematic and random error on the sulfur apportionment were estimated. The amount of sulfur associated with the Colorado River valley sources was rather insensitive to both types of error. For the two sites in the Grand Canyon National Park, the fraction of total particulate sulfur from the Colorado River valley source is estimated to be in the range of 27-65% at Meadview and 11-28% at Hopi Point.     

Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

Sulfur (S)-induced enhancement of iron plaque formation in the rhizosphere reduces arsenic accumulation in rice (Oryza sativa L.) seedlings

The effects of two sulfur (S) sources (SO(4)(2-), S(0)), and three rates of S application (0, 30, 120 mgS/kg) on the formation of iron plaque in the rhizosphere, and on the root surface of rice, and As (arsenic) uptake into rice (Oryza sativa L.) were studied in a combined soil-sand culture experiment. Significant differences in As uptake into rice between +S and -S treatments were observed in relation to S sources, and rates of S application. Concentrations of As in rice shoots decreased with increasing rates of S application. The mechanism could be ascribed to sulfur, induced the formation of iron plaque, since concentrations of Fe in iron plaque on quartz sands in the rhizosphere, and on the root surface of rice increased with increasing rates of S application. The results suggest that sulfur fertilization may be important for the development approaches to reducing As accumulation in rice.     

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.     

Natural desulfurization in coal-fired units using Greek lignite

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

氧化亚铁硫杆菌对双底物的利用

氧化亚铁硫杆菌是脱硫领域的重要微生物之一。研究了在亚铁和含硫基质双底物存在的条件下,氧化亚铁硫杆菌对2种能源物质的利用情况,结果表明,Thiobacillus ferrooxidans在双底物利用过程中,铁氧化系统首先启动,随Fe2＋浓度的下降,硫氧化系统开始启动,之后两者协同作用;3种含硫基质的存在对Fe2＋的氧化有不同的影响,S对Fe2＋的氧化不产生抑制作用,而Na2S2O3和Na2SO3对Fe2＋的氧化有一定的抑制,尤其是Na2SO3的抑制作用更明显,亚铁完全氧化所需的时间更长。     

Performance and Problems of Claus Plant Operation on Coke Oven Acid Gases

The application of Claus Plant sulfur recovery units to the coke oven gas (COG) acid gases at three Bethlehem Steel Corporation plants is discussed. While many of the problems encountered are not unique to coke oven gas-derived acid gases, it was found that special consideration must be given to the effect of components not normally encountered in the typical Claus plant application to petroleum derived gases. It is perhaps fortunate that the feed composition to the three units was sufficiently different to expedite recognition of the source of some of these difficulties. One substance of concern is the hydrogen cyanide normally found in COG acid gases. In the absence of some means of removing or decomposing this material before it enters the Claus Plant extensive corrosion within the unit is observed after a short period of time. This is due to the fact that, contrary to expectation, a substantial quantity of this material survives the burner flame. The various alternatives in its elimination are discussed. A second major contaminant in COG acid gases is particulate iron sulfide and iron cyanide. While the exact source of these materials is in doubt, there is little doubt that in the absence of their removal, inorganic blockages within the Claus Plant will occur. By properly accounting for the special properties of coke oven gas-derived acid gas we have recently achieved short term sulfur recovery efficiencies of 95% and higher.     

IV. Recovery of Flue Gas Sulfur as Ammonium Phosphate

The present development in industry has greatly increased the consumption of fossil fuel all over the world. The sulfur present in these fuels on combustion impairs the atmosphere and has to be removed before or after combustion. Direct desulfurization is still in its initial stage of commercial application and is thought to be rather expensive. Most projects today are concerned with flue gas desulfurization and a few people have been successful in the pilot plant scale. Flue gas sulfur is usually recovered as sulfuric acid or ammonium sulfate. The Kiyoura-T.I.T. process employs a completely dry method to recover this sulfur as ammonium sulfate. However, the present trends in fertilizers show that there is a marked drop in the consumption of this type of fertilizer except for China and other Asian countries.

Experiments were carried out to produce a high grade phosphatic fertilizer with a larger field of application. The authors were successful in rendering the phosphate in phosphate rock water soluble by reacting it with the sulfate radical of the ammonium sulfate. Ammonium acid sulfate was used in the experiments and the phosphate radical was determined by a colorimeter utilizing the ammonium molybdate method.

The results showed a conversion and an extractability of 98%, when the molecular ratio of ammonium acid sulfate to the CaO in phosphate rock was in the vicinity of 1:1.4-1.5. The reaction time was 120-180 minutes.

The extracted liquid was crystallized and put through X ray diffractometer experiments which showed that most of the crystals were ammonium phosphate containing about 15% N and 39% P₂O₅ on a dry basis. Thus, it is evident that this could be effectively applied in a commercial scale plant, recovering the flue gas sulfur as ammonium phosphate. The Kiyoura-T.I.T. process can be utilized to recover the flue gas sulfur either as the sulfate or as the phosphate.     

Canadian Activities in Ambient Air Quality Criteria and Development of Standards

Within recent years, increasing attention has been directed to the determination of contaminant levels in urban and industrial areas involving particulate matter (dustfall, suspended matter and smoke), sulfur dioxide, hydrogen sulfide, fluorides, ozone or oxidant, oxides of nitrogen and polycyclic aromatic hydrocarbons. However, with regard to criteria and evaluation of effects, none of these pollutants has been studied as thoroughly as sulfur dioxide. Presently, three provinces in Canada have adopted acts or regulations dealing with the control of air pollution. The Ontario Act, passed in 1958 and amended in 1963 and 1964, is the most comprehensive in scope. The Damage by Fumes Arbitration Act of Ontario provides for the awarding of compensation where crops, trees or other vegetation is damaged by sulfur fumes arising from the smelting or roasting of nickel-copper ore or iron ore or from the treatment of sulfides for the production of sulfur of sulfuric acid for commercial purposes. Regulations have also been enacted in Manitoba and Alberta. A provincial act is under consideration in Saskatchewan.     

Odor and Fallout Control in a Kraft Pulp Mill

Lead dioxide cylinders are inexpensive sampling devices commonly used for an assessment of sulfur oxides in the atmosphere. This paper will report the results of basic studies intended to characterize some of the critical parameters of this method. The behavior of the system in the region of the critical loading percentages was determined as well as the effects of lead dioxide particle size, presence of reduced sulfur compounds, and use of different binders. From these studies it has been possible to show a definite relationship between allowable exposure times and atmospheric concentrations of sulfur dioxide with particle size as a major parameter     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.