Combined Removal of SO2, H2S AND NOx from Gas Streams by Chemical Absorption with Aqueous Solution of 12-Molybdophosphoric Acid and its Reduced Species

Selective removal of SO₂, H₂S and NO_x from gas streams (air or towngas) was investigated using aqueous solutions of 12-molybdophosphoric acid and its reduced molybdenum blue species. The experimental results showed that H₂S and SO₂ in the gas streams can be removed quantitatively by yellow solution of 12-molybdophosphoric acid. The H₂S was oxidized into recoverable elemental sulfur and SO₂ into H₂SO₄, while the yellow solution was reduced into blue species (reduced molybdenum blue). The obtained reduced molybdenum blue solution was then used for the quantitative removal of NO_x, which was reduced into N₂ and the blue solution was then oxidized back into yellow species. It is possible that the regenration of scrubbing solution is not required and no chemical is consumed during absorption, when NO_x, SO₂ and/or H₂S coexisted in wastegases and the molar ratios of NO₂/(SO₂ + H₂S) is just equal to 1/2, although, in most cases, the ratio in real practical wastegases is not always equal to the value. The absorption mechanism was studied in detail. It was found that only one molybdenum atom in 12-molybdophosphoric acid was reduced from Mo(VI) to Mo(V) by H₂S or H₂SO₃ and the Mo(V) was oxidized back into Mo(VI) in the case of No_x absorption. 12-molybdophsophoric acid used in this work is inexpensive, commercially available, easily regeneratable, relatively nontoxic, and gives no secondary pollutant in the process.     

Absorption Kinetics of Nitrogen Oxides using Sodium Chlorite Solutions in Twin Spray Columns

NO _X is a major pollutant that causes acid deposition and photochemical smog. A large amount of NO _X is emitted from combustion sources such as power plants. As some articles have indicated, NO _X removal with NaClO₂ solution in an absorption column is an effective control approach. In this approach, first insoluble NO is oxidized into water-soluble NO₂ under acidic conditions, then NO₂ is removed in alkaline NaClO₂ solutions. The results indicate that the reaction rate constant is 9.1×10⁴ (L)^4.4/cm⁶/s/mol^2.4 in the first absorption column with acidic conditions, and the reaction orders with respect to NO and NaClO₂ are 1.4 and 2, respectively. In the second absorption column with alkaline conditions, the reaction rate constant is 3.2×10⁷ (L)^5.2/cm⁶/s/mol^3.2 and the reaction orders with respect to NO and NaClO₂ are 1.6 and 2.5, respectively. The activation energies in the first and second absorption column are 71.8 and 139.6 kJ/mol, respectively.     

Validation of Soil Phosphate Removal by Alkaline and Acidic Reagents in a Vertosol Soil using XANES Spectroscopy

There is a paucity of information on the soil phosphorus (P) forms removed by alkaline and acidic reagents in Vertosols. The first aim of this study was to identify which soil phosphates are removed by a two-step sequential fractionation (0.1 M NaOH and 1 M HCl) and by a dilute acid extractant (0.005 M H₂SO₄; Bureau of Sugar Experiment Stations (BSES) soil P test) on an “untreated” Vertosol using P K-edge x-ray absorption near-edge structure (XANES) at the Australian Synchrotron. There was supporting evidence that the 0.1 M sodium hydroxide (NaOH), 1 M hydrochloric acid (HCl), and 0.005M sulfuric acid (H₂SO₄) extractants remove soil phosphates according to the chemical solubility of known P minerals. The XANES spectra revealed the 1 M HCl and 0.005 M H₂SO₄ extractants remove calcium (Ca) phosphates from Vertosols, suggesting the latter extractant could be used as an alternative for a rapid and cost-effective measure of Ca phosphates in Vertosols.     

A regional scale model for the calculation of episodic concentrations and depositions of acidifying components

An eulerian long-range transport model for the calculation of concentrations of SO₂, SO₄, NO _x , and NO₃ and wet and dry depositions of SO _x (sum of SO₂ and SO₄) and NO _y (sum of NO, NO₂ and NO₃) over Europe is presented. The model is developed in such a way that only routinely available, analyzed or prognostic meteorological fields are required as input data. In this way it is possible to obtain a forecast of the air quality during smog episodes. For evaluation of smog episodes the model provides a way to estimate the contributions of different sources and the effect of emission scenarios. The model has been evaluated for four winter and three summer episodes. The modeled concentrations of SO₂ and SO, are in agreement with the available measurements. A less good agreement is found for NO₂ and NO _x (sum of NO and NO₂) concentrations. For these components the model tends to underpredict the measured values.     

Influence of ambient acidity on the absorption of NO3 − and NH4 + by tomato punts

Abstract

The effects of ambient acidity on NO₃ ^? and Nh₄ ⁺ absorption by 26‐day‐old tomato plants (Lycopersicon esculentum Mill.) were examined in solution culture. The absorption rate per unit root mass was measured for 6 hr. The NO₃ ^? absorption rate from 0.4 mM NaNO, was 36% greater at pH 4.5 than at pH 6.5. In contrast, the NhY absorption rate was approximately 42% greater at pH 5.5 or 6.5 than at pH 4.5. The presence of equimolar NHr from 0.4 mM NH^NO, decreased the NO, absorption rate at pH 5.5 or 6.5 but did not reduce the rate at pH 4.5. The NO, absorption rate was inhibited less at pH 5.5 when equimolar NHr was supplied from 0.2 mM (NH₄)₂S0₄ as opposed to NH₄NO₃. At pH 5.5, the N0₃ ^? absorption rate increased with increased #OPNH₄#CP₂SO₄ concentration. The presence of equimolar NO₃ ^? supplied as either NaNO₃ or NH₄NO₃ had no effect on the NH₄ ⁺ absorption rate at pH 5.5 or 6.5. However, at pH 4.5, the NH₄ ⁺ absorption rate was slightly reduced from NH₄NO₃ solutions relative to that from a (NH₄)₂S0₄ solution.     

Determination of phosphate in solution at different ionic composition using malachite green

Abstract

The malachite green method was sometimes used to determine low concentrations of inorganic phosphate due to its high sensitivity. The aim of this work was to test the suitability of this method for the determination of phosphorus (P) extracted by various reagents, e.g., KCl 0.01–1.20M, CaCl₂ 0.01–0.1M, Na₂SO₄ 0.01–0.40M, NaHCO₃ 0.1M at pH 8.5, and NaOH 0.1M+NaCl 1M. The malachite green method was also compared with the traditional molybdenum blue method on 35 soil extracts. Color development reached stability within 2 hrs and was stable for up to 24 hrs for dilute solutions. For concentrated solutions the stability was inversely proportional to the concentration of the reagent. Salt concentration appeared to have no effect on absorbance in KCl extracts of up to 1.2M and in Na₂SO₄ extracts of up to 0.05M. Higher concentrations of sodium sulfate induced flocculation and precipitation of the dye complex, as did CaCl₂ above 0.04 M. A strong correlation was found between the malachite green and the molybdenum blue method. The malachite green method can be used for P determination in soil extracts when appropriate time of color development is provided and salt concentration is taken into account.     

Control technology for coal-fired combustion in northeastern U.S.

The status of air pollution control technology for coal fired industrial and power plant boilers has been surveyed. Lime and limestone based scrubbers are capable of removing as much as 93% of flue gas SO₂ at facilities supplying 800 MW power. A sludge containing SO _x ions must be discarded in the process, usually requiring landfill or a settling pond. The Wellman-Lord, thiosorbic, and citrate processes are capable of producing salable products instead of the sludge. They are successful (85 to 90% removal) on demonstration-scale units. The Wellman-Lord process is currently being tested on large-scale coal fired units. Electrostatic precipitators, the mahor control device for removing particulates, can eliminate 99.5% of the fine particles. Fabric filtration can remove 99.9% and is more efficient in the 0.2 to 2μm size range than ESPs. Utilization of fabric filters is expected to increase significantly from its present 5% of the particulate removal market. Nitrogen oxide concentrations in coal fired systems are usually reduced by modification of the combustion system. No significant NO _x reduction on full-scale boilers has yet been reported, but demonstrations are planned over the next few years. Various process capital and annualized costs are reported for SO₂ and particulate removal systems. The status of fluidized bed combustion, fuel desulfurization, conversion of coal to gaseous and liquid fuels, and flue gas denitrification is also discussed. Part A deals with S emission; Part B with NO _x , particulates, and combined systems.     

Phosphorus in sequentially extracted fen peat soils: A K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy study

The speciation of phosphorus (P) in native and degraded peat soils is an analytical challenge, and synchrotron‐based P K‐edge X‐ray absorption near‐edge structure (XANES) is a suitable method to gain information on P species in soils and organic materials. The objective of the present study was to test if P K‐edge XANES reflected differences in P fractions in fen peat due to sequential extraction and peat degradation. We investigated each one top‐ and subsoil sample of a Fibric Histosol, which differed in the degree of humification (H8 vs. H5) and concentration of total P (P_t) (1944 mg kg^–1 vs. 436 mg kg^–1). In the topsoil, residual P, H₂SO₄‐P, and NaOH‐P accounted for roughly the same proportions of P_t (≈30%). In the subsoil, residual P (64% of P_t) was more abundant than NaOH‐P (21% of P_t) and H₂SO₄‐P (10% of P_t). Among many different P reference standards, the P XANES spectra reflected differences in mineral P more distinctive than in organic P compounds. Phosphorus XANES spectra of the residues after each sequential extraction step all showed a prominent white‐line peak at around 2152 eV. Stepwise removal of resin‐P, NaHCO₃‐P, and NaOH‐P were reflected mainly by the peak intensity but scarcely by distinct spectral features. Extraction with H₂SO₄ led to the disappearance of spectral features of Ca and Mg phosphates which is a first direct hint to these compounds in the peat. In conclusion, a combined sequential fractionation and spectroscopic (³¹P NMR, P K‐ and L‐edge XANES with linear‐combination fits) approach is proposed to overcome limitations of the present study and gain more insight into the P species in peat soils.     

Solubility of the labile forms of soil carbon and nitrogen in K2SO4 of different concentrations

The general pattern of the changes in the solubility of the labile carbon and nitrogen compounds with the changes in the concentration of the salt extractant (0.05 and 0.5 M K₂SO₄) has been determined for soils differing in their acidity and in their contents of organic matter and nitrogen. Different forms of extracted compounds react differently to changes in the salt concentration. The solubility of inorganic nitrogen compounds (NH ₄ ⁺ and NO ₃ ^? ) does not depend on the concentration of K₂SO₄. In most cases, the carbon and nitrogen of the microbial biomass manifest a tendency for increasing extractability with an increase in the concentration of the K₂SO₄ solution. A fundamental difference is characteristic of the organic carbon and nitrogen compounds, the solubility of which in 0.5 M K₂SO₄ increases in different soils by 1.5–3.9 times in comparison with their solubility in 0.05 M K₂SO₄.     

The calculation of transboundary and deposition fluxes of SO2 and sulfate by means of aircraft measurements

Aircraft measurements of the air pollutants SO₂ and sulfate (SO_x is defined as SO₂ plus sulfate), plus data on wind velocity, wind direction and depth of the planetary boundary layer, enable the calculation of transboundary mass fluxes of SO_x. When emission data are available, an emission-deposition balance of SO_x can be determined. The results of a measurement flight, carried out on 12 February, 1986, are presented. Two tracks were flown, along the eastern and along the western border of the Netherlands, respectively. The wind was easterly. The calculated deposition flux of SO_x is converted to an area-averaged dry deposition velocity (ν _d ). The result, ν _d = 1.2 × 10^?2 m s^?1, seems to be in good agreement with literature data.     

Trends of Air Pollution and Its Present Situation in Hiroshima Prefecture

The ambient concentration of SO₂, NOx and O_x in the atmosphere of Hiroshima, Fukuyama and Fuchu city which were monitored by the prefectural monitoring stations, are examined to give a picture of the typical air pollution at these sites. Results show that the yearly concentrations of SO₂ in these areas are significantly fall from 20 to 6 ppb during 1978–1996 when the NOx concentrations having no such significant change which varies from 40 to 30 ppb. The Photo-chemical Oxidant (Ox) increases annually at the rate of 0.3 ppb to 0.6 ppb in Hiroshima city only. To know the present situation of air pollution the Differential Optical Absorption Spectroscopy (DOAS) system is used in the city of Higashi Hiroshima. The daily average concentrations of SO₂, NO₂, O₃ and HONO measured during the period of August 1999 to March 2000 ranged from 1.4 ppb to 2.8 ppb, 13 ppb to 26.9 ppb, 21 ppb to 53.6 ppb and 1 ppb to 4.3 ppb respectively. The patterns of concentrations of NO₂ and O₃ measured by DOAS look similar to the seasonal patterns of NOx and Ox by the conventional system.     

Determination of (Nitrate + Nitrite )‐N in alkaline permanganate solutions

Abstract

The quantitative reduction of nitrate in an acid medium with reduced Fe was applied to the alkaline permanganate solution used to absorb NO and NO₂ evolved from soils during denitrification reactions. The method involves addition of H₂SO₄ to acidify the solution and ensure oxidation of nitrite to nitrate, and treatment with reduced Fe at 100°C to reduce nitrate to ammonium. The solution is made alkaline with NaOH and ammonium determined by standard distillation procedures. It is simple and precise, and applicable to nitrogen isotope ratio analysis of NO and NO₂ evolved from soils.     

Experimental studies on SO2 injuries in higher plants III: Inhibitory effect of suite ion on 14 CO 2 fixation

Photosynthesis decreases reversibly in plants exposed to SO₂. Photosynthesis recovers when the exposure to SO₂ is discontinued. Inactivation of a photosynthetic enzyme, ribulose-1,5-diphosphate carboxylase, by sulfonation of its SH groups was investigated as a cause of the reversible reduction of photosynthesis. The relationship between the sulfite ion concentration in the reaction mixture and ¹⁴CO₂ fixation catalized by the enzyme which was prepared from alfalfa leaves was explored by using radioactive NaHCO₃. About 50% and 85% inhibitions of ¹⁴CO₂ fixation were observed at 3 × 10^?3 M and 3 × 10^?2 M concentration of sulfite ion in the reaction mixture, respectively. The accumulation of 3 × 10^?4 M sulfite ion on the reaction site of the enzyme involved in the plants which were exposed to SO₂ could considerably reduce the CO₂ assimilation of the plant.     

Global emissions and natural processes for removal of gaseous pollutants

This review briefly illustrates the state of the art in the recognition of the various sources and natural sinks of gaseous pollutants. The removal mechanisms include absorption by vegetation, soil, stone, and water bodies, precipitation scavenging, and chemical reactions within the atmosphere. The nature and magnitude of anthropogenic and natural emissions of the gases (H₂S, SO₂, N₂O, NO, NO₂, NH₃, CO, O₃, and hydrocarbons), along with their ambient background concentrations and information on their major sinks identified to date, are discussed.     

Characteristics of Raindrop Acidification by Co-Washout of SO2(G)-H2O2(G)-HNO3(G)

In order to investigate the acid rain formation under the coexistence of SO₂(g), H₂O₂(g), and HNO₃(g) in the air, a mathematical model has been built and some numerical simulations have been carried out with use of the model. The simulation reveals that SO₂(g) absorbed into a raindrop is released and then re-absorbed as the fall distance increases. The desorption and re-absorption processes of SO₂(g) are caused by: (1) the fact that the equilibrium concentration of H₂O₂(aq) and HNO₃(aq) in raindrops are much higher than that of SO₂(aq), and (2) the fact that the oxidation reaction rate of HSO₃ ^? with H₂O₂(aq) increases with H⁺ concentration in raindrops. The degree of acidification of the rainwater has been estimated by introducing a raindrop size distribution. The acidification is mainly caused by the adsorption of SO₂(g) in the usual case where the atmospheric concentration of SO₂(g) is much higher than that of HNO₃(g). With the increase in the atmospheric concentration of HNO₃(g), the concentration of H⁺ generated from SO₂(g) decreases and the contribution of HNO₃(g) to the generation of H⁺ becomes dominant.

     

Visibility Variation with Air Qualities in the Metropolitan Area in Southern Taiwan

Principal component analysis (PCA) was used to analyze variationsin visibility compared with (1) variations in meteorological variables in the period 1961 to 1998, and (2) criteria air pollutant (SO₂, CO, O₃, NO_x and PM₁₀) concentrations monitored between 1994 and 1998, in the Kaohsiungmetropolitan area. Whilst average visibility during the 1960'sexceeded 20km, it had deteriorated to 5–10 km in theperiod 1994 to 1998. PCA identified seven components witheigenvalues greater than one. The principal componentsidentified accounted for variability related to PM₁₀concentration, ozone-related pollutants, oil combustion,and traffic emissions. Furthermore, spatial and temporalvariations in PM₁₀ were consistent throughout thecity. Variation in SO₂ levels followed a similarpattern at Tsoying, Shanming, Chiankin and Chiancheng.Industrial pollution and traffic emissions, SO₂, COand NO_x, from the Hsiaokang area remained within thearea. However, similar patterns of SO₂ andNO_xat Fengshan and Jenwu indicate that industrial emissionsfrom the latter were probably transported to the former.Much of the first principal component is based onPM₁₀ variability, suggesting that, of the fivecriteria pollutants studied, PM₁₀ is the majorcontributor to visibility deterioration. It is known thatPM_2.5 concentration is more closely associated withvisibility changes than is PM₁₀. However, becausePM₁₀ and PM_2.5 are strongly associated inKaohsiung, a targeting reduction in PM₁₀ may imply areduction in visibility.     

Water,NaHCO3−, NaH2PO4− and NaCl-extractable SO42− in acid forest soils

A variety of different methods have been used for the determination of inorganic soil SO₄^2? in the past, which makes it difficult to compare SO₄^2? contents of soils. Sulfate was extracted with the four commonly used extraction solutions 0.5 M NaHCO₃, 0.02 M NaH₂PO₄, 0.1 M NaCl and H₂O from A-, Bw- and Bs-horizons of six acid forest soils. 5 g of field moist soil were percolated with a flow rate of 5 ml/h and percolations were repeated as long as SO₄^2? was detectable in the percolate (> 0.5 mg SO₄·l^?1). NaCl and NaHCO₃ extracted highest amounts of total inorganic SO₄^2? in A-horizons, but NaHCO₃ caused analytical problems. NaHCO₃ and NaH₂PO₄ yielded highest amounts in B-horizons. With the exception of Bs-horizons more than 70% of the total inorganic SO₄^2? was H₂O-soIuble. Thus, if H₂O-soluble SO₄^2? is defined as reversibly bound, the greater part of the inorganic SO₄^2? in the investigated acid forest soils was reversibly bound. This SO₄^2? fraction can potentially be released, if SO₄^2? deposition decreases.     

Stability Studies of Waste Produced in Pilot-Plant Testing using Ferrous-EDTA and Magnesium-Enhanced Lime for Combined Sulfur-Dioxide/Nitrogen Oxides Removal

A pilot-plant-scale study of combined sulfur dioxide/nitrogen oxides (SO₂/NO_x) removal has been performed by the Dravo Lime Company at the Cincinnati Gas and Electric Company's Miami Fort Station in North Bend, Ohio. This study used Dravo's patented Thiosorbic® lime process along with Argonne National Laboratory's (ANL's) patented process for combined SO₂/NO_x removal using the chelate ferrous·ethylenediaminetetraacetate (Fe·EDTA). For approximately nine months, scrubbing tests were carried out, and waste samples were collected. Waste testing at ANL involved two types of long-term chemical stability experiments. In one test, the gas-phase composition above several different samples was studied by mass spectrometry over 22 months. Unexpectedly, production of carbon dioxide and hydrogen sulfide was observed in some of the samples. The other experiment involved solid-phase leaching. Samples were stored for up to 14 months before leaching. Each leachate was tested for total Kjeldahl nitrogen and for the nitrogen-containing ions nitrite, nitrate, and ammonium. Significant amounts of ammonium ions were found in two of the samples. Total leachable nitrogen was found to stabilize after about the first 7 months of storage.     

Influence of nitrate and chloride on the adsorption and transport of sulphate in soils

The adsorption and desorption of SO₄ was investigated as a function of KCI and KNO₃ concentration using soils with contrasting surface-charge properties. In the net negatively-charged soils, additions of C1 or NO₃ of up to about 0.05–0.10 M increased the adsorption of SO₄ but at higher concentrations adsorption decreased. In contrast, adsorption by the net positively-charged soils decreased with concentration increase over the entire range (0 to 1 M) investigated. The effects of CI and NO₃ on the adsorption of SO₄ were practically identical. The different pattern of SO₄ adsorption in the two groups of soils in response to addition of KCI or KNO₃ can at least partly be explained in terms of the effect of electrolyte on soil pH. The depression in pH of net negatively-charged soils induced by an indifferent electrolyte favours adsorption of SO₄; but, because pH changes in the opposite direction in positively-charged soils, SO₄ adsorption decreases in these soils. The distribution of a pulse of 35S-labelled SO₄ in soil columns after leaching with KCI solutions, ranging in concentration from 0 (H₂O) to 0.10 M, clearly reflected the manner in which electrolyte concentration affected the adsorption of SO₄. The distribution of ³⁵S was reasonably well simulated using the general transport equation combined with the Freundlich equation to describe the adsorption/desorption of SO₄. In contrast to other inorganic anions (H₂PO₄ and OH) applied in agricultural practice, C1 and NO₃ may have beneficial effects on the S economy of many soils by decreasing leaching losses of SO₄.     

The short-term effects of nitrification inhibitors on the abundance and expression of ammonia and nitrite oxidizers in a long-term field experiment comparing land management

Microcosms were set up to evaluate the effect of nitrification inhibitors (DCD, c-PTiO, and NaClO₃) on the abundance and expression of ammonia-oxidizing bacteria (AOB) and archaea (AOA), as well as the nitrite-oxidizing bacteria (NOB) Nitrospira and Nitrobacter. Both DCD and NaClO₃ inhibited the net nitrification rate, while c-PTiO had no significant effects, and NaClO₃ had a much greater inhibitory effect (> 60%) in all soils than DCD. No significant changes in total microbial abundance were observed with DCD and NaClO₃. DCD limited only the growth of AOB; however, NaClO₃ inhibited growth of both AOA and Nitrospira-NOB with no significant effects on AOB and Nitrobacter-NOB. Probably NaClO₃ inhibited both ammonia oxidation and nitrite oxidation. This is the first report to reveal the inhibitory effects of NaClO₃ on a specific nitrification process, helping to clarify the ecological niche of nitrifiers and the potential of nitrification inhibitors applied to soil.