Microbial coal desulphurization: calculation of costs

The sulphur found in coal is either part of the molecular structure, is contained in minerals such as pyrite (FeS₂), or occurs in minor quantities in the form of sulfate. When pyrite crystals are finely distributed within the coal matrix, mechanical cleaning can only remove part of the pyrite. It can, however, be removed by microbial action requiring only mild reaction conditions. The process involves simple equipment, almost no chemicals, but relatively long reaction times and, eventually, disposal of dissolved iron sulfate. Investment and operating costs are estimated for different process configurations on an industrial scale.     

An investigation of the efficacy of biological additives for the suppression of pyritic sulphur during simulated froth flotation of coal

The biological molecule responsible for the suppression of pyritic sulfur in fine coal simulated froth flotation treated with bacteria was identified. Protein was found to be the most effective agent in pyrite suppression of the three cell components (protein, lipid, and carbohydrate) assayed. Coal recovery and ash removal of the flotation process were only slightly reduced by this treatment. Other protein-containing materials were evaluated for their ability to suppress pyrite flotation. Whey was found to be the most cost-effective flotation additive of those assayed. The sulfur content of the whey-treated float was reduced by 84.0% in a synthetically prepared fractionated coal (10.7% sulfur), by a raw whey dosage of 20 muL/g coal. The inorganic sulfur component of a natural high sulfur coal fraction (10.9%) was completely depressed by this whey addition. The effect of particle size and pulp density upon the process were investigated.     

Effects of organic sulfur compounds on extraction and determination of inorganic sulfate

The common methods for determining inorganic soil sulfate may be affected by the extraction of sulfate from organic sulfur compounds such as ester sulfates. In order to test this, various synthetic organic sulfur compounds (ranging from ester sulfates to sulfonates and C-bonded sulfur) were extracted with deionized water or with two common sulfate extractors (0.5 M NaHCO₃ and 0.02 M NaH₂PO₄). Similar amounts of dissolved sulfate were detected in all extracts of the aromatic ester sulfate hydroxyquinoline sulfate. Sulfate was not released from aliphatic ester sulfates or C-bonded sulfur. Ion chromatography was compared to a turbidimetric method for the determination of sulfate. The latter method, based on BaSO₄-precipitation, appeared to be unsuitable for determining sulfate in organically influenced solutions. Barium precipitated sulfate as well as ester sulfates. Furthermore, the photometry of BaSO₄ was influenced by specific absorption of dissolved organic compounds, leading to a misinterpretation of the sulfate concentration in the solution.     

Biological removal of pyritic sulfur from coal by the thermophilic organism Sulfolobus acidocaldarius

More than 90% of initial pyritic sulfur was removed from bituminous coal samples (containing 2.1% pyritic sulfur) using the thermophilic organism Sulfolobus acidocaldarius. Microbial desulfurization rate was improved nearly ten fold by adjusting the N/P and N/Mg ratios in the nutrient medium. Environmental conditions were optimized. The optimal values of temperature and pH were 70 degrees C and 1.5, respectively. The influence of certain process variables (such as coal pulp density, particle size, and initial cell number density) on the rate of pyritic sulfur removal were determined. A pulp density of 20%, particle size of D (p) < 48 mum, and an initial cell number density of 10(12) cells/g pyrite in coal were found to be optimal. The carbon dioxide enriched air did not improve the rate of pyritic sulfur removal compared to pure air at 10% pulp density of coal samples containing 2.1% pyritic sulfur. The kinetics of microbial leaching of pyritic sulfur from coal was investigated. The rate of leaching was found to be first order with respect to pyritic sulfur concentration in the reaction medium.     

Karst development and sulfur deposit formation in the Ordos Basin: The role of bacterial sulfate reduction

Bacterial sulfate reduction is significant for the karst development and pyrite formation within the Ordovician weathering crust in the Ordos Basin of China. Bacterial communities were studied to determine their potential geomicrobiological functioning by constructing 16S rRNA clone library for in situ samples. The results showed that 147 positive clones sequenced were divided into 23 operational taxonomic units (OTUs), 8 OTUs accouting for 80% of all the selected clones belonged to the genus Desulfosporosinus. Bacterial sulfate reduction has been demonstrated to take place in the Ordovician by the classical hydrogeological information together with the stable sulfur isotope analysis from both the pyrite in the weathering crust and the products of the laboratory experiments on the dissolution of sulfate rock. The H₂S produced by bacterial sulfate reduction combined with iron to form pyrite, resulting in the development of hypogenic karst in the weathering crust. This process provided a reasonable interpretation for karst development in the vicinity of sulfur deposits in the Ordos Basin.     

Desulfurization of coal by microbial column flotation

Twenty-three strains capable of oxidizing iron were isolated from coal and ore storage sites as well as coal and ore mines, volcanic areas, and hot spring. Four strains were found to have high iron-oxidizing activity. One strain (T-4) was selected for this experiment since the strain showed the fastest leaching rate of iron and sulfate from pyrite among the four strains. The T-4 strain was assigned for Thiobacillus ferrooxidans from its cultural and morphological characteristics.Bacterial treatment was applied to column flotation. An increase of cell density in the microbial column flotation resulted in the increase of pyrite removal from a coal-pyrite mixture (high sulfur imitated coal) with corresponding decrease of coal recovery. The addition of kerosene into the microbial column flotation increased the recovery of the imitated coal from 55% (without kerosene) to 81% (with 50 muL/L kerosene) with the reduction of pyrite sulfur content from 11% (feed coal) to 3.9% (product coal). The kerosene addition could reduce the pyritic sulfur content by collecting the coal in the recovery. However, the addition could not enhance separation of pyrite from the coal-pyrite mixture, since pyrite rejection was not affected by the increase of the kerosene addition. An excellent separation was obtained by the microbial flotation using a long column which had a length-diameter (L/D) ratio of 12.7. The long column flotation reduced the pyritic sulfur content from 11% (feed coal) to 1.8% (product coal) when 80% of the feed coal was recovered without the kerosene addition. The long column flotation not only attained an excellent separation but also reduced the amount of cells for desulfurization to as little as one-tenth of the reported amount. (c) 1994 John Wiley & Sons, Inc.     

Microbial removal of pyrite from coal using a percolation bioreactor

Summary To compare the suspension and the percolation process system for the microbial desulphurization of coal the microbial pyrite oxidation in coal during storage in dumps was investigated in laboratory experiments with Thiobacillus ferrooxidans using a percolation bioreactor and resulted in a removal of 75% of pyrite within 70 days. In the initial desulphurization phase 450 mg pyritic-S/kg coal per day were oxidized at maximum rate, while the overall rate was determined to 130 mg pyritic-S/kg coal per day. During the desulphurization the mean particle size of the coal was reduced from 0.55 mm to 0.175 mm. As shown by microscopy and elemental analyses of the coal the pyrite was completely removed from small coal particles, whereas parts of it remained in the core of the greater particles.     

Intermediary sulfur compounds in pyrite oxidation: implications for bioleaching and biodepyritization of coal

Accumulation of elemental sulfur during pyrite oxidation lowers the efficiency of coal desulfurization and bioleaching. In the case of pyrite bioleaching by Leptospirillum ferrooxidans, an iron(II)-ion-oxidizing organism without sulfur-oxidizing capacity, from the pyritic sulfur moiety about 10% elemental sulfur, 2% pentathionate, and 1% tetrathionate accumulated by a recently described cyclic pyrite oxidation mechanism. In the case of pure cultures of Thiobacillus ferrooxidans and mixed cultures of L. ferrooxidans and T. thiooxidans, pyrite was nearly completely oxidized to sulfate because of the capacity of these cultures to oxidize both iron(II) ions and sulfur compounds. Pyrite oxidation in acidic solutions, mediated chemically by iron(III) ion, resulted in an accumulation of similar amounts of sulfur compounds as obtained with L. ferrooxidans. Changes of pH to values below 2 or in the iron ion concentration are not decisive for diverting the flux of sulfur compounds. The literature on pyrite bioleaching is in agreement with the findings indicating that the chemistry of direct and indirect pyrite leaching is identical. Received: 20 April 1998 / Received revision: 27 August 1998 / Accepted: 3 September 1998     

Solubilization of Minerals by Bacteria: Electrophoretic Mobility of Thiobacillus ferrooxidans in the Presence of Iron, Pyrite, and Sulfur

Thiobacillus ferroxidans is an obligate acidophile that respires aerobically on pyrite, elemental sulfur, or soluble ferrous ions. The electrophoretic mobility of the bacterium was determined by laser Doppler velocimetry under physiological conditions. When grown on pyrite or ferrous ions, washed cells were negatively charged at pH 2.0. The density of the negative charge depended on whether the conjugate base was sulfate, perchlorate, chloride, or nitrate. The addition of ferric ions shifted the net charge on the surface asymptotically to a positive value. When grown on elemental sulfur, washed cells were close to their isoelectric point at pH 2.0. Both pyrite and colloidal sulfur were negatively charged under the same conditions. The electrical double layer around the bacterial cells under physiological conditions exerted minimal electrostatic repulsion in possible interactions between the cell and either of its charged insoluble substrates. When Thiobacillus ferrooxidans was mixed with either pyrite or colloidal sulfur at pH 2.0, the mobility spectra of the free components disappeared with time to be replaced with a new colloidal particle whose electrophoretic properties were intermediate between those of the starting components. This new particle had the charge and size properties anticipated for a complex between the bacterium and its insoluble substrates. The utility of such measurements for the study of the interactions of chemolithotrophic bacteria with their insoluble substrates is discussed.     

Bacterial formation of phosphatic laminites off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01′ S and 10°24′ S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS₂) and sphalerite (ZnS). Low δ³⁴S_pyrite values (average ?28.8‰) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide‐oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate‐reducing bacteria and associated sulfide‐oxidizing bacteria. Following an extraction–phosphorite dissolution–extraction procedure, molecular fossils of sulfate‐reducing bacteria (mono‐O‐alkyl glycerol ethers, di‐O‐alkyl glycerol ethers, as well as the short‐chain branched fatty acids i/ai‐C_15:0, i/ai‐C_17:0 and 10MeC_16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate‐reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate‐reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate‐reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate‐reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.     

Occurrence and activity of iron- and sulfur-oxidizing microorganisms in alkaline coal strip mine spoils

Spoils samples collected from a coal strip mine in southeastern Montana were examined for populations and activities of iron- and sulfur-oxidizing bacteria. Spoils examined were of three types: (a) acidic pyrite-rich waste coal, (b) oxidation halo material, and (c) alkaline material, which was the most widespread type. Bacterial numbers, sulfur oxidation, and¹⁴CO₂ uptake activity declined to low levels in the summer when spoils were dry. Even in wetter spring months pyritic spoils contained relatively low numbers of acidophilic iron- and sulfur-oxidizing bacteria, probably indicative of water stress since the same spoils incubated with excess water or dilute mineral salts showed considerably greater bacterial numbers and activity. Certain wells in coal and spoils aquifers contained substantial populations of iron-oxidizing acidophilic bacteria. However, these wells were always of alkaline or neutral pH, indicating that bacterial pyrite oxidation occurred where groundwaters contacted either replaced spoils or coal that contained pyrite or other metal sulfides. Bacterial activity may contribute to trace metal and sulfate leaching in the area.     

Removal of Sulfur Compounds from Coal by the Thermophilic Organism Sulfolobus acidocaldarius

The thermophilic, reduced-sulfur, iron-oxidizing bacterium Sulfolobus acidocaldarius was used for the removal of sulfur compounds from coal. The inclusion of complex nutrients such as yeast extract and peptone, and chemical oxidizing agents, 0.01 M FeCl₃ into leaching medium, reduced the rate and the extent of sulfur removal from coal. The rate of sulfur removal by S. acidocaldarius was strongly dependent on the sulfur content of the coal and on the total external surface area of coal particles. Approximately 96% of inorganic sulfur was removed from a 5% slurry of coal which had an initial total sulfur content of 4% and an inorganic (pyritic S and sulfate) sulfur content of 2.1%. This resulted in removal of 50% of initial total sulfur present in coal.     

Pyrite formation in marshes during early diagenesis

Pyrite was removed from peat cores by draining the sediments and allowing the pyrite to oxidize. Then the peat cores were placed back into intertidal salt marsh sediments to incubate. Pyrite accumulated rapidly in peat incubated in situ. A greater accumulation of pyrite was observed in peat that contained living grass than peat in which the grass had been killed.

Resin‐imbedded samples of peat from nearby sediments showed that small single crystals of pyrite were abundant, supporting the idea that pyrite in marshes forms rapidly through direct precipitation. Pyrite was also observed filling vascular channels in roots. It had been proposed that pyrite fills root channels in freshwater environments where the primary sulfur source used by sulfate‐reducing bacteria is organic sulfur rather than sulfate. The widespread occurrence of pyrite filling vascular channels in salt marsh peat makes it unlikely that pyrite morphology can be used to infer the salinity of the overlying water.

Marsh sediments are characterized by higher carbon/sulfur ratios and pyritization (Fe‐pyritel(Fe‐pyrite + Fe‐HCl)) indices than marine subtidal sediments. Within wide ranges these indices do not seem to be very sensitive to salinity of flooding water or carbon concentrations in sediments. Oxidation and iron availability appear to be the major controls on pyrite accumulation in marshes. While pyrite concentrations in submerged sediments can be used as indicators of relative rates of sulfate reduction, sulfur storage in intertidal marsh sediments is not as tightly linked to this microbial process.     

Mathematical modeling of biological sulfide removal in a fed batch bioreactor

In this study, biological sulfide removal is investigated in a fed batch bioreactor. In this process, sulfide is converted into elemental sulfur particles as an intermediate in the oxidation of hydrogen sulfide to sulfate. The main product is sulfur at low dissolved oxygen or at high sulfide concentrations and also more sulfates are produced at high dissolved oxygen. According to the carried out reactions, a mathematical model is developed. The model parameters are estimated and the model is validated by comparing with some experimental data. The results show that, the proposed model is in a good agreement with experimental data. According to the experimental result and mathematical model, sulfate and sulfur selectivity are sensitive to the concentration of dissolved oxygen. For sulfide concentration 0.2 (mM) in the bioreactor and dissolved oxygen of 0.5 ppm, only 10% of sulfide load is converted to sulfate, while it is 60% at the same sulfide concentration and dissolved oxygen of 4.5 ppm. At high sulfide load to the bioreactor, the concentration of uneliminated sulfide increases; it leads to more sulfur particle selectivity and consequently, less sulfate selectivity.     

In situ S‐isotope compositions of sulfate and sulfide from the 3.2 Ga Moodies Group,South Africa: A record of oxidative sulfur cycling

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO₄). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ³³S_sulfate values through the Paleoarchean.     

Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer

Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ¹³C_DIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed (³⁴ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate‐driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment.     

Effect of Reduced Sulfur Species on Chemolithoautotrophic Pyrite Oxidation with Nitrate

We compared the response at neutral pH of some denitrifiers to different electron donors such as reduced sulfur (pyrite, S(0), and marcasite) and reduced Fe. Chemolithoautotrophic oxidation of pyrite with nitrate as electron acceptor was not possible when the pyrite was in a pure crystalline form, whereas oxidation of synthesized FeS₂ of low crystallinity and of S(0) with nitrate as electron acceptor was possible. Neither nitrite nor sulfate was formed when Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 was tested. Microbial reduction of nitrate appears to be induced via S oxidation but not via Fe oxidation.     

Precipitation of greigite and pyrite induced by Thermococcales: an advantage to live in Fe- and S-rich environments?

Thermococcales, a major order of archaea inhabiting the iron- and sulfur-rich anaerobic parts of hydrothermal deep-sea vents, have been shown to rapidly produce abundant quantities of pyrite FeS₂ in iron–sulfur-rich fluids at 85°C, suggesting that they may contribute to the formation of ‘low temperature’ FeS₂ in their ecosystem. We show that this process operates in Thermococcus kodakarensis only when zero-valent sulfur is directly available as intracellular sulfur vesicles. Whether in the presence or absence of zero-valent sulfur, significant amounts of Fe₃S₄ greigite nanocrystals are formed extracellularly. We also show that mineralization of iron sulfides induces massive cell mortality but that concomitantly with the formation of greigite and/or pyrite, a new generation of cells can grow. This phenomenon is observed for Fe concentrations of 5 mM but not higher suggesting that above a threshold in the iron pulse all cells are lysed. We hypothesize that iron sulfides precipitation on former cell materials might induce the release of nutrients in the mineralization medium further used by a fraction of surviving non-mineralized cells allowing production of new alive cells. This suggests that biologically induced mineralization of iron-sulfides could be part of a survival strategy employed by Thermococcales to cope with mineralizing high-temperature hydrothermal environments.     

Coal Depyritization by the Thermophilic Archaeon Metallosphaera sedula

The kinetics of pyrite oxidation by Metallosphaera sedula were investigated with mineral pyrite and two coals with moderate (Pittsburgh no. 8) and high (New Brunswick, Canada) pyritic sulfur content. M. sedula oxidized mineral pyrite at a greater rate than did another thermophile, Acidianus brierleyi, or a mesophile, Thiobacillus ferrooxidans. Maximum rates of coal depyritization were also greater with M. sedula, although the magnitude of biological stimulation above abiotic rates was notably less than with mineral pyrite. Coal depyritization appears to be limited by the oxidation of pyrite with ferric ions and not by the rate of biotic oxidation of ferrous iron, as evidenced by the maintenance of a high ratio of ferric to ferrous iron in solution by M. sedula. Significant precipitation of hydronium jarosite at elevated temperature occurred only with New Brunswick coal.