Corrosion of Pipe Steel Samples and Conjugated Conversion of Sulfur Compounds by Thionic Bacteria <Emphasis Type="Italic">Halothiobacillus neapolitanus</Emphasis> DSM 15147

The kinetics of conversion of sulfur compounds by Halothiobacillus neapolitanus DSM 15147 bacteria was studied in the presence of steel samples. It was shown that the presence of steel altered the known pathway of sulfur compound oxidation by thionic bacteria. Production of atomic hydrogen via the interaction between biogenic sulfuric acid and steel enhanced secondary production of intermediates and decreased the content of sulfate produced previously. The process was accompanied by pH elevation and continuation of intense growth of the thionic bacterium culture. Thionic bacteria formed a corrosive medium, which caused metal destruction. The protective properties of anticorrosive coatings 225 LS and 640 mk were tested. It was shown that these coatings protected steel from the destructive effect of biogenic sulfuric acid.     

A new test procedure for biogenic sulfuric acid corrosion of concrete

A new test method is described for biogenic sulfuric acid corrosion of concrete, more specifically in sewer con-ditions.The aim of the new test method is the development of an accelerated and reproducible procedure formonitoring the resistance of different types of concrete with regard to biogenic sulfuric acid corrosion. This exper-imentalprocedure reflects worst case conditions by providing besides H₂S, also an enrichment of thiobacilli andbiologically produced sulfur. By simulating the cyclic processes occurring in sewer pipes, significant differencesbetween concrete mixtures could be detected after 51 days. Concrete modified by a styrene-acrylic ester polymerdemonstrated a higher resistance against biogenic sulfuric acid attack.     

Influence of polymer addition on biogenic sulfuric acid attack of concrete

A simple and reproducible microbiological simulation procedure in combination with a chemical procedure was used to test concrete for its potential resistance towards biogenic sulfuric acid. Concerning fundamental aspects of the corrosion reaction, it was shown that particularly the penetration of H₂S inside the concrete crevices accelerated the corrosion process. The influence of different polymer types and silica fume additions on the resistance of the concrete samples was determined. The addition of the styrene acrylic ester polymer resulted in an increased resistance while the addition of the acrylic polymer or silica fume caused less resistant concrete. For the vinylcopolymer and the styrene butadiene polymer, no significant effect was observed on the resistance of the concrete samples. The results of the two different test methods confirmed the difference between corrosion due to purely chemical sulfuric acid and corrosion due to microbiologically produced sulfuric acid.     

The reactions of the sulfur-containing amino acids with phosphoric and sulfuric acids

Both cystine and cysteine react very differently toward 6.0 M phosphoric and sulfuric acids. With phosphoric acid, extensive decomposi tion occurs; with sulfuric acid, very little.Cystine, in phosphoric acid at 100 °C. produces hydrogen sulfide, free sulfur, cysteic acid, ammonia, alanine, serine, and pyruvic acid. Cysteine produces a similar series but with marked quantitative differences.Cystine, in sulfuric acid, is merely racemized.Methionine is largely demethylated by sulfuric acid under these conditions. It is practically inert toward phosphoric acid.The behavior of hair toward phosphoric and sulfuric acids is similar to that of cystine but is modified by reactions of other hydrolytic products.     

Mucosubstances of rabbit granulocytes studied by means of electron-microscopic radioautography and X-ray microanalysis

Summary Rabbit bone marrow cells have been studied by means of light-and electron-microscopic radioautography and X-ray microanalysis. Carrier free sulfuric acid was used as the radioactive precursor in this experiment. Immature granulocytes showed more active incorporation than mature ones. Silver grains were observed in the Golgi apparatus and granules in three kinds of granulocytes. Electron-microscopically, immature granules showed the incorporation of inorganic sulfate, while mature ones did not. Sulfur was detected in all kinds of granules of the three granulocyte types by X-ray microanalysis. It is concluded that incorporated inorganic sulfur may be utilized for the synthesis of acid glycosaminoglycans and the sulfur detected by X-ray microanalysis may be that contained in the acid glycosaminoglycan. The sulfur detected in the specific granules of the heterophil probably derives from proteins or polypeptides incorporating sulfur containing amino acids.     

Mucosubstances of rabbit granulocytes studied by means of electron-microscopic radioautography and X-ray microanalysis.

Rabbit bone marrow cells have been studied by means of light- and electron-microscopic radioautography and X-ray microanalysis. Carrier free sulfuric acid was used as the radioactive precursor in this experiment. Immature granulocytes showed more active incorporation than mature ones. Silver grains were observed in the Golgi apparatus and granules in three kinds of granulocytes. Electron-microscopically, immature granules showed the incorporation of inorganic sulfate, while mature ones did not. Sulfur was detected in all kinds of granules of the three granulocyte types by X-ray microanalysis. It is concluded that incorporated inorganic sulfur may be utilized for the synthesis of acid glycosaminoglycans and the sulfur detected by X-ray microanalysis may be that contained in the acid glycosaminoglycan. The sulfur detected in the specific granules of the heterophil probably derives from proteins or polypeptides incorporating sulfur containing amino acids.     

Effect of different forms of nitrogen in the biosynthesis of gentamicin by a Micromonospora purpurea var. violacea 1935 culture]

The effect of different inorganic sources of reduced and oxidized nitrogen on biosynthesis of gentamicin was studied. It was shown that both the ammonium and the nitrate nitrogen were consumed by the antibiotic-producing organism. Out of all the salts tested only ammonium sulfate stimulated the biosynthesis of gentamicin. The positive role of this salt was due to both the ammonium and the sulfogroup, since the presence of the sulfogroup alone in sodium sulfat, magnesium or sulfuric acid resulted only in partial stimulation of gentamicin biosynthesis. Simultaneous addition of sulfuric acid ammonium nitrate which suppressed the antibiotic biosynthesis when used alone was equal to introduction of ammonium sulfate.     

ON THE GROWTH AND RESPIRATION OF SULFUR-OXIDIZING BACTERIA

1. It is shown that Sulfomonas thiooxidans oxidizes elementary sulfur completely to sulfuric acid. Sodium thiosulfate is oxidized by this organism completely to sulfate. Sulfomonas thiooxidans differs, in this respect, from various other sulfur-oxidizing bacilli which either produce elementary sulfur, from the thiosulfate, or convert it into sulfates and persulfates. 2. The organism derives its carbon from the CO₂ of the atmosphere, but is incapable of deriving the carbon from carbonates or organic matter. 3. The S:C, or ratio between the amount of sulfur oxidized to sulfate and amount of carbon assimilated chemosynthetically from the CO₂ of the atmosphere, is, with elementary sulfur as a source of energy, 31.8, and with thiosulfate 64.2. The higher ratio in the case of the thiosulfate is due to the smaller amount of energy liberated in the oxidation of sulfur compound than in the elementary form. 4. Of the total energy made available in the oxidation of the sulfur to sulfuric acid, only 6.65 per cent is used by the organism for the reduction of atmospheric CO₂ and assimilation of carbon. 5. Sulfates do not exert any injurious effect upon sulfur oxidation by Sulfomonas thiooxidans. Any effect obtained is due to the cation rather than the sulfate radical. Nitrates exert a distinctly injurious action both on the growth and respiration of the organism. 6. There is a definite correlation between the amount of sulfur present and velocity of oxidation, very similar to that found in the growth of yeasts and nitrifying bacteria. Oxidation reaches a maximum with about 25 gm. of sulfur added to 100 cc. of medium. However, larger amounts of sulfur have no injurious effect. 7. Dextrose does not exert any appreciable injurious effect in concentrations less than 5 per cent. The injurious effect of peptone sets in at 0.1 per cent concentration and brings sulfur oxidation almost to a standstill in 1 per cent concentration. Dextrose does not exert any appreciable influence upon sulfur oxidation and carbon assimilation from the carbon dioxide of the atmosphere. 8. Sulfomonas thiooxidans can withstand large concentrations of sulfuric acid. The oxidation of sulfur is affected only to a small extent even by 0.25 molar initial concentration of the acid. In 0.5 molar solutions, the injurious effect becomes marked. The organism may produce as much as 1.5 molar acid, without being destroyed. 9. Growth is at an optimum at a hydrogen ion concentration equivalent to pH 2.0 to 5.5, dropping down rapidly on the alkaline side, but not to such an extent on the acid, particularly when a pure culture is employed. 10. Respiration of the sulfur-oxidizing bacteria can be studied by using the filtrate of a vigorously growing culture, to which a definite amount of sulfur is added, and incubating for 12 to 24 hours.     

Microbial Synthesis of Nanoparticles: Mechanisms,Characteristics, and Applications

Cadmium sulfide (CdS) and zinc sulfide (ZnS) biogenic nanoparticles (NPs) were produced by microbial synthesis using bacteria of different taxonomic groups: Gram-negative (Shewanella oneidensis MR-1) and Gram-positive (Bacillus subtilis 168) bacteria in a liquid medium under aerobic conditions in the presence of salts of the respective metals and sulfur. It was shown that the stabilization of nanoparticles in aqueous suspensions is due to the presence of certain protein molecules of the outer membrane of cells, that is, proteins of the families of various receptors, porins, and flagellin, on the nanoparticle (NP) surface. The effect of the protein coating on stability, luminescence, zeta-potential, hydrodynamics diameter and other physiochemical characteristics of nanoparticles was studied. Decolorization of methylene blue dye under the exposure to UV irradiation was used as a model to demonstrate the photocatalytic properties of NPsCdS. This opens the possibility of using biogenic nanoparticles in photocatalysis for industrial wastewater treatment.

     

PRODUCTS OF THE OXIDATION OF THIOSULFATE BY BACTERIA IN MINERAL MEDIA

Various cultures (previously described), which oxidize thiosulfate in mineral media have been studied in an attempt to determine the products of oxidation. The transformation of sodium thiosulfate by Cultures B, T, and K yields sodium tetrathionate and sodium hydroxide; secondary chemical reactions result in the accumulation of some tri- and pentathionates, sulfate, and elemental sulfur. As a result of the initial reaction, the pH increases; the secondary reactions cause a drop in pH after this initial rise. The primary reaction yields much less energy than the reactions effected by autotrophic bacteria. No significant amounts of assimilated organic carbon were detected in media supporting representatives of these cultures. It is concluded that they are heterotrophic bacteria. Th. novellus oxidizes sodium thiosulfate to sodium sulfate and sulfuric acid; the pH drops progressively with growth and oxidation. Carbon assimilation typical of autotrophic bacteria was detected; the ratio of sulfate-sulfur formed to carbon assimilated was 56:1. It is calculated that 5.1 per cent of the energy yielded by the oxidation of thiosulfate is accounted for in the organic cell substance synthesized from inorganic materials. This organism is a facultative autotroph. The products of oxidation of sodium thiosulfate by Th. thioparus are sodium sulfate, sulfuric acid, and elemental sulfur; the ratio of sulfate sulfur to elemental sulfur is 3 to 2. The pH decreases during growth and oxidation. The elemental sulfur is produced by the primary reaction and is not a product of secondary chemical changes. The bacterium synthesizes organic compounds from mineral substances during growth. The ratio of thiosulfate-sulfur oxidized to carbon assimilated was 125:1, with 4.7 per cent of the energy of oxidation recovered as organic cell substance. This bacterium is a strict autotroph.     

Accelerated biodegradation of cured cement paste by Thiobacillus species under simulation condition

Biodegradation is one of the most important types of cement deterioration. Complex microbial populations take part in the biodegradation process of cement-based materials. Studies in this field show that the sulfur-oxidizing bacteria, including Acidithiobacillus thiooxidans, due to sulfuric acid formation, play a key role in this process. In this study, with the accelerated leaching process of calcium hydroxide of cement paste, cured under running tap water and exposed to sterile biogenic sulfuric acid for 6 days, the surface pH of the cement was reduced to a more favorable level for bacterial growth. In this case, the growth of Thiobacillus proceeded in the presence of cured cement paste specimens. After 90 days of exposure to a semi-continuous culture of A. thiooxidans with its pH less than 2 and continuous removal of damaged layers the compressive strength, length and mass of the samples dropped by 96%, 11% and 43%, in the order given. The mechanism of degradation and the structure of degraded specimens were analyzed by test laboratory techniques such as, XRD, SEM and EDAX analyses.     

A simple method for the synthesis of benzyl 4-O-benzylhexopyranosides

The kinetics of hydrolysis in dilute sulfuric acid of xylo-oligosaccharides ranging between the di- and penta-oligosaccharides has been studied. One of the two terminal bonds and each internal bond of all xylo-oligosaccharides tested were hydrolysed at the same rate. The hydrolytic rate of the other terminal bond was the same as that of xylobiose, which was 1.8 times greater than that of an internal bond. The rates of hydrolysis of xylo-oligosaccharides have been described as functions of the reaction temperature and concentration of sulfuric acid. It has been shown that the yield of xylose in hydrolysis of xylo-oligosaccharides by sulfuric acid may be calculated from the ratio ( 1.8) of the rate for xylobiose to that of an internal bond and the empirical equation that describes the rate-constant for xylobiose.     

Microbial metabolism of methanesulfonic acid

Methanesulfonic acid is a very stable strong acid and a key intermediate in the biogeochemical cycling of sulfur. It is formed in megatonne quantities in the atmosphere from the chemical oxidation of atmospheric dimethyl sulfide (most of which is of biogenic origin) and deposited on the Earth in rain and snow, and by dry deposition. Methanesulfonate is used by diverse aerobic bacteria as a source of sulfur for growth, but is not known to be used by anaerobes either as a sulfur source, a fermentation substrate, an electron acceptor, or as a methanogenic substrate. Some specialized methylotrophs (including Methylosulfonomonas, Marinosulfonomonas, and strains of paragraph signHyphomicrobium and Methylobacterium) can use it as a carbon and energy substrate to support growth. Methanesulfonate oxidation is initiated by cleavage catalysed by methanesulfonate monooxygenase, the properties and molecular biology of which are discussed.     

Biodeterioration of mineral materials by microorganisms—biogenic sulfuric and nitric acid corrosion of concrete and natural stone

In general, microorganisms such as chemolithotrophic and chemo‐organotrophic bacteria, cyanohacteria, algae, fungi, and lichens living on and in stone material may be of importance in biodeterioration. These groups contribute substantially to the deterioration of mineral materials such as natural stone, concrete, ceramics, and glass. The attack on mineral materials may be either strongly or mildly aggressive or both. A strongly aggressive attack is caused by biogenic mineral or organic acids. A mildly aggressive attack results from hydrophilic slimes such as heteropolysaccharides and/or proteins (biofilm) and their ability to accumulate water and salts. Attack by exoenzymes seems to be unimportant.

In recent years it has become possible to test the resistance of mineral materials to microbial attack by means of a biotest. Three simulation apparatuses were constructed; each allowed the incubation of test materials under microbiologically optimized conditions. Biodeterioration involving biogenic sulfuric acid corrosion, which under natural conditions needs eight times as long, was detectable within a few months. The results differed from those of purely chemical and/or physical tests of materials. Physical/chemical test methods are not sufficient to determine the resistance of materials to biological attack, because they do not include the interactions between microorganisms and their substrate, the mineral material. In the case of biogenic sulfuric acid corrosion, simulation experiments demonstrated differences in resistance of various concrete types, which ranged from I to 20% weight loss of test blocks within I year. With chemical testing only negligible differences in weight loss were noted. This was also the case with biogenic nitric acid corrosion. Thus, biotests assist in the selection of appropriate materials from many different ones.     

Involvement of Sulfur- and Iron-Transforming Bacteria in Heaving of House Foundations

About 1,000 houses built on excavated nonweathered mudstone sediments, originally deposited in the Neogene, have been damaged by microbially induced heaving of foundations. The maximal height of the heaving was 48 cm. The presence of sulfate-reducing, sulfur-oxidizing, and acidophilic iron-oxidizing bacteria in the mudstone indicated that the joint activity of these three types of bacteria could account for the heaving. A hypothesis is presented in which, first, the temperature of the newly exposed mudstone sediments increased above 25 °C, which stimulated the sulfate-reducing bacteria in the mudstone to actively reduce sulfate to hydrogen sulfide. The mudstone sediments under the houses gradually dried, and became permeable to air. Consequently, sulfur-oxidizing bacteria oxidized the hydrogen sulfide to sulfuric acid and the environmental pH decreased to approximately 3. Next, the acidophilic iron-oxidizing bacteria actively oxidized the sulfur in pyrite to produce much more acid. The resulting sulfuric acid reacted with calcium carbonate and with ferric and potassium ions to produce gypsum and jarosite, respectively. A combination of the increased volume of gypsum and jarosite crystals and the production of CO 2 as a by-product of their formation made the mudstone sediments bulky. The end result was widespread heaving.     

Acetylation of glycerol to biofuel additives over sulfated activated carbon catalyst

Oxygenated fuel additives can be produced by acetylation of glycerol. A 91% glycerol conversion with a selectivity of 38%, 28% and 34% for mono-, di- and triacetyl glyceride, respectively, was achieved at 120 °C and 3 h of reaction time in the presence of a catalyst derived from activated carbon (AC) treated with sulfuric acid at 85 °C for 4h to introduce acidic functionalities to its surface. The unique catalytic activity of the catalyst, AC-SA5, was attributed to the presence of sulfur containing functional groups on the AC surface, which enhanced the surface interaction between the glycerol molecule and acyl group of the acetic acid. The catalyst was reused in up to four consecutive batch runs and no significant decline of its initial activity was observed. The conversion and selectivity variation during the acetylation is attributed to the reaction time, reaction temperature, catalyst loading and glycerol to acetic acid molar ratio.     

Increased bioclogging and corrosion risk by sulfate addition during iodine recovery at a natural gas production plant

Iodine recovery at a natural gas production plant in Japan involved the addition of sulfuric acid for pH adjustment, resulting in an additional about 200 mg/L of sulfate in the waste brine after iodine recovery. Bioclogging occurred at the waste brine injection well, causing a decrease in well injectivity. To examine the factors that contribute to bioclogging, an on-site experiment was conducted by amending 10 L of brine with different conditions and then incubating the brine for 5 months under open air. The control case was exposed to open air but did not receive additional chemicals. When sulfate addition was coupled with low iodine, there was a drastic increase in the total amount of accumulated biomass (and subsequently the risk of bioclogging) that was nearly six times higher than the control. The bioclogging-associated corrosion rate of carbon steel was 84.5 μm/year, which is four times higher than that observed under other conditions. Analysis of the microbial communities by denaturing gradient gel electrophoresis revealed that the additional sulfate established a sulfur cycle and induced the growth of phototrophic bacteria, including cyanobacteria and purple bacteria. In the presence of sulfate and low iodine levels, cyanobacteria and purple bacteria bloomed, and the accumulation of abundant biomass may have created a more conducive environment for anaerobic sulfate-reducing bacteria. It is believed that the higher corrosion rate was caused by a differential aeration cell that was established by the heterogeneous distribution of the biomass that covered the surface of the test coupons.     

An “ex situ” microbial process for the removal of heavy metals from polluted soil: A case study of Ada rice field,Adani, Enugu State,Nigeria

An “ex situ” microbial method for the removal of heavy metals from soil is described. Elemental sulfur was added to generate the lixiviant in shaker flask experiments in which soil sampled from a polluted agricultural field was treated. The biotic oxidation of sulfur to sulfuric acid resulted in significant drop in pH of the bioleaching liquor from 6.94 to 1.8 after 50 days. In batches operated at very low (10 g/kg) sulfur concentrations, pH changed from 6.94 to 5.45. The 50 g/kg soil sulfur concentration was found to be most beneficial to the solubilization process because more than 95% of metals such as zinc (Zn), cadmium (Cd), and nickel (Ni) were recovered while approximately 67% of manganese (Mn) got solubilized. The least concentration of dissolved metals was lead (Pb) – (25%) and chromium (Cr) – (10%). Sulfate accumulation rose to 47% in samples spiked with 50 g/kg soil of sulfur. At lower sulfur concentrations, the sulfates generated were higher than the amount of sulfur added. The microbial process compared well to the abiotic process involving extraneous addition of sulfuric acid except that very high concentrations of acid had to be used. The treatment of the bioleaching wastewater promoted precipitation of the dissolved metals into insoluble hydroxides making discharge of the effluent into the environment safe. The leached soil recovered sufficiently for agricultural use after quick lime and animal manure was used to improve, stabilize, and restore its physical, chemical, and biological conditions.     

Microbial corrosion monitoring by an amperometric microbial biosensor developed using whole cell of Pseudomonas sp.

A microbial biosensor was developed for monitoring microbiologically influenced corrosion (MIC) of metallic materials in industrial systems. The Pseudomonas sp. isolated from corroded metal surface was immobilized on acetylcellulose membrane and its respiratory activity was estimated by measuring oxygen consumption. The microbial biosensor was used for the measurement of sulfuric acid in a batch culture medium contaminated by microorganisms. A linear relationship between the microbial sensor response and the concentration of sulfuric acid was observed. The response time of biosensor was 5 min and was dependent on the immobilized cell loading of Pseudomonas sp., pH, temperature and corrosive environments. The microbial biosensor response was stable, reproducible and specific for sensing of sulfur oxidizing bacterial activity.     

Oxidation of Elemental Sulfur by Sulfolobus acidocaldarius

Oxidation of elemental sulfur by Sulfolobus acidocaldarius, an autotroph which grows at high temperatures and low pH, was examined by use of (35)S-labeled elemental sulfur. When cultured at pH 3.2 and 70 C, S. acidocaldarius oxidized elemental sulfur essentially quantitatively to sulfuric acid. Oxidation rate paralleled growth rate and decrease in pH of the culture medium. Elemental sulfur was not oxidized under these conditions if the culture was poisoned with formaldehyde. During the growth phase, the proportion of cells attached to the sulfur crystals increased progressively, and in the later phases of growth over 10 times more cells were attached to sulfur than were free. Doubling times for eight strains growing on elemental sulfur varied from 37 to 55 h. The organism grows much more rapidly on yeast extract than on sulfur. In a medium containing both sulfur and yeast extract, sulfur oxidation was partially inhibited, although growth was excellent.