The influence of sunlight on the localized corrosion of UNS S31600 in natural seawater

Tests were conducted on the performance of UNS S31600 stainless steel (SS) in a natural day/night cycle vs full darkness under conditions of natural marine biofilm accumulation. In quiescent flowing seawater tests in the laboratory as well as under natural immersion in the sea, diffuse sunlight (～10% of natural) counteracted the influence of marine biofilms and produced substantial inhibition of the corrosion of SS. Thus, the probabilities (percentage attack) and propagation rates (depths of attack) in multiple crevice tests were substantially lower in the day/night cycle than in the dark. A benefit was also observed for welded SS in terms of the time to corrosion initiation and the mass loss. SS in the passive state showed broader passive regions, well-defined breakdown potentials and markedly smaller anodic and cathodic current densities under the diurnal cycle. The overall reduction in corrosion is attributed to a combination of electrochemical photoinhibition and simultaneous photoinactivation of microbially mediated metal redox reactions linked to cathodic kinetics. These data offer fresh insights into the behaviour of SS under practical seawater situations and the proposed potential use of illumination in the mitigation of biologically influenced consequences.     

Stainless steel in coastal seawater: sunlight counteracts biologically enhanced cathodic kinetics

The influence of sunlight of varying intensity on the performance of UNS S30400 stainless steel (SS) was explored under conditions of natural biofilm development in coastal seawater. In a series of tests performed outdoors under an opaque roof, a range of shades were fashioned to impart varied amounts of diurnal light. These were an ambient level where the underwater illumination was ~ 5% of full sunlight, two intermediate ranges of lighting with ~ 2.5% and ~ 1% of the daylight, and a condition of full darkness. In comparison with the dark, increments of sunlight rendered the SS progressively less aggressive as cathodes in galvanic couples with UNS C70600 alloy. Likewise, welded SS with pre-initiated localized corrosion sites exhibited substantially lower rates of propagation with light. Thus, biofilms and sunlight affected cathodic kinetics in opposite ways. Surface analytical tests showed that the accumulation of manganese (Mn) within the biofilms was small relative to reports from waters of lower salinity. These results not only reveal that extremely low amounts of sunlight are adequate to offset the microbial effect, but also highlight the lack of convincing evidence for Mn cycling as a potent mechanism for enhanced cathodic kinetics in full-strength seawater.     

Cathodic protection and microbially induced corrosion

Cathodic protection, using sacrificial anodes or impressed current, has been recognized for a long time as an effective way to prevent marine corrosion. Cathodic polarization leads to the formation of a protective calcareous layer on the surfaces. It is well documented that the attachment of bacteria to metal surfaces and subsequent biofilm formation changes some physical and chemical parameters at the interface and influences the corrosion process. The objective of this study was to determine whether there is a relationship between cathodic polarization and development of biofilms on surfaces exposed to both synthetic and natural seawater. Experiments were conducted on clean surfaces, biofilmed surfaces, in natural or synthetic seawater using bacterial monocultures and cocultures. In marine sediments, cathodically produced hydrogen encouraged growth of hydrogenase-containing sulphate-reducing bacteria while in aerated seawater biofilms competed with the magnesium and calcium deposition. Both low pH induced by bacterial metabolism and exopolymers affect the deposition process and the stability of the calcareous layer.     

Environmental fate of sacrificial zinc anodes and influence of a biofilm

Laboratory experiments were performed to determine the environmental fate of zinc compounds formed during sacrificial dissolution of zinc anodes in seawater and to further determine the role of biofilms in mobilizing/immobilizing zinc corrosion products. Experimental conditions simulated cathodic protection and overprotection (40x normal) of ship ballast tanks with an anode to cathode ratio of 0.091. Anodic dissolution and percentage of soluble zinc increased with the level of protection. For normal cathodic protection in abiotic seawater, approximately 3% of the sacrificed zinc was dissolved in solution. Additionally, weight loss and percent soluble products increased dramatically in the presence of an agar film, but were unchanged due to the presence of natural marine biofilms. Under overprotection conditions, weight loss did not vary in the presence of surface films. Solid zinc corrosion products were precipitated, suspended in solution, and attached to electrode surfaces. Experimental data were compared with zinc concentrations measured in ballast tanks for two United States Navy surface ships.     

Effect of W–TiO2 composite to control microbiologically influenced corrosion on galvanized steel

Microorganisms tend to colonize on solid metal/alloy surface in natural environment leading to loss of utility. Microbiologically influenced corrosion or biocorrosion usually increases the corrosion rate of steel articles due to the presence of bacteria that accelerates the anodic and/or cathodic corrosion reaction rate without any significant change in the corrosion mechanism. An attempt was made in the present study to protect hot-dip galvanized steel from such attack of biocorrosion by means of chemically modifying the zinc coating. W–TiO₂ composite was synthesized and incorporated into the zinc bath during the hot-dipping process. The surface morphology and elemental composition of the hot-dip galvanized coupons were analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The antifouling characteristics of the coatings were analyzed in three different solutions including distilled water, seawater, and seawater containing biofilm scrapings under immersed conditions. Apart from electrochemical studies, the biocidal effect of the composite was evaluated by analyzing the extent of bacterial growth due to the presence and absence of the composite based on the analysis of total extracellular polymeric substance and total biomass using microtiter plate assay. The biofilm-forming bacteria formed on the surface of the coatings was cultured on Zobell Marine Agar plates and studied. The composite was found to be effective in controlling the growth of bacteria and formation of biofilm thereafter.     

深红红螺菌吸氢酶缺失突变株在管式光合反应器中的产氢

本研究设计了一种2 L分体式管式光合反应器, 并研究了深红红螺菌(Rhodospirillum rubrum)吸氢酶缺失突变株在该反应器中分别利用人工光源(持续光照与光暗交替)和自然光的产氢规律。结果表明在人工光照条件下R. rubrum的产氢可维持5 d, 持续光照和光暗交替条件下(12 h: 12 h)的氢产量可分别达到5752 mL/PBR ± 158 mL/PBR和5012 mL/PBR ± 202 mL/PBR; 自然光条件下, 最适产氢光照强度为30000 Lux~40000 Lux; 在此光照条件下, R. rubrum产氢可维持6 d~ 10 d, 最高氢产量可达到2800 mL/PBR。尽管利用自然光的氢产量比利用人工光源氢产量低, 但是利用自然光的产氢比较经济, 并且该光合产氢系统操作简单, 该工艺有望开发为低成本的光合细菌产氢技术。     

Cathodic behaviour of stainless steel in coastal Indian seawater: calcareous deposits overwhelm biofilms

Type-316 stainless steel (SS) was investigated as the cathode in galvanic couples in full-strength seawater from the Gulf of Mannar on the southeast coast of India. Tests were devised to examine the impact of SS cathodes on anode materials with or without the accrual of marine biofilms. Biofilmed SS cathodes significantly enhanced the rate of corrosion of nickel, causing noble shifts in the couple potentials. With mild steel and zinc as the anodes, calcareous deposits developed quite rapidly on the SS cathodes and led to a significant reduction of bacterial numbers. The calcareous deposits also caused substantial reduction of galvanic corrosion rates for mild steel, whereas there was no difference for zinc. The deposits were identified by XRD as essentially carbonates, oxides and hydroxides of calcium and magnesium. Potentiodynamic polarization performed on the actual couples after disconnection and equilibration provided reasonable interpretations of the galvanic corrosion trends. Data from this work suggest that a potential of about ?0.70 V vs. saturated calomel electrode (SCE) should provide optimum protection of SS in warmer, full-strength seawater that supports the precipitation of calcareous deposits. The criterion commonly recommended for temperate conditions of lower water temperature and estuarine waters of lower alkalinity is ?1.0 V (SCE).     

Studies on microbiologically influenced corrosion of SS304 by a novel manganese oxidizer, Bacillus flexus

A manganese oxidizing bacterium was isolated from the surface of steel scraps and biochemical tests and 16S rRNA sequencing analysis confirmed the isolate as Bacillus flexus. Potentiodynamic polarization curves showed ennoblement of open circuit potential, increased passive current, a lowering of breakdown potential, active re-passivation potential and enhanced cathodic current in the presence of B. flexus. Adhesion studies with B. flexus on SS304 specimens with different surface treatments demonstrated decreased adhesion on passivated and FeCl(3) treated specimens due to the removal of MnS inclusions. The present study provides evidence that surface treatment of stainless steels can reduce adhesion of this manganese oxidizing bacterium and decrease the probability of microbiologically influenced corrosion.     

Direct Electrolytic Splitting of Seawater: Activity,Selectivity, Degradation,and Recovery Studied from the Molecular Catalyst Structure to the Electrolyzer Cell Level

Seawater electrolysis faces fundamental chemical challenges, such as the suppression of highly detrimental halogen chemistries, which has to be ensured by selective catalyst and suitable operating conditions. In the present study, nanostructured NiFe‐layered double hydroxide and Pt nanoparticles are selected as catalysts for the anode and cathode, respectively. The seawater electrolyzer is tested successfully for 100 h at maximum current densities of 200 mA cm^?2 at 1.6 V employing surrogate sea water and compared to fresh water feeds. Different membrane studies are carried out to reveal the cause of the current density drop. During long‐term dynamic tests, under simulated day‐night cycles, an unusual cell power performance recovery effect is uncovered, which is subsequently harnessed in a long‐term diurnal day‐night cycle test. The natural day‐night cycles of the electrolyzer input power can be conceived as a reversible catalyst materials recovery treatment of the device when using photovoltaic electricity sources. To understand the origin of this reversible recovery on a molecular materials level, in situ extended X‐ray absorption fine structure and X‐ray near‐edge region spectra are applied.     

Daily Oscillation of Fatty Acids and Malondialdehyde in the Dinoflagellate Lingulodinium polyedrum

The levels of the fatty acids, cis eicosahexenoic acid and cis linolenic acid, as well as the extent of lipoperoxidation, measured as malondialdehyde (MDA), were analyzed in the photosynthetic marine dinoflagellate Lingulodinium polyedrum at different times during the light : dark (L : D) cycle. Levels of MDA were twice as high during the day phase than during the night phase. This may be related to the circadian rhythm in photosynthesis as during photosynthetic electron flux, electrons can 'leak' and react with molecular oxygen producing reactive oxygen species (ROS) which in turn react with lipids, proteins, and DNA among other biomolecules. Fatty acid levels were highest during the day phase. Our findings indicate that unsaturated fatty acids are more susceptible to attack and degradation when L. polyedrum is exposed to light and that the cells compensate for this by an increased fatty acid content during the day. Excessive lipoperoxidation during the light phase could result in a higher level of chloroplast or plasma membrane disruption leading to cell death.     

Sulphide production and corrosion in seawaters during exposure to FAME diesel

Experiments were designed to evaluate the corrosion-related consequences of storing/transporting fatty acid methyl ester (FAME) alternative diesel fuel in contact with natural seawater. Coastal Key West, FL (KW), and Persian Gulf (PG) seawaters, representing an oligotrophic and a more organic- and inorganic mineral-rich environment, respectively, were used in 60 day incubations with unprotected carbon steel. The original microflora of the two seawaters were similar with respect to major taxonomic groups but with markedly different species. After exposure to FAME diesel, the microflora of the waters changed substantially, with Clostridiales (Firmicutes) becoming dominant in both. Despite low numbers of sulphate-reducing bacteria in the original waters and after FAME diesel exposure, sulphide levels and corrosion increased markedly due to microbial sulphide production. Corrosion morphology was in the form of isolated pits surrounded by an intact, passive surface with the deepest pits associated with the fuel/seawater interface in the KW exposure. In the presence of FAME diesel, the highest corrosion rates measured by linear polarization occurred in the KW exposure correlating with significantly higher concentrations of sulphur and chlorine (presumed sulphide and chloride, respectively) in the corrosion products.     

Manganese biofouling and the corrosion behavior of stainless steel

Manganese- and iron-oxidizing bacteria (MFOB) are widely implicated in microbially influenced corrosion, often in association with sulfate-reducing bacteria (SRB). Traditionally MFOB have been assigned a passive role in the corrosion process, promoting differential aeration cells, and providing oxygen depleted conditions conducive to the growth and corrosive attack of SRB. Recent work, summarized in this article, demonstrates that manganese biofouling alters the electrochemical behavior of stainless steel (SS), and suggests that MFOB are more active in localized corrosion than traditionally held. The paper discusses the chemistry and potentially corrosive impact of manganese and iron oxides on SS, explores the possible relationship between MFOB and SRB, and proposes a model to describe the synergistic influence these organisms may exert in the corrosion process.     

Biofilms and corrosion interactions on stainless steel in seawater

Biofouling and biocorrosion lead to an important modification of the metal/ solution interface inducing changes in the type and concentration of ions, pH values, oxygen levels, flow velocity, etc. Metal dissolution in seawater is mainly conditioned by two different processes: (a) biofouling settlement and (b) corrosion products formation.Corrosion-resistant alloys such as stainless steel present an ideal substratum for microbial colonization, rather similar to inert non-metallic surfaces, due to the lack of corrosion products. Stainless steels are sensitive to pitting and other types of localized corrosion in chloride-containing media such as seawater. Biofilms and bacterial metabolism may accelerate the initiation of crevice attack by depletion of oxygen in the crevice solution due to microbial respiration. Bacterial colonization occurs within a period of 24–72 h on stainless steel samples exposed to natural seawater and, depending on environmental conditions, a copious and patchy biofilm is generally formed.Different interpretations of biofilms' effects on corrosion are critically discussed. A practical case, involving polluted harbour seawater, is reported to illustrate biofilm and corrosion interactions on stainless steel samples.     

Influence of cathodic protection of mild steel on the growth of sulphate‐reducing bacteria at 35°C in marine sediments

In order to protect metallic structures from marine corrosion, cathodic protection using sacrificial anodes or impressed current is widely used. In aerated seawater steel is considered to be protected when a cathodic potential of — 800 mV/SCE (Saturated Calomel Electrode) is applied. However, in many cases, this potential must be lowered due to the presence and activity of microorganisms such as acid‐producing bacteria or sulphate‐reducing bacteria (SRB). SRB are obligate anaerobes using sulphate as an electron acceptor with resultant production of sulfides. Some SRB are able to use hydrogen as an electron donor causing thereby depolarization of steel surfaces.

An experiment was performed in marine sediments to determine the relationship between cathodically produced hydrogen and growth of SRB in marine sediments both at ambiant temperature (Therene, 1988) and at 35°C. Results concerning the latter experiments are reported here.

Analytical techniques included microbiological analyses, lipid biomarker studies and electrochemical measurements including AC impedance spectroscopy. Results indicated a change in the bacterial community structure both on the steel and sediment as a function of time and potential. The results also showed that cathodically‐produced hydrogen promoted the growth of SRB with the Desulfovibrio genus predominating.     

Studies on microbiologically influenced corrosion of SS304 by a novel manganese oxidizer,Bacillus flexus

A manganese oxidizing bacterium was isolated from the surface of steel scraps and biochemical tests and 16S rRNA sequencing analysis confirmed the isolate as Bacillus flexus. Potentiodynamic polarization curves showed ennoblement of open circuit potential, increased passive current, a lowering of breakdown potential, active re-passivation potential and enhanced cathodic current in the presence of B. flexus. Adhesion studies with B. flexus on SS304 specimens with different surface treatments demonstrated decreased adhesion on passivated and FeCl₃ treated specimens due to the removal of MnS inclusions. The present study provides evidence that surface treatment of stainless steels can reduce adhesion of this manganese oxidizing bacterium and decrease the probability of microbiologically influenced corrosion.     

Identification of key factors in Accelerated Low Water Corrosion through experimental simulation of tidal conditions: influence of stimulated indigenous microbiota

Biotic and abiotic factors favoring Accelerated Low Water Corrosion (ALWC) on harbor steel structures remain unclear warranting their study under controlled experimental tidal conditions. Initial stimulation of marine microbial consortia by a pulse of organic matter resulted in localized corrosion and the highest corrosion rates (up to 12-times higher than non-stimulated conditions) in the low water zone, persisting after nine months exposure to natural seawater. Correlations between corrosion severity and the abundance and composition of metabolically active sulfate-reducing bacteria (SRB) indicated the importance and persistence of specific bacterial populations in accelerated corrosion. One phylotype related to the electrogenic SRB Desulfopila corrodens appeared as the major causative agent of the accelerated corrosion. The similarity of bacterial populations related to sulfur and iron cycles, mineral and tuberculation with those identified in ALWC support the relevance of experimental simulation of tidal conditions in the management of steel corrosion exposed to harbor environments.     

Bacterial corrosion of iron in seawater in situ, and in aerobic and anaerobic model systems

Abstract A screening of twenty-two marine isolates was made to examine their effects on corrosion of carbon steel ASTM A619. In batch cultures, sixteen of the isolates gave a lower corrosion than the control. Aerobic and anaerobic biofilm populations were formed by immersing iron coupons in natural seawater under aerobic and anaerobic conditions. The effects of the biofilms depended on a balance between the presence of oxygen and the type of population. An anaerobic population attached to the surface increased the corrosion rate if immersed in a suspension of Vibrio sp. DW1. The vibrio population probably 'protected' the anaerobic population from oxygen and may have provided nutrients, thereby creating conditions that allowed production of corrosive metabolites close to the metal. In contrast, coupons without a biofilm showed a decrease in the corrosion when immersed in the same vibrio suspension. The protective effect of a dense suspension of bacteria found earlier [5,6] was tested in situ in seawater. Iron coupons were immersed in dialysis bags with a suspension of Vibrio sp. DW1. Coupons immersed in dialysis bags with DW1 showed a lower degree of corrosion than coupons immersed in bags with seawater.     

Persistent infectivity of a disease-associated herpesvirus in green turtles after exposure to seawater

Herpesviruses are associated with several diseases of marine turtles including lung-eye-trachea disease (LETD) and gray patch disease (GPD) of green turtles (Chelonia mydas) and fibropapillomatosis (FP) of green, loggerhead (Caretta caretta), and olive ridley turtles (Lepidochelys olivacea). The stability of chelonian herpesviruses in the marine environment, which may influence transmission, has not been previously studied. In these experiments, LETD-associated herpesvirus (LETV) was used as a model chelonian herpesvirus to test viral infectivity after exposure to seawater. The LETV virus preparations grown in terrapene heart (TH-1) cells were dialyzed for 24 to 120 hr against aerated artificial or natural seawater or Hank's balanced salt solution (HBBS). Fresh TH-1 cells were inoculated with dialyzed LETV, and on day 10 post-infection cells were scored for cytopathic effect. Virus samples dialyzed up to 120 hr were positive for the herpesvirus DNA polymerase gene by polymerase chain reaction. Electron microscopy revealed intact LETV nucleocapsids after exposure of LETV to artificial seawater or HBSS for 24 hr at 23 C. LETV preparations remained infectious as long as 120 hr in natural and artificial seawater at 23 C. Similar results were obtained with a second culturable chelonian herpesvirus, HV2245. LETV infectivity could not be detected after 48 hr exposure to artificial seawater at 30 C. Since LETV and HV2245 remain infectious for extended periods of time in the marine environment, it is possible that FP-associated and GPD-associated herpesviruses also may be stable. These findings are significant both for researchers studying the epidemiological association of herpesviruses with diseases of marine turtles and for individuals who handle turtles in marine turtle conservation efforts.     

Sulphide production and corrosion in seawaters during exposure to FAME diesel

Experiments were designed to evaluate the corrosion-related consequences of storing/transporting fatty acid methyl ester (FAME) alternative diesel fuel in contact with natural seawater. Coastal Key West, FL (KW), and Persian Gulf (PG) seawaters, representing an oligotrophic and a more organic- and inorganic mineral-rich environment, respectively, were used in 60?day incubations with unprotected carbon steel. The original microflora of the two seawaters were similar with respect to major taxonomic groups but with markedly different species. After exposure to FAME diesel, the microflora of the waters changed substantially, with Clostridiales (Firmicutes) becoming dominant in both. Despite low numbers of sulphate-reducing bacteria in the original waters and after FAME diesel exposure, sulphide levels and corrosion increased markedly due to microbial sulphide production. Corrosion morphology was in the form of isolated pits surrounded by an intact, passive surface with the deepest pits associated with the fuel/seawater interface in the KW exposure. In the presence of FAME diesel, the highest corrosion rates measured by linear polarization occurred in the KW exposure correlating with significantly higher concentrations of sulphur and chlorine (presumed sulphide and chloride, respectively) in the corrosion products.     

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.