Testing the Test: A Comparative Study of Marine Microbial Corrosion under Laboratory and Field Conditions.

Microbially influenced corrosion (MIC) is an aggressive type of corrosion that occurs in aquatic environments and is sparked by the development of a complex biological matrix over a metal surface. In marine environments, MIC is exacerbated by the frequent variability in environmental conditions and the typically high diversity of microbial communities; hence, local and in situ studies are crucial to improve our understanding of biofilm composition, biological interactions among its members, MIC characteristics, and corrosivity. Typically, material performance and anticorrosion strategies are evaluated under controlled laboratory conditions, where natural fluctuations and gradients (e.g., light, temperature, and microbial composition) are not effectively replicated. To determine whether MIC development and material deterioration observed in the laboratory are comparable to those that occur under service conditions (i.e., field conditions), we used two testing setups, in the lab and in the field. Stainless steel (SS) AISI 316L coupons were exposed to southeastern Pacific seawater for 70 days using (i) acrylic tanks in a running seawater laboratory and (ii) an offshore mooring system with experimental frames immersed at two depths (5 and 15 m). Results of electrochemical evaluation, together with those of microbial community analyses and micrographs of formed biofilms, demonstrated that the laboratory setup provides critical information on the early biofilm development process (days), but the information gathered does not predict deterioration or biofouling of SS surfaces exposed to natural conditions in the field. Our results highlight the need to conduct further research efforts to understand how laboratory experiments may better reproduce field conditions where applications are to be deployed, as well as to improve our understanding of the role of eukaryotes and the flux of nutrients and oxygen in marine MIC events.

Electrochemical Bacterial Enrichment from Natural Seawater and Its Implications in Biocorrosion of Stainless-Steel Electrodes.

Microbial electrochemical technologies have revealed the opportunity of electrochemical enrichment for specific bacterial groups that are able to catalyze reactions of interest. However, there are unsolved challenges towards their application under aggressive environmental conditions, such as in the sea. This study demonstrates the impact of surface electrochemical potential on community composition and its corrosivity. Electrochemical bacterial enrichment was successfully carried out in natural seawater without nutrient amendments. Experiments were carried out for ten days of exposure in a closed-flow system over 316L stainless steel electrodes under three different poised potentials (-150 mV, +100 mV, and +310 mV vs. Ag/AgCl). Weight loss and atomic force microscopy showed a significant difference in corrosion when +310 mV (vs. Ag/AgCl) was applied in comparison to that produced under the other tested potentials (and an unpoised control). Bacterial community analysis conducted using 16S rRNA gene profiles showed that poised potentials are more positive as +310 mV (vs. Ag/AgCl) resulted in strong enrichment for Rhodobacteraceae and Sulfitobacter. Hence, even though significant enrichment of the known electrochemically active bacteria from the Rhodobacteraceae family was accomplished, the resultant bacterial community could accelerate pitting corrosion in 316 L stainless steel, thereby compromising the durability of the electrodes and the microbial electrochemical technologies.

Chlorine Reduction Kinetics and its Mass Balance in Copper Premise Plumbing Systems During Corrosion Events.

Hypochlorous acid has been reported as the main oxidant agent responsible for the corrosion of copper plumbing systems in chlorinated water supplies. However, there is little information about chlorine consumption kinetics in a combined system (i.e., with dissolved oxygen (DO) and free chlorine), as well as its complete mass balance within a copper pipe during stagnation. The results of our experiments using copper pipes filled with synthetic drinking water, with a moderate alkalinity (pH = 7.2; dissolved inorganic carbon = 80 mg as CaCO3 /L), and tested under chlorine concentrations from 0 to 8 mg/L, show that chlorine depletion is associated with pipe wall reactions (i.e., copper oxidation and scale formation processes). Free chlorine was depleted after 4 h of stagnation and its kinetic constant depend on the initial concentration, probably due to diffusion processes. Surface analysis including scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and total reflection X-ray fluorescence (T-XRF) suggest chlorine precipitation, probably as CuCl. The obtained kinetics of chlorine and DO reduction would be critical for modeling and prediction of corrosion events of copper premise plumbing systems. In addition, our results indicate that the pipe's surface reactions due to corrosion induces a loss of free chlorine in the bulk water, decreasing chlorine added for disinfection and the subsequent effect on water quality.

Copper Corrosion and Biocorrosion Events in Premise Plumbing.

Corrosion of copper pipes may release high amounts of copper into the water, exceeding the maximum concentration of copper for drinking water standards. Typically, the events with the highest release of copper into drinking water are related to the presence of biofilms. This article reviews this phenomenon, focusing on copper ingestion and its health impacts, the physicochemical mechanisms and the microbial involvement on copper release, the techniques used to describe and understand this phenomenon, and the hydrodynamic effects. A conceptual model is proposed and the mathematical models are reviewed.

Boron stress response and accumulation potential of the extremely tolerant species Puccinellia frigida.

Phytoremediation is a promising technology to tackle boron toxicity, which restricts agricultural activities in many arid and semi-arid areas. Puccinellia frigida is a perennial grass that was reported to hyperaccumulate boron in extremely boron-contaminated sites. To further investigate its potential for phytoremediation, we determined its response to boron stress under controlled conditions (hydroponic culture). Also, as a first step towards understanding the mechanisms underlying its extreme tolerance, we evaluated the presence and expression of genes related with boron tolerance. We found that P. frigida grew normally even at highly toxic boron concentrations in the medium (500mg/L), and within its tissues (>5000mg/kg DW). We postulate that the strategies conferring this extreme tolerance involve both restricting boron accumulation and an internal tolerance mechanism; this is consistent with the identification of putative genes involved in both mechanisms, including the expression of a possible boron efflux transporter. We also found that P. frigida hyperaccumulated boron over a wide range of boron concentrations. We propose that P. frigida could be used for boron phytoremediation strategies in places with different soil characteristics and boron concentrations. Further studies should pave the way for the development of clean and low-cost solutions to boron toxicity problems.

Modeling MIC copper release from drinking water pipes.

Copper is used for household drinking water distribution systems given its physical and chemical properties that make it resistant to corrosion. However, there is evidence that, under certain conditions, it can corrode and release unsafe concentrations of copper to the water. Research on drinking water copper pipes has developed conceptual models that include several physical-chemical mechanisms. Nevertheless, there is still a necessity for the development of mathematical models of this phenomenon, which consider the interaction among physical-chemical processes at different spatial scales. We developed a conceptual and a mathematical model that reproduces the main processes in copper release from copper pipes subject to stagnation and flow cycles, and corrosion is associated with biofilm growth on the surface of the pipes. We discuss the influence of the reactive surface and the copper release curves observed. The modeling and experimental observations indicated that after 10h stagnation, the main concentration of copper is located close to the surface of the pipe. This copper is associated with the reactive surface, which acts as a reservoir of labile copper. Thus, for pipes with the presence of biofilm the complexation of copper with the biomass and the hydrodynamics are the main mechanisms for copper release.

Multi-technique approach to assess the effects of microbial biofilms involved in copper plumbing corrosion.

Microbially influenced corrosion (MIC) is recognized as an unusual and severe type of corrosion that causes costly failures around the world. A microbial biofilm could enhance the copper release from copper plumbing into the water by forming a reactive interface. The biofilm increases the corrosion rate, the mobility of labile copper from its matrix and the detachment of particles enriched with copper under variable shear stress due to flow conditions. MIC is currently considered as a series of interdependent processes occurring at the metal-liquid interface. The presence of a biofilm results in the following effects: (a) the formation of localized microenvironments with distinct pH, dissolved oxygen concentrations, and redox conditions; (b) sorption and desorption of labile copper bonded to organic compounds under changing water chemistry conditions; (c) change in morphology by deposition of solid corrosion by-products; (d) diffusive transport of reactive chemical species from or towards the metal surface; and (e) detachment of scale particles under flow conditions. Using a multi-technique approach that combines pipe and coupon experiments this paper reviews the effects of microbial biofilms on the corrosion of copper plumbing systems, and proposes an integrated conceptual model for this phenomenon supported by new experimental data.

Differential arsenic binding in the sediments of two sites in Chile's lower Loa River basin.

Fluvial sediments from two lower Loa River basin sites in northern Chile were compared in order to probe the effects of vegetation and organic matter (OM) on As accumulation in fluvial environments. The two sites were the Sloman dam, which lacks macrophytes and has a low OM content (2.4%) in sediments, and the Quillagua Oasis, which is 23 km downstream from the Sloman site and has a higher OM (6.2%) in sediments and abundant aquatic plant life. The Quillagua site had preferential As enrichment with a co-occurrence pattern that differed from that of the Sloman site, which had a lower As concentration (1528 vs. 262 mg/kg d.w., respectively). At the Quillagua site, As concentration was strongly correlated with Mn and OM (r = 0.91 and 0.85, respectively); while at the Sloman site, As concentration in sediments was significantly correlated with Ca and Sr (r = 0.63 and 0.54, respectively). Sequential extraction analyses showed that the Sloman site had higher percentage of easily exchangeable As within the surface sediment (12%, 45 mg/kg d.w.) compared with the Quillagua site (3%, 40 mg/kg d.w.). These contrasting results suggest that both vegetation and OM control the immobilization and accumulation of As in the arid Loa River basin.

Natural attenuation process via microbial oxidation of arsenic in a high Andean watershed.

Rivers in northern Chile have arsenic (As) concentrations at levels that are toxic for humans and other organisms. Microorganism-mediated redox reactions have a crucial role in the As cycle; the microbial oxidation of As (As(III) to As(V)) is a critical transformation because it favors the immobilization of As in the solid phase. We studied the role of microbial As oxidation for controlling the mobility of As in the extreme environment found in the Chilean Altiplano (i.e., > 4000 meters above sea level (masl) and < 310 mm annual rainfall), which are conditions that have rarely been studied. Our model system was the upper Azufre River sub-basin, where the natural attenuation of As from hydrothermal discharge (pH 4-6) was observed. As(III) was actively oxidized by a microbial consortium, leading to a significant decrease in the dissolved As concentrations and a corresponding increase in the sediment's As concentration downstream of the hydrothermal source. In-situ oxidation experiments demonstrated that the As oxidation required biological activity, and microbiological molecular analysis confirmed the presence of As(III)-oxidizing groups (aroA-like genes) in the system. In addition, the pH measurements and solid phase analysis strongly suggested that the As removal mechanism involved adsorption or coprecipitation with Fe-oxyhydroxides. Taken together, these results indicate that the microorganism-mediated As oxidation contributed to the attenuation of As concentrations and the stabilization of As in the solid phase, therefore controlling the amount of As transported downstream. This study is the first to demonstrate the microbial oxidation of As in Altiplano basins and its relevance in the immobilization of As.

Enhanced copper release from pipes by alternating stagnation and flow events.

Traditional studies of copper release in plumbing systems assume that the water extracted from a pipe follows a plug-type flow and that the pipe surface does not interact with the bulk water under flow conditions. We characterized actual stagnation-flushing cycles in a household pipe undergoing corrosion in the presence of a microbial biofilm. The mass of copper released in 10 experiments was on average 8 times the value estimated by using the plug-flow assumption. The experimental copper release pattern was explained by an advection-diffusion model only if a high copper concentration occurs near the pipe surface after stagnation. Microscopic examination of the pipe surface showed a complex assemblage of biotic and abiotic features. X-ray diffraction analyses identified only malachite, while X-ray absorption spectroscopy also revealed cupric hydroxide and cuprite. These results indicate that the surface serves as a storage compartment of labile copper that may be released under flow conditions. Thus, the diffusive transport from the pipe surface to the bulk during stagnation is not the only control of the flux of copper to the tap water when porous reactive microstructures cover the pipe. Our results highlight the need for models that consider the interaction between the hydrodynamics, chemistry, and structure at the solid-water interface to predict the release of corrosion byproducts into drinking water.