RESUMEN
Methanogenic archaea have long been implicated in microbially influenced corrosion (MIC) of oil and gas infrastructure, yet a first understanding of the underlying molecular mechanisms has only recently emerged. We surveyed pipeline-associated microbiomes from geographically distinct oil field facilities and found methanogens to account for 0.2 to 9.3% of the 16S rRNA gene sequencing reads. Neither the type nor the abundance of the detected methanogens was correlated with the perceived severity of MIC in these pipelines. Using fluids from one pipeline, MIC was reproduced in the laboratory, both under stagnant conditions and in customized corrosion reactors simulating pipeline flow. High corrosion rates (up to 2.43 mm Fe0 · yr-1) with macroscopic, localized corrosion features were attributed to lithotrophic, mesophilic microbial activity. Other laboratory tests with the same waters yielded negligible corrosion rates (<0.08 mm Fe0 · yr-1). Recently, a novel [NiFe] hydrogenase from Methanococcus maripaludis strain OS7 was demonstrated to accelerate corrosion. We developed a specific quantitative PCR (qPCR) assay and detected the gene encoding the large subunit of this hydrogenase (labeled micH) in corrosive (>0.15 mm Fe0 · yr-1) biofilms. The micH gene, on the other hand, was absent in noncorrosive biofilms, despite an abundance of methanogens. Reconstruction of a nearly complete Methanococcus maripaludis genome from a highly corrosive mixed biofilm revealed micH and associated genes in nearly identical genetic configuration to that in strain OS7, thereby supporting our hypothesis that the encoded molecular mechanism contributed to corrosion. Lastly, the proposed MIC biomarker was detected in multiple oil fields, indicating a geographically widespread involvement of this [NiFe] hydrogenase in MIC.IMPORTANCE Microorganisms can deteriorate built environments, which is particularly problematic in the case of pipelines transporting hydrocarbons to industrial end users. MIC is notoriously difficult to detect and monitor and, as a consequence, is a particularly difficult corrosion mechanism to manage. Despite the advent of molecular tools and improved microbial monitoring strategies for oil and gas operations, specific underlying MIC mechanisms in pipelines remain largely enigmatic. Emerging mechanistic understanding of methanogenic MIC derived from pure culture work allowed us to develop a qPCR assay that distinguishes technically problematic from benign methanogens in a West African oil field. Detection of the same gene in geographically diverse samples from North America hints at the widespread applicability of this assay. The research presented here offers a step toward a mechanistic understanding of biocorrosion in oil fields and introduces a binary marker for (methanogenic) MIC that can find application in corrosion management programs in industrial settings.
Asunto(s)
Proteínas Arqueales/química , Hidrogenasas/química , Residuos Industriales , Yacimiento de Petróleo y Gas , Acero/química , Aguas Residuales/microbiología , Archaea/genética , Archaea/metabolismo , Proteínas Arqueales/genética , Proteínas Arqueales/metabolismo , Carbono , Corrosión , Hidrogenasas/genética , Hidrogenasas/metabolismo , Metano/metabolismo , Reacción en Cadena de la Polimerasa , ARN Ribosómico 16S/genéticaRESUMEN
Conversion of benzene to chlorobenzenes and monochlorophenols by reaction with chlorine radicals (Cl*) in the cool-down zone of a plug-flow combustor has been studied, and a mechanistic analysis of the initial steps of the oxy-chlorination process is proposed. Superequilibrium concentrations of Cl* are formed during combustion of chlorocarbon species and persist at significant concentration levels even after a substantial reduction in the flue gas temperature (T = 500-700 degrees C). At these temperatures, Cl* attack on benzene present in trace concentrations (initial benzene concentration of 300 ppmv or 1080 ppmv were used for the experiments) in the post-flame gas is shown to result in stable chlorinated products (chlorobenzenes and chlorophenols) and loss of benzene. These results suggest that Cl* attack on trace level aromatics and possibly other organic species may be the initial step in the formation of a broad class of chlorinated and oxy-chlorinated pollutants in the post combustion zone.