Ist Quarter, 2012 6 Bacterial attachment to metal substrate and its effects on microbiologically-influenced corrosion in transporting hydrocarbon pipelines by Faisal M AlAbbas*', John R Spear’, Anthony Kakpovbia', Nasser M Balhareth', David L Olson’, and Brajendra Mishra? ' Inspection Department, Saudi Aramco, Dhahran, Saudi Arabia * Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO, USA * Department of Civil and Environmental Science and Engineering Colorado School of Mines, Golden, CO, USA | ‘ARGON STEEL PIPELINES ARE considered the mos ficient and economic method of ranportng hydrocarbon prodvetsin the oll and gas industry During oland gas operations piping heceenae oe subjected to diferent corrosion deterioration mechanismsjincluding microbiologealhinfusrecdeen canes (IC) which resus rom accelerated deterioration caused ty ciferene microbial actvices ponent he hydrocarbon systems. The bacterial adhesion i detrimental stp inthe MIC procese The PIG proces starts withthe atichment of planktonic micro-organisms that establish bial andr ura lead te nang | deteroraton.The tendency ofa bacterium to adhere to the metal surce can be svuated Oy ake thermodynamic approaches vi interaction enerles This paper coversan overview ofthe dhermrodyparing and surface-energy approaches of bacterial adhesion, the factors affecting the bacterial adheeion ce he metal surface, the subsequent physical invration between te bof and substratum and te plesoen on the MIC in pipeline systems Sear ewes ee ene «erosion corrosion, andl dealloyingl24], Iris believed thar MIC isone of the most damaging mechanisms to pipeline steel materials, Microbial activities are thought to be responsible for greater than 75% of the corrosion in proxtuctive oil wells plants, pipelinesystems, and exporting te ancl for greater than 50% of the failures of pipeline sytem responsible ran increaseincorrosion rateduethepresence — [5, 6], MIC has been estimated to aecoun for 2053 that accelerate the rate of all internal pipeline corrosion costs. In 2006, MIC was {1}. MICdoesnotproduce suspected as one of the two major factors that shutdown the major Alaska Prudhoe Bay oilfield pipeline. This leak caused turmoil in the global oil market [7]. ss treating facilites such as refineries of of microbial metabolic activit Different microorganisms thrivein oil and gos transporting systems for the reason that all of the essential elements for life are present in these enviconments. Microbial life reeds four basic things to thrive in an environment: a carbon source, water, an electron donor, and an electronFig. FESEM Image for a dense biofilm developed by SRB, Dene be required for the calculation, as shown in equation 9 below 142-44) AGadh = ack + aGah, (10) Equation ofstateis considered relatively easy method fo compute AGqs, (Equa 4). It becomes more complicated whensurfacefrevenergycomponentsy", ‘y" and parameters and y'are included as shown in thesecond and thirdapproaches|40-42].Furthermore, and based on the thermodynamic model, Power etal [45] developed anovel model that caleulates Gibbs free energy (AGadh) of adhesion for the inital bacterial attachment process. The merit ofthis model is that it climinares the need to calculate interfacial free ‘energies and instead relies on measurable contact angles. In theit work, they were able to calculate the AGadh of adhesion for a Pseudomonas putida bacterium interacting with a mercaptoundecanol and dodecanethiol selfassembled monolayer. They developed the following Gibls fee energy: 1 AG oan = 5 Yi (1 — £08 8p1)(1 — C08 8,,)44 (11) ‘The term yi fee energy of liquid, and Oy and 8, are the ‘contact angles measured from the bacteria/airliquid and substrateairliquid interfaces, respectively. DLVO approach ‘The drawback of the thermedynamies approach is that it ‘ignores the electrical doublelayerinteraction with thebacteria, ssillustrated by Fig 4. Thisassamption isinvalidasthe bacterial cellshavea surfacenegativeor-positivecharge. Incontrast, the DLVO approach displaysabalancebecween arractiveLifshite van det Waals(AGLW)and epulsiveorattraciveelectrostaic forces (AGEL). These to forces are function of the distance (2) between che bacteria and surface. In order to calculate the adhesion free energy (AGadh, the electrostatic interactions between surfaces should he included. The inclusion of electrostatic interactions requires thatthe zeta potentials of theinteractingsurfacesbe measured, insldition tomeasuring, contactangles| 41.45, 46 Sothetotalfreeenengyexpression is: AGsan = AG” (A) + AG" (d) ry ‘The ateractive Litshirevan det Waals AGLW is calculated by tw. TAR a6 = and A 3) ‘The repulsive or armactive electrostatic forces AGPas shown, in Equation 4 below. The term A is the Hamakar constant, gy and @; are she zeta potentials of the bacreria and the flat surface, Ris the sphere radius assuming the bacteria is sphere shapes, €, and «, are the electrical permittivity ofthe vacuum and tedium respectively, « is Debye- Huckel parameter, and d is the distance in nm [41,46 I has been found chat the medium ionic strength has no {influence on the Lifshitevan der Waals acraction, whereas both the range and che magnitude of the elecerostatic lnteractions decrease with increasing ionic strength due ro shielding of surface charges. lu case of high ionie strengths, clectrostatic interactions have lost thei influence [41], Extended DLVO approach ‘Theextended DIVO theory relates theorigin ofhydrophobic interactions in microbial achesion and includes. four fundamental interaction enetgies: Lifthitevan der Waals, clectrostatie, Lewis acid-base, and Brownian motion forces as shown in Equation 15 below. ‘The effect of acid-based inteeaction is higher than those for the electrical and the Lifshitz van der Waals energies; however, it is short range and requizes a close diseance (© Sim) between the bacteria and the surface. On the other ysl = (WF = fey +2 (vii + rive ~ Vers — Vive) ” H+ exp(—ka)] soap nae el EBD « tt ret-n)} Gacy = AG”(d) + AGE (d) +64") + AGE (4) ay)Isc Quarter, 2012 hhand, the Brownian motion comprise (1/2) KT per degree of freedom and the AGBIW of adhered bacterin toa surface equals IKT = 0.414 x10® J [41,46] Subsequent physical-chemical interaction between the biofilm in the pipeline ‘The subsequene influence of the biofilm on linepipe see is the development of MIC or biofouling. MIC is not new rype lof eormosion process, hut i incorporates the role of aceria and resulted biofilm in the corrosion processes. There are diverse ypes of corusion resulting from MIC. Generally, MIC produces localized corrosion that exhibits pitting. (Other types of corrosion include crevice corrosion, under leposit corrosion, cracking, enhanced erosion corrosion, and dealloying [24] Corrosion is classified as an interfacial process, and the thermodynamics and kinetics of che process are strongly Influenced by the physicochemical environment at the Interface including the pH, oxygen concentrations, salt, conductive, developed cxides, and redox potentials. Iris well cstablished thae the metabolic activities andthe biofilm have the ability to alter these factors [24,47], and the type and cextentofdamage dependson thebacterialtypeancl associated «vironment, Themain rypesorbacteriaasociated with merale in pipeline systems sre sulphateseducing bacteria (SRB), ironeducing bacteria, and irom and manganescoidising Iracteria [5]. Among them, SRB has been recognized t9 be the major MIC causative microorganismsin pipelinesystems, According to Iverson's estimation, 77% of the corrosion in. the producing oil wells in the United States is introduced! by SRB [47]. Therefore, the following discussion willbe limited tothe influence ofthe physicalchemical interactions between the SRB, biofilm and inepipe surface, Sulphatereducingbacteria SRB) arerelated tothe Bacterial domain: SRB are anaerobic and do not need oxygen to survive; rather, they use sulphate ions asa terminal acceptor and produce hydrogen sulphide (H2S). Furthermore, this type of bacterium has the ability to reduce nitrate and thiosulphate. SRB can manage to stay alive in an aerobic environment until the environment becomes suitably aerobic for them to grove. In this case, the aerobie type (ie. IRB) of bacteria consumes the oxygen faster than the ‘oxygen diffusion towards the biofilm, so the environment deeperin thebiofilmwillhecomesnaerobicand, in turn, SRB will thrive, SRB obtain thei energy from organic nutrients, such as lactate, and they can grow in a pH range from 4 to ‘9.5and tolerate pressure up to 500 atmospheres. Most SRB ‘exist in temperature ranges of 25-60°C. SRB can be found exerywhere in the oil and gas production facilities, both deep in the well, and extending to the treatment facilities. The environment inside the pipeline systems has anaerobic ‘or low exygen concentsation, considering SRB as the main contributor to biocorrasion [2-4 8, 48, 49) 6 ‘There ate different ways thae SRB and the resulting biofilm produce MIC damage inthe pipeline, Accondingtothe clasical theory; SRB consume the cathodic hylrogen by av enayme Iknown as hydrogenase to obtain the clectron required for ‘metabolic activities. Therefore, the removal of hyiogen from themeralaurficewillcarakzethe reviableactvationofhycrogen and in rum will fore the ton to dissohe atthe anode 24, 47 In 1934, Khur and Viugt [3] proposed thatthe reactions that over the classical theory as follows: Fe 4 + 8 anodic reaction (18) BHP + 8 8H cathodic reaction (17) SO#+8H=S2+4H7O SRB metabolism (18) Fees RS corrosion products (19) Fes + 6H: 3F(OH Miller and King [3] related the corrosion effects of SRB to both the hydrogenase and inon/iron sulphide galvanic cell. As proposed the iron sulphide will act as a cathode and absorb ‘themolecular hydrogen, andtheareabeneath willbetheanode sires Inanacrobieconditions theemygen-fe environmentthat isa prerequisite for SRB growth, the concentration ofhydrogen ions will be extremely lew and will noe be ale to form layer cof atomic hydrogen. For this reason, an additonal cathodic reaction has een considered, suchas H Sreduction asfollows: HS te FHS +44, 20) Furthermore, the biofilm forms on the meta susface & heterogeneous in nacue and forms community centres of Iracteria. Those sites may be chesen based on chemical and metallurgical profiles, such s inclusions and roughness that induce atachmentsies forthe bacteria, These colonies produce EPS that attract more bacteria and organic materials to these sites Subsequently the conditions under these colonies = uch, aseaygen level, ion concentrations, and pH - will be different fromthosein the buikstream and, nur, leseltothe formation ‘of concentration cells, pitting, and ereviee conosion. Other literature propesed that the area beneath the biofilm will ace as anodic sites while the outside region will be eathodic. The fixing community centre wil form fixing anodic sites tha are affected by the immobile bacteria growth, their activites and thebiofilm developed underthese colonies. This behaviourwill initiate pits under those colonics and will ecome fixed anodic sites under an immobile community; as a consequence those pits wil grow with time (3,47, SOL Some strains of SRB, such as Desujoubrio, use the organic carbon source inthe nutrition system sich as lactate to procice the hydrogen necessary as electron donor and yield pyruvate fr acetate, which is excreed to the bulk as these bacteria are nonacetatecnidizers as follows: 4CH\CHOHCOO- +80, + 4CH,COO-+ 4HCOy +HS+HS +H" cc)Fig. Extensive pitting induced by SRB, Desulfovibrio africanus sp, on API SL X65 carbon liepipe ste! coupons [19]. 2CH,CHOHCOO- + 80,2 > 2CH,COO' + 2HCO,+HS + HS + CO, (22) ‘Therefore, the deposit of acetic acid as a result of the above reaction will form an aggresive environment tothe linepipe steel when concentrated under colony or other corrosion product and leads to localized metal dissolution beneath it 3, 48, Figure 5 shows extensive pitting resulting from MIC caused by SRB on low alloy eazbon steel surfaces [19] Conclusions ‘The MIC process starts with the attachment of planktonic bacteria to linepipe surfaces, which leads tothe formation of the biofilm and subsequently results in metal deterioration: Bacterial surface,and medium characteristics playsignificant roles in the extent of bacterial transfer rate, adhesion, and resulting biofilm size. The bacteria characteristics include te, and hydrophobicity; the surface properties include chemical compositions, roughness, incl 8 potent sions, crevices, oxides, and I and the aqueous ‘medium properties include pH, eof the system. The tencencyofabacteriuin toadhere ionic strength, and flow to the surface can be evaluated using different approaches via interaction energies, and these include thermodynamics, DLVO, and extended DLVO. These approaches are based oon the fundamentals of interaction forces berween the bacteria and the surface, and in order ro have an adequate description of this interaction, both long sage and shore range forces should be considered ‘The main ypes of bacteria associated with MIC in pipeline nsare sulphate-edhcing bacteria (SRB), iron seducing bbactera,and iron-and manganesesidizinghacteria. Among them, SRB has been recognised toe the major MIC causa tive bacteria in il and active metabolisms of SRB alter theelectroch -quently change the pH level, produce more H25, 3 operations. The biofilm and the ial process and introduce multiple cathodic side reactions, all of which enhances the reduction quality of the system anc! acceler: ates the anodic dissolution. Moreover, the accumulation of iron sulphide on the stel surfaces forms a valvanic cell attack of the iron surface adjacent to deposits of iron sulphide. Most, the with iron, resulting in localized galvani nature of SRB damage is local zed extensive pitting attacks References 1, EMansfeld, 2007. The inceraction of bacteria andl metal surfaces. Electrochimica Acta, 52, 1670-7680. B.Little and J.Lee, 2007. Microbiologically influenced corrosion. Wileylarerscience. 3. RJavahersashti, 2008, Miceobiologicallyinfluens rosionsan engineering insight Springer-Verlag London, 4. Ravaherdashti, 2010. MIC and cracking af mild and scainless steel. VDM Verlage, Germany, 5. EMiranda, M.Bethencour, FJ-Borana, and MJ.Cano, 2006. Biocorrosion of catbon steel alloys by anhydtog enofrophic sulfate-reducing bacterium Desulfow capillarus isolated from a Mexican oil field separator, Corrosion Science, 48, 2417-2431. 6. H.GFlemming, 1996, Ecenomical and technical ove: view. In: E.Heitz, H.C.Flemming, and W'Sand, (Ed), 1996, Microbially influenced coreosion of materials, Springer Verlag, Berlin, New York, pp5-l4l G.AJacabson, 2007, Corssion at Prudhoe Bay — lesson on the line, Materisls Performance, 46, 27:34, 8. -M.Madigan, 2009, Brock biology of microorganisms; 12th Edn. Pearson Benjamin Cummings, San Francisco, USA. 9. LB.Beech and J Sunner, 2004. Biocortosion covsards understanding interactions benween biofilms and met: als, Curr. Opin.Biotechno., 15, 181-186 10. M.Walch, 1992, Correxion, microbial, In: J.Lederberg (Ed,), Encyclopedia of Microbiology, Academie Press, New York, 1, 58559, IL 1.B Beech and C.C-Gaylarde, 1999. Recent advances in the study of bioeorrosion: an overview. Rev, Mierobic, 30, 177-190,Ist Quarcer, 2012 12, DAJones and PSAmy, 2002. A thermodynamic in- terpretation of microbiologieally influenced corrosion Corrosion, 58, 938945. 13. Tingyue Gu, KZhao, and S.Nesie, 2008, A new mecha- nistic model for MIC based on a bioeatalytic cathodic sulfate reduction cheory. Paper 09390, NACE Confer- ence, Houston, TX, USA. 14 Xiaoxia Sheng, Yen Peng Ting, and Simo-Okevi Pehko- nen, 2007, Foroe measurements of bacterial adhesion fon metals using a cell probe atomic force microscope. Journal of Colloid and Ineerfe Science, 310, 661669. 15.Y.Ong, A.Raatos, G.Georgious, and MM.Sharma, 1999. Adhesion forces becween E. coli bacteria and biomaterial surfaces, Langenuie, 15, 2719-2725 16. Clan Oss, RJ.Good, and M.K.Chaudhury, 1986. “The ole of van cer Waals forces and hydrogen bonds in bydrophobic interactions berween biopolymers and low energy surfaces, J, Colloid Interface Set, 111, 378390, 17, J.W.Morgan, LM Bvison, and C.F Forster, 1991, Exami- nation into the compesition of extracellular polymers ‘extracted from anaerobic sludges polymers seem to be responsible for microbial attachmenteithert0 asupport medium or within the sludge granule. Process Saferyand Environmental Protection, 69, 231-236. 18, Arundhati Paland A. K Paul, 2008, Microbial extracellu- larpolymericsubstances: central elements in heavy metal bioremediation. Indian J.of Microbiology, 48, 4964. 19, FAbAbhas, A.Kekpovbia, BMishra, D.Olson, and JSpeat, 2011, Utilization of nondestructive electro: chemical techniques in characterizing microbiologieally influenced corrosion (MIC) of APLSLX65 carbon line pipe stel: laboratory study. Proc. QNDE Conference, Burlingwon, VT, USA. 20.D.RKorber, A.Choi, O.M.Wolfsardt, S.Cngham, and D.E-Caldwel, 1997, Substrarum ropogeaphy inf ences susceptibility of Salmonella enteritidis biofilms (© trisodium phosphate. Appl. Environ. Microbiol., 63, 33523358, - R-Kurissery,R Sreekuumaria,N-Kanavilil,and A Yasushi, 2001. Bacterial attachment to stainless steel wekls: significance of substratum microstructure. Biofouling, 17, 303.316, 22, B.Litle, P Wagner, and J Jacobus, 1998, The impact of sulfatereducing bacteria on welded coppetnickel sea- water piping systems. Material Performance, 27, 7.61 23.E.Medilanskia, K-Kaufmanna, L-Y.Wicka, and (O.Wanner, 2002. Influence of the surface topography of stainless steel on bacterial adhesion. Biofouling, 18, 193.203. 24.RArmona, J Starosvetsky, M.Dancygiecband, and DiStarosvetsky, 2001. Adsorption of flavobacteri umbreve and pseudomonas fluorescens on different metals: electrochemical polarization effet. Biofouling, 17, 289.301 25.M-Fede Romero, J Parra, and R.Rule, 2006. Cathode polarization effect on sessile SRB growth and iron protection. Paper 06526, NACE Conference, Houston, TX USA, 2 a 26.B.Li and B.E.Logan, 2004, Bacterial adhesion to glass and mecaloxide surfaces, colloids and surtaces. Bko interfaces, 36, 8190. 27. WPJohnson, MJ. Martin, MJ.Gross, and BEELogan, 1996, Facilitation of bacterial reansport through porous media by changes in sokution and surface propertics. Colloid Suries, 17,263 28.KAWhitehead and ).Verran, 2008. The effect of substratum properties on the survival of attached mie ‘croorganisms on inert surfaces. Marine and Industrial Biofouling, SpringerVeriag Bedin, pp13-34 29,SN.Avery, NG Howlett, and S.Radiee, 1996. Copper toxicity towards Saecharomyoes cerevisiae: dependence fon plasma membeane faty acid composition. Appl. Environ Microbiol, 62, 39603966, 30.TJ Starr and M-E Jones, 1957. The effet of copper on the growth of bacteria isolated from marine environ ments. Limnol Oceanog, 2, 3336. 31. R.B,Jonas, 1989. Acute copper and cupric ion eoxiciy in an estuarine microbial community. Appl. Environ. Microbiol, 55, 4349. 52.C.W.keesil, 2001, Antibacterial properties of copper and brass demonstrate potential t© combat eexieE. coli outbreaks in the food processing industry, Paper presented at the Symposium on Copper and Health, CEPAL, Santiago, Chile 33.5.M.Gerchakov, DS Marstalek, F).Roth, BSallman, and LR.Uges, 1977. Observations om mierafouling applicable to OTEC systems, Proc. OTEC Biofouling and Corrosion Symposium, WA, pp63-75. 34. M-Hermansson, 1999, The DEVO theory in microbial adhesion. Colloids and Surfaces B: Biointerfaces, 14, 105.19, 35. $Xiaowia,PT-Yen,andS.O. Pehkonen,2008. Theinilu- ence of ionic strength, nutrients and pH on bacterial adhesion to metals, Journal of Colloid and Ineerface Science, 2, 256264 36.M.Fletcher, 1988. Attachment of Pseudomonas fluorescens co glass and influence of electrolytes on bacteriamaubstracumseparation distance. J. Bacteriol, 170, 2027-2030, 37. MM.Cowana, TM.Wasten, and M.Fletcher, 1991 Mixed-pecies colonization of solid surfaces in labora: tory biofilms. Biofouling, 3, 23:34 38.1 Shunichi, .Koki, H.Unno, and K.Hori, 2004, Two morphological types of ell appendages on a strongly axthesive bacterium, Acinetobactersp-Steain Tol5.Ap- plied and Environmental Microbiology, 8, 50265029. 39.D.Davies, 1003, Smallscale systems for in vivo deus delivery. Nat. Rex. Drug Discos, 2, 114122. 40.R.Bos, H.C.van der Mei, and HJ-Bustcher, 1999, Physico-chemistry of inital enierobal adhesive interac. tions its mechanisms snd methods for study. FEMS Microbiology Reviews, 23, 179.230. 41. A.W.Neumann, Rj.Good, CJ Hope, and M.Sejpal, 1974. An equation-ofstare approach to determine sur face tensions of lowencrgy solids from contactaigls. J. Colloid Interface Si, 49, 2913042 42.J.R.Dann, 1970. Forces involved in the adhesive proc: ‘es, [:ciitical surface tensions of polymeric solids as determined with polar liquids J. Colloid interface Set, 32, 302-520. 43.[d.19T0. Forces involved in the adhesive process. Il: Nondlispetsion forces at solidliquid interfaces. Ibid., 32, 321331, 44.D.K.Owens and R.C.Wendr1969. Estimation of the surface free energy of polymers. J. Appl. Polymer Sci, 13, 174.1747. 45.1 Power, Stier, M.Hawton, and H Schraft, 2007. Time: lapse confocal microscopy studies of bacterial adhesion. ‘toselfassemblel monolayersand confirmationofancvel approach to the thermodynamic model. Langmuir, 23, 56225629. 46. S.Bayoudh, AOthmane, LMora, and H.Ben Ounda, ‘The Journal of Pipeline Engineering 2009, Assesing bacterial adhesion using DLVO and XDLVO theories and the jet impingement technique Colloids and Surfaces Biotnterfaces, 73, 19. 42. FXwang, J. Wang, L-Yan, and D.Zhang, 2007. Effects of suatereducing bacteria on the cortosion behavior fof carbon steel. Elecreochimica Acta, 52, 60846088. 48. H.Videla, CSwords, and R.Edycean, 2002. Corrosion pproductsand biofilm interactions in the SRB influenced corrosion of stel, Paper 2557, NACE Conf., Houston, TX, USA. 49. HA Videla, 1996, Manual of biocorrosion. CRC Lewis Publishers, Boea Raton, EL, USA. 50.H.Castaneda and X.Benetton, 2008. SRB-biofilm influence in active corrosion sites formed at the steel electrolyte interface when exposed to artificial seawater conditions. Corrosion Selence, 50, 1169-1183,