Clare, A.S.

di Fino, A.

Heissler, S.

Mohamed, T.

Rosenhahn, A.

Senkbeil, T.

Fino, A. di

Clare, A. S.

KITopen

I it t di f b l id t i XRF d in s u s u es o  arnac e cypr  cemen  us ng  an  m cro-Raman spectroscopyT. Mohamed1,2, T. Senkbeil1,2, S. Heissler1, A. Di Fino3, A. S. Clare3,A. Rosenhahn1,3 1Institute for Functional Interfaces (IFG), KIT, Germany2Applied physical chemistry, Heidelberg University, Germany. 3School of marine science and technology, Newcastle University, UKIntroduction Average spectrum for 4 individual Raman spectra recorded within an 1st, 2nd, 3rd rings and antennule region of  the 4 days settlement a) B. i i d b) B hit it j il b l C F di kMarine biofouling is caused by the adhesion of marineorganisms (barnacles, macroalgae, microbial slimes, etc.)on submerged man-made and/or natural surfaces. It is aworldwide problem in marine industry and causes increasedmaintenance costs. Barnacles are a good model forresearch on permanent underwater adhesion and the widerprocess of marine biofouling.[1]AimApplication of in-situ spectroscopy to understand thechemistry of marine adhesives of barnacles during thedifferent settlement stages (cyprid to adult). Knowledgemprov sus an  . amp r e uven e arnac es on a 2 s .(a) (b)about the adhesive mechanism is supposed to inspire novelantifouling approaches in the future.MethodsBarnacle cyprids (Balanus amphitrite and Balanusimprovisus) cultured by Newcastle University were allowedto settle and investigated in-situ by spectromicroscopy.Kapton was used as substrate with good transmission for X-rays, whereas the calcium fluoride disks were used forRaman studies.Barnacle bodySea waterμ-Ramanμ-XRF Chemical analysisElemental analysiskapton CaF2Permanent glueHolderJuvenile barnacle Base plate of juvenile barnacle consists of several ring like structure. The spectra show high calcium concentrations (277 and 1085 cm-1)[3] are only present at the rim and elevated at the 3rd ring of the barnacle incase of Balanus amphitrite compared to Balanus improvisus where it is only in the first and second ring. Amide rich components (e.g. proteins) are located on the inner ring close to where mineralization happens and is more in Balanus amphitrite. In the case Balanus improvisus there are strong peaks of C=C stretching in the range of 1520 cm-1.[4]This diagram shows schematically the experimental setupfor the two different in-situ spectroscopies: X-ray µ-fluorescence for elemental analysis and µ-Raman analysisfor the determination of chemical composition of theadherent base plate. For both techniques a specific holderhas been developed which allows to handle and investigateliving barnacles in sea water. X-ray fluorescence results for 4 days juvenile barnacle a) B. improvisus and b) B. amphitrite settled on kapton sheet.Sr Mn ArKCa(a)K Sr ArCa Mn(b)Although the two species are different but the spectra look similar so far as the chemical composition of cement glue is conserned.Characterization1) Micro-Raman spectroscopy for chemical composition. 2) X-ray fluorescence (XRF) for elemental distribution.Barnacle life cycle.Results Interestingly, calcium is mainly concentrated on the rims of the base plate and moves along with the growth of the young barnacle. In case of Balanus improvisus Cl , Sn,Cr and V are more concentrated at the rim but are absent in Balanus amphitrite. Element distribution correlates for iron zinc and copper near the center of the base plateFePSPbBrCu Zn AsNiVClCrSnCu Fe Zn As BrNi S Cl PypridFirst attachment Metamorphosis JuvenileNauplius, , .Bromium does not correlate well with the othe relements and frequently shows two bright spots on the surface.ConclusionThe base  plate of juvenile barnacle of both spieces (B. amphitrite and B. improvisus) were measured by Micro-Raman spectroscopy without sample invasion or isolation. The presence of calcite at the rim of juvenile barnacle gives evidence that the cyprid started to build its shell by secretion cement glue after settlement.Presence of Amide components in the antennule region could be  related to the cement glue and/or soft tissue of organism.Future experimentsExtending the work with confocal Raman spectroscopy to have a map of the distribution of their different chemical composition for settled  barnacles at different life stages (cyprids, metamorphosis, Juvenile and adult) Extending work on adhesives to algae (Ulva linza, brown seaweed, Navicula and perminuta) ReferencesKIT – University of the State of Baden-Württemberg andNational Research Center of the Helmholtz Association T.mohamed@uni-heidelberg.deThe barnacle life cycle is characterized by 3 major steps.The planktonic phase can be subdivided into six stages ofnauplius, the plankto-benthic phase involves the cypridsand surface exploration, and the final benthic phase inwhich the barnacles are a sessile organism.[2]C The colocalization in the center points and especially the presence of iron points towards a contribution to the circulating vessel system.Hemolymphs of invertebrates are being considered to contain Cu butto our knowledge it was not shown that iron, bromine and zinc co-localize. Probably the data could be interesting in the context of curingof adhesives.1) D. Meseguer et al., 2004, Progress in Organic Coatings 50, 75–104.2) N. Aldred et al., 2008, Biofouling, 24, 351–63.3) D. Barlowet al., 2009, Biofouling 25, 359–66.4) M. Schmidt et al., 2009, J. of Adhesion, 85, 139–51.

In situ studies of barnacle cyprid cement using XRF and micro-Raman spectroscopy

https://publikationen.bibliothek.kit.edu/220085829/3815962

In situ studies of barnacle cyprid cement using XRF and micro-Raman spectroscopy

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