Early diagenetic alteration of chlorophyll-a and bacteriochlorophyll-a in a contemporaneous marl ecosystem; Florida Bay

Abstract This report covers the analyses of tetrapyrrole pigments in sediments and numerous source biota from northern central Florida Bay. Sediment cores were all carbonate marls and ‘bedrock’ (Pleistocene limestones) was typically at 0.6–1.2 m bsf. (below sea floor). Extraction of the sediments was performed using tetrahydrofuran, shown to be 3–7 times as effective as more common solvents. Surficial sediments were found to contain a pigment distribution indicating a diatomaceous-cyanobacterial biofilm/mat underlain with purple sulfur bacteria as the microphytobenthos. Downhole trends in pigment diagenesis revealed differences due to paleoenvironment. That is, when bacteriochlorophyll-a (BCHLa) plus derivatives were elevated, indicating strong syn-depositional anoxia, the pheophytins-a (PTINsa) were the major chlorophyll-a (CHLa) derivatives. Conversely, when BCHL-a plus derivatives were low, indicating oxic to dys-oxic syn-depositional conditions, then pyropheophorbide-a (pPBIDa) and 132, 172-cyclopheophorbide-a (CYCLO) were strongly dominant. The generation of cyclopheophorbide in carbonate marls with weakly anoxic to dysoxic syn-depositional conditions may yield an oil-source paleoenvironmental marker for bitumen containing compounds such as bicycloalkanoporphyrins (BiCAPs). Downhole conversions were observed for the following diagenetic steps; CHLa to pheophytin-a (PTINa), PTINa to pyropheophytin-a (pPTINa), pPBIDa to CYCLO, BCHLa to bacteriopheophytin-a (BPTINa), and BPTINa to bacteriopyropheophytin-a (BpPTINa).

[1]  Paul J. Harradine,et al.  Sedimentary sterols and steryl chlorin esters: distribution differences and significance , 1998 .

[2]  G. W. Lynts,et al.  BENTHIC MARINE DIATOM ASSOCIATIONS: UPPER FLORIDA BAY (FLORIDA) AND ASSOCIATED SOUNDS 1 , 1978 .

[3]  E. Zass,et al.  Über enolisierte Derivate der Chlorophyllreihe. 132‐Desmethoxycarbonyl‐173‐desoxy‐132,173‐cyclochlorophyllid a‐enol und eine Methode zur Einführung von Magnesium in porphinoide Ligandsysteme unter milden Bedingungen. (Vorläufige Mitteilung) , 1975 .

[4]  P. Swart,et al.  Interstitial water geochemistry and carbonate diagenesis in the sub-surface of a Holocene mud Island in Florida Bay , 1989 .

[5]  A. Gossauer,et al.  Chlorophyll catabolism. Isolation and structure elucidation of chlorophyll b catabolites in Chlorella protothecoides , 1994 .

[6]  J. Maxwell,et al.  Identification of chlorophyll transformation products in a lake sediment by combined liquid chromatography - mass spectrometry , 1991 .

[7]  E. W. Baker,et al.  Application of Chlorophyll and Carotenoid Pigments for the Chemotaxonomic Assessment of Seston, Periphyton, and Cyanobacterial Mats of Lake Okeechobee, Florida , 1997 .

[8]  L.,et al.  Chlorophyll destruction by Calanus spp. grazing on phytoplankton: kinetics, effects of ingestion rate and feeding history, and a mechanistic interpretation , 1996 .

[9]  S. Wright,et al.  Analysis of phytoplankton of the Australian sector of the Southern Ocean: comparisons of microscopy and size frequency data with interpretations of pigment HPLC data using the \'CHEMTAX\' matrix factorisation program , 1996 .

[10]  A. Eschenmoser,et al.  Über Enolderivate der Chlorophyllreihe. Darstellung von 132,173-Cyclophäophorbid-enolen. Vorläufige Mitteilung , 1975 .

[11]  B. Lapointe,et al.  Eutrophication and trophic state classification of seagrass communities in the Florida Keys , 1994 .

[12]  J. Clardy,et al.  New Chlorophyll-A-Related Compounds Isolated as Antioxidants from Marine Bivalves , 1993 .

[13]  A. Buchs,et al.  A novel sedimentary lacustrine chlorin: Characterisation and geochemical significance , 1993 .

[14]  J. Zieman,et al.  Total epiphyte and epiphytic carbonate production on Thalassia testudinum across Florida Bay , 1994 .

[15]  T. Goodwin.  Chemistry and biochemistry of plant pigments , 1976 .

[16]  E. W. Baker,et al.  11 – Geochemistry of Porphyrins , 1978 .

[17]  E. W. Baker,et al.  Porphyrins in the geological record , 1986 .

[18]  D. Dolphin,et al.  Stereoselective Synthesis of New Chlorophyll a Related Antioxidants Isolated from Marine Organisms , 1996 .

[19]  H. Thomas,et al.  Chlorophyll Breakdown in Senescent Leaves , 1996, Plant physiology.

[20]  Y. Sorokin,et al.  Structure and functioning of the anthropogenically transformed Comacchio lagoonal ecosystem (Ferrara, Italy) , 1996 .

[21]  D. G. Moore,et al.  Guaymas Basin: Sites 477, 478, and 481 , 1982 .

[22]  H. Wanless,et al.  Origin, growth and evolution of carbonate mudbanks in Florida Bay , 1989 .

[23]  E. W. Baker,et al.  Products of Chlorophyll Diagenesis in Japan Trench Sediments, Deep Sea Drilling Project Sites 438, 439, and 440 , 1980 .

[24]  M. Sohn.  Organic marine geochemistry , 1986 .

[25]  Paul J. Harradine,et al.  Characterisation of naturally occurring steryl esters derived from Chlorophyll a , 1993 .

[26]  R. Johns,et al.  Biological markers in the sedimentary record , 1988 .

[27]  James W. Fourqurean,et al.  Distribution, abundance and productivity of seagrasses and macroalgae in Florida Bay , 1989 .

[28]  E. Phlips,et al.  Blooms of the picoplanktonic cyanobacterium Synechococcus in Florida Bay, a subtropical inner‐shelf lagoon , 1999 .

[29]  J. Bauer,et al.  Pyrophaeophorbide-a as a tracer of suspended particulate organic matter from the NE Pacific continental margin , 1998 .

[30]  E. W. Baker,et al.  Characterization of the photoautotrophic algal and bacterial communities in a large, shallow, subtropical lake using HPLC-PDA based pigment analysis , 1998 .

[31]  N. Marcus,et al.  Minireview: The importance of benthic‐pelagic coupling and the forgotten role of life cycles in coastal aquatic systems , 1998 .

[32]  C. Llewellyn,et al.  The rapid determination of algal chlorophyll and carotenoid pigments and their breakdown products in natural waters by reverse-phase high-performance liquid chromatography , 1983 .

[33]  P. Karuso,et al.  132,173-cyclopheophorbide enol, the first porphyrin isolated from a sponge , 1986 .

[34]  E. W. Baker,et al.  Chlorophyll-a degradation during cellular senescence and death , 1998 .

[35]  P. Herman,et al.  Microphytobenthos biomass and community composition studied by pigment biomarkers: importance and fate in the carbon cycle of a tidal flat , 1997 .

[36]  G. Thayer,et al.  Responses of plant communities in western Florida Bay to the die-off of seagrasses , 1994 .

[37]  E. Phlips,et al.  Spatial variability in phytoplankton standing crop and composition in a shallow inner-shelf lagoon, Florida Bay, Florida , 1996 .

[38]  H. Paerl,et al.  Microalgal Pigment Assessments Using High-Performance Liquid Chromatography: A Synopsis of Organismal and Ecological Applications , 1993 .

[39]  D. Repeta,et al.  Novel pyropheophorbide steryl esters in Black Sea sediments , 1991 .

[40]  L. Verzegnassi,et al.  A new series of steryl chlorin esters: Pheophorbide a steryl esters in an oxic surface sediment , 2000 .

[41]  G. Thouzeau,et al.  Variabilité spatio-temporelle de la biomasse microphytobenthique en rade de Brest et en Manche occidentale , 1998 .

[42]  Kevin M. Smith,et al.  Porphyrins and metalloporphyrins. , 1975 .

[43]  R. Ocampo,et al.  Structural comparison of nickel, vanadyl, copper, and free base porphyrins from Oulad Abdoun oil shale (Maastrichtian, Morocco) , 1990 .

[44]  W. Schlesinger.  Biogeochemistry: An Analysis of Global Change , 1991 .

[45]  R. Huene,et al.  Initial reports of the deep sea drilling project: National Science Foundation, Washington, D.C., 1969, 672 pp., U.S. $ 10.25 , 1971 .

[46]  A. Treibs.  Chlorophyll‐ und Häminderivate in organischen Mineralstoffen , 1936 .

[47]  Paul J. Harradine,et al.  Pyrophaeoporphyrins c1 and c2: grazing products of chlorophyll c in aquatic environments , 1998 .

[48]  F. Montforts,et al.  Discovery and Synthesis of Less Common Natural Hydroporphyrins , 1994 .

[49]  M. Veldhuis,et al.  SEPARATION OF CHLOROPHYLLS c1c2, AND c3 OF MARINE PHYTOPLANKTON BY REVERSED‐PHASE‐C18‐HIGH‐PERFORMANCE LIQUID CHROMATOGRAPHY 1 , 1992 .

[50]  S. Wakeham,et al.  Phorbin steryl ester formation by macrozooplankton in the Sargasso Sea , 1996 .

[51]  J. Pennock,et al.  THE RELATIVE CONTRIBUTION OF BENTHIC MICROALGAE TO TOTAL MICROALGAL PRODUCTION IN A SHALLOW SUB-TIDAL ESTUARINE ENVIRONMENT , 1995 .

[52]  E. W. Baker,et al.  Early Products of Chlorophyll Diagenesis in Japan Trench Sediments of Deep Sea Drilling Project Sites 434, 435, and 436 , 1980 .

[53]  J. Maxwell,et al.  High molecular weight chlorins in a lacustrine shale , 1991 .

[54]  L. Yarbro,et al.  Relationship of sediment sulfide to mortality of Thalassia testudinum in Florida Bay , 1994 .

[55]  N. Guha,et al.  Enzymatic Formation of Pheophorbide and Pyropheophorbide during Chlorophyll Degradation in a Mutant of Chlorella fusca Shihira Ee Kraus , 1988 .

[56]  A. Gossauer,et al.  Chlorophyll catabolism — structures, mechanisms, conversions , 1996 .

[57]  A novel fossil porphyrin with a fused ring system: Evidence for water column transformation of chlorophyll? , 1986 .

[58]  R. Parkes,et al.  FORMATION OF MESOPYROPHAEOPHORBIDE A DURING ANAEROBIC BACTERIAL-DEGRADATION OF THE MARINE PRYMNESIOPHYTE EMILIANIA- HUXLEYI , 1995 .

[59]  E. W. Baker,et al.  The biogeochemistry of chlorophyll , 1986 .

[60]  E. Head,et al.  Chlorophyll and carotenoid transformation and destruction by Calanus spp. grazing on diatoms , 1992 .

[61]  L. Yarbro,et al.  Mass mortality of the tropical seagrass Thalassia testudinum in Florida Bay (USA) , 1991 .

[62]  E. W. Baker,et al.  Geochemistry of Tetrapyrrole, Carotenoid, and Perylene Pigments in Sediments from the San Miguel Gap (Site 467) and Baja California Borderland (Site 471), Deep Sea Drilling Project Leg 63 , 1981 .

[63]  Paul J. Harradine,et al.  Triterpenoid chlorin esters: water column transformation products of chlorophyll a , 1996 .

[64]  K. Sakata,et al.  Chlorophyllone-a, a new pheophorbide-a related compound isolated from ruditapes philippinarum as an antioxidative compound , 1990 .

[65]  J. Maxwell,et al.  NMR studies of sedimentary tetrapyrroles , 1990 .