A novel sedimentary lacustrine chlorin: Characterisation and geochemical significance

Chillier, Xavier Fr. D.; Gülaçar, Fazil O.; Buchs, Armand

doi:10.1016/0045-6535(93)90121-k

Cited by 21 publications

(11 citation statements)

References 15 publications

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“…Recently, Chlone a 1 and CPP516 have been found in marine and lacustrine sediments (Chillier et al 1993;Harris et al 1995;Ocampo et al 1999). CPP516, in particular, was found to be the major Chl a degradation product in sediments from the Black Sea and the Peru margin and was found in particulate organic matter (POM) collected in sediment traps (Ocampo et al 1999).…”

mentioning

confidence: 99%

Distribution and sources of cyclic pheophorbides in the marine environment

Goericke

Strom

Bell

2000

Limnology & Oceanography

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The labile chlorophyll a (Chl a 1 ) degradation product, 13 2 , 17 3 -cyclopheophorbide a enol (CPP516), was only recently found in marine sediments, where it can contribute a significant fraction to solvent-extractable sedimentary chlorins. We developed a new chromatographic method for the analysis of CPP516 to study its distribution and sources in the marine environment. We found high concentrations of CPP516 in surficial sediments and particulate matter collected in sediment traps. It contributed 40 to 70% to the sum of all Chl a 1 degradation products in fecal material from herbivorous microzooplankton and macrozooplankton. We did not find CPP516 in exponentially growing or stationary phase algal cultures. These data suggest that a major source of CPP516 is herbivores feeding on phytoplankton. We also found a series of compounds similar to CPP516 in sediments and sediment-trap samples. Mass-spectrometric and ultraviolet(UV)/visible-spectrometric analyses suggest that these are CPP516 analogs of divinyl-Chl a and Chl bs and Chl cs, conclusions that have to be confirmed by synthesis. CPP516, dissolved in organic solvents, easily degrades to 13 2 -oxopyropheophorbide a and chlorophyllone a under oxic conditions. When associated with particles, CPP516 is stable in oxic aquatic environments on a timescale of days, possibly stabilized by the chelation of metal cations. The chromophore of CPP516 differs substantially from that of other Chl a 1 degradation products; it has absorption maxima at 360, 426, and 688 nm. CPP516 does not fluoresce as other Chl a 1 degradation products. As a consequence, it is invisible to fluorescence-based analyses of ''pheopigments.'' Thus, rates of grazing and growth derived from such measurements, as used in conjunction with the gut fluorescence and the Chl-budget method, will be underestimates of true rates when CPP516 contributes significantly to total chlorins.

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confidence: 99%

Distribution and sources of cyclic pheophorbides in the marine environment

Goericke

Strom

Bell

2000

Limnology & Oceanography

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“…Extraction and separation of sedimentary pigments were done according to published procedures (King and Repeta, 1991;Chillier et al, 1993). In brief, approximately 500 g of wet sediment (containing about 80% water) was extracted ultrasonically (5 min) with four portions of acetone (250 ml) followed by three portions of methylene chloride (250 ml).…”

Section: Methodsmentioning

confidence: 99%

“…4. This fraction was obtained using the procedure described in our original paper (Chillier et al, 1993), i.e., including a TLC separation step on silica gel. The large predominance of 2S over 2R clearly indicates that, if not all, at least the major part of the sedimentary chlorophyllone is not an analytical artifact.…”

Section: Compoundmentioning

confidence: 99%

“…In recent years however, we have identified another type of chlorin as a major transformation product of chlorophyll a (Chl, Fig. 1, 1) in the surface sediments of a eutrophic lake, namely chlorophyllone a (Chlone a, 2) (Chillier et al, 1993). This compound was subsequently found in many other lacustrine and marine sediments (Harris et al, 1995a;Cariou-Le Gall et al, 1998;Kowalewska et al, 1999;Villanueva and Hastings, 2000;Airs et al, 2001) and considered to be the link between chlorophyll a and the bicycloalkanoporphyrin (3) found in older sediments (Keely et al, 1994;Harris et al, 1995b).…”

Section: Introductionmentioning

confidence: 99%

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On the sedimentary occurrence of chlorophyllone a

2003

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The 13 2 ,17 3 -cyclopheophorbide a enol (CPP) is shown to convert mainly to a $1:1 mixture of (13 2 R=S) chlorophyllones a (Chlone), when chromatographed over silica gel or alumina supports. 15 1 -hydroxychlorophyllonelactone a and some other chlorophyll a related compounds are also tentatively identified as minor transformation products of CPP. This raises the possibility that the chlorophyllones reported in recent sediments may be analytical artifacts from CPP. However, data for the surface sediments from Lake Motte as well as literature data for other contemporary sediments show that, (i) they are not artifacts, (ii) considering that CPP is the intermediate compound in the formation of chlorophyllones from chlorophyll a, the hydroxylation of CPP in the sedimentary environment involves an enzymatic process leading preferentially to 13 2 S chlorophyllone a.

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“…Such pheopigments were first found in sponges (13 2 ,17 3 -cyclopheophorbide-a enol; 5a; Karuso et al, 1986) and the viscera of macrobenthic suspension feeders (chlorophyllone-a; 4; Sakata et al, 1990;Yamamoto et al, 1992), and subsequently in marine and lacustrine surface sediments (chlorophyllone-a; 4; Chillier et al, 1993;Harris et al, 1995;Aydin et al, 2003; and 13 2 ,17 3 -cyclopheophorbide a enol; 5; and its analogs; Ocampo et al, 1997Ocampo et al, , 1999Goericke et al, 2000) and sinking particles and particulate organic matter (chlorophyllone-a; Walker and Keely, 2004; and 13 2 ,17 3 -cyclopheophorbide-a enol; Goericke et al, 2000). Goericke et al (2000) demonstrated that (1) 13 2 ,17 3 -cyclopheophorbide enol was not detected in pure algal cultures, but that (2) the fecal materials of various micro-and macrozooplanktons in pure cultures contain a significant amount (40-71% of the total pheopigments).…”

Section: Origins Of 3-nor-and 8-nor-dpepmentioning

confidence: 99%

Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments

et al. 2008

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Abstract. We determined both the nitrogen and carbon isotopic compositions of various vanadyl alkylporphyrins isolated from siliceous marine sediments of the Onnagawa Formation (middle Miocene, northeastern Japan) to investigate the biogeochemistry and ecology of photoautotrophs living in the paleo-ocean. The distinctive isotopic signals support the interpretations of previous works that the origin of 17-nor-deoxophylloerythroetioporphyrin (DPEP) is chlorophylls-c 1−3 , whereas 8-nor-DPEP may have originated from chlorophylls-a 2 or b 2 or bacteriochlorophylla. Although DPEP and cycloheptanoDPEP are presumably derived from common precursory pigments, their isotopic compositions differed in the present study, suggesting that the latter represents a specific population within the photoautotrophic community. The average δ 15 N value for the entire photoautotrophic community is estimated to be -2 to +1‰ from the δ 15 N values of DPEP (-6.9 to -3.6‰; n=7), considering that the empirical isotopic relationships that the tetrapyrrole nuclei of chloropigments are depleted in 15 N by ∼4.8‰ and enriched in 13 C by ∼1.8‰ relative to the whole cells. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N 2 -fixation by diazotrophic cyanobacteria. Based on the δ 13 C values of DPEP (-17.9 to -15.6‰; n=7), we estimated isotopic fractionation associated with photosynthetic carbon fixation to be 8-14‰. This range suggests the importance of β-carboxylation and/or active transport of Correspondence to: Y. Kashiyama (chiro@jamstec.go.jp) the carbon substrate, indicating in turn the substantial contribution of diazotrophic cyanobacteria to primary production. Based on the δ 15 N values of 17-nor-DPEP (-7.4 to -2.4‰; n=7), the δ 15 N range of chlorophylls-c-producing algae was estimated to be -3 to +3‰. This relative depletion in 15 N suggests that these algae mainly utilized nitrogen regenerated from diazotrophic cyanobacteria. Given that diatoms are likely to have constituted the chlorophylls-cproducing algae within the biogenic-silica-rich Onnagawa Formation, cyanobacteria-hosting diatoms may have been important contributors to primary production.

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A novel sedimentary lacustrine chlorin: Characterisation and geochemical significance

Cited by 21 publications

References 15 publications

Distribution and sources of cyclic pheophorbides in the marine environment

Distribution and sources of cyclic pheophorbides in the marine environment

On the sedimentary occurrence of chlorophyllone a

Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments

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