Analytical phytoplankton carbon measurements spanning diverse ecosystems

The measurement of phytoplankton carbon (Cphyto) in the field has been a long-sought but elusive goal in oceanography. Proxy measurements of Cphyto have been employed in the past, but are subject to many confounding influences that undermine their accuracy. Here we report the first directly measured Cphyto values from the open ocean. The Cphyto samples were collected from a diversity of environments, ranging from Pacific and Atlantic oligotrophic gyres to equatorial upwelling systems to temperate spring conditions. When compared to earlier proxies, direct measurements of Cphyto exhibit the strongest relationship with particulate backscattering coefficients (bbp) (R2=0.69). Chlorophyll concentration and total particulate organic carbon (POC) concentration accounted for ~20% less variability in Cphyto than bbp. Ratios of Cphyto to Chl a span an order of magnitude moving across and within distinct ecosystems. Similarly, Cphyto:POC ratios were variable with the lowest values coming from productive temperate waters and the highest from oligotrophic gyres. A strong relationship between Cphyto and bbp is particularly significant because bbp is a property retrievable from satellite ocean color measurements. Our results, therefore, are highly encouraging for the global monitoring of phytoplankton biomass from space. The continued application of our Cphyto measurement approach will enable validation of satellite retrievals and contribute to an improved understanding of environmental controls on phytoplankton biomass and physiology.

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of the ultraviolet screening pigment scytonemin: characteristic fragmentations

Atmospheric pressure chemical ionisation reversed-phase high-performance liquid chromatography/multistage mass spectrometry has been used to study the mass spectral fragmentation of the cyanobacterial sheath pigment scytonemin and its reduced counterpart. The two pigments exhibit characteristic fragment ions in their MS2 and MS3 spectra that are of value in confirming the identification of the structures in extracts from natural environments.

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of bacteriochlorophylls from Chlorobiaceae: characteristic fragmentations

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry/mass spectrometry (APCI-LC/MS/MS) has been applied to the study of bacteriochlorophylls c, d, and e of phototrophic prokaryotes. Cultures of Chlorobiaceae containing bacteriochlorophyll c, d or e were examined using a high-resolution high-performance liquid chromatography (HPLC) method and APCI-LC/MS/MS employing post-column addition of formic acid. The results reveal complex distributions of bacteriochlorophyll homologues, with some closely eluting species giving isobaric protonated molecules. On-line LC/MS/MS studies reveal characteristic fragment ions for bacteriochlorophylls c, d, and e. Fragmentations involving loss of the extended alkyl substituents that are unique to bacteriochlorophylls c, d and e and their derivatives have been rationalised by studying the phaeophorbides and the results applied to the direct study of the bacteriochlorophylls.