Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

A high resolution study of the chlorophyll and bacteriochlorophyll pigment distributions in a calcite/gypsum microbial mat

Application of a high resolution high performance liquid chromatography-mass spectrometry method to the study of a microbial mat system has permitted the identification of a greater number of pigments derived from green bacteria than reported in a previous study. Although the green bacteria found in the mat were identified as Chloroflexus-like, bacteriochlorophylls and bacteriophaeophytins c that can be attributed to Chloroflexaceae on the basis of literature reports account for less than 10% of the pigments derived from green bacteria in the mat. Analysis of the bacteriochlorophylls and bacteriophaeophytins c and d using atmospheric pressure chemical ionisation-liquid chromatography-tandem mass spectrometry reveals complex depth profiles, signalling inputs from a number of organisms. The pigment compositions provide evidence for green bacteria living in close proximity to the living cyanobacterial mat. Depth profiles of pigments derived from green, purple and cyanobacteria indicate that the remnants of mats present in the deeper part of the section contain a record dominated by signatures from anoxygenic photoautotrophs.

Development and application of a high resolution liquid chromatographic method for the analysis of complex pigment distributions

Ternary and binary gradient systems have been developed for the high-performance liquid chromatographic analysis of complex pigment distributions typical of natural samples. Improved chromatographic resolution reveals significantly more pigment components in extracts from a sediment (Priest Pot, Cumbria, UK), a microbial mat (les Salines de la Trinital, South Catalonia, Spain) and a culture (C. phaeobacteroides) including novel bacteriochlorophyll derivatives. The methods developed are directly suited to LC–MS analysis and the automated acquisition of MS/MS data for pigments.