Quantification of chlorophyll a, chlorophyll b and pheopigments a in lake sediments through deconvolution of bulk UV-VIS absorption spectra

Assessments of aquatic paleoproduction and pigment preservation require accurate identification and quantification of sedimentary chlorophylls. Using chromatographic techniques to analyze long records at high resolution is impractical because they are expensive and labor intensive. We have developed a new rapid and low-cost approach to infer the concentrations of chlorophyll a, chlorophyll b and related chlorophyll derivatives (pheopigments a) from the mathematical decomposition of UV-VIS measured bulk spectrophotometer absorption spectra of standard solutions and sediment extracts. We validated our method against high-performance liquid chromatography (HPLC) measurements on standard solutions and on varved, anoxic sediment from eutrophic Lake Lugano (Ponte Tresa sub-basin, southern Switzerland), where the history of productivity is relatively well known for the twentieth century. Our mathematical approach quantifies the concentration of chlorophyll b (R-adJ(2) = 0.99, RMSEP similar to 5.9%), chlorophyll a (R-adJ(2) = 0.98, RMSEP similar to 5.0%), and pyropheophorbide a (R-adJ(2) = 0.99, RMSEP similar to 7.8%) in standard solutions. We obtain comparable results for total chloropigment a (chlorophyll a + pheopigments a), chlorophyll a and diagenetic products (pheopigments a) in the sediment samples of our case study (Ponte Tresa). Here, HPLC concentrations of chlorophyll b are very low. The method has, however, the potential to achieve values for chlorophyll b concentrations in sediments with chlorophylls a/chlorophylls b ratios lower than 3.4. The pigment stratigraphy of the Ponte Tresa sediments correspond very well with the paleoproduction and eutrophication history of the twentieth century. The ratio between chlorophyll a and pheopigments a used as a qualitative indicator of sedimentary chlorophyll preservation (chlorophyll a/ {chlorophyll a + pheopigments a}) is only weakly correlated with aquatic paleoproduction (r(adj) = 0.35, p-value = 0.045) and remained remarkably constant in the recent century despite strong anthropogenic eutrophication. The new method is useful for obtaining, in a cost- and time-efficient way, information about major sedimentary pigment groups that are relevant to inferring paleoproduction, potentially green algae biomass, pigment preservation and early diagenetic effects.