Fluorescence peak integration ratio IC:IT as a new potential indicator tracing the compositional changes in chromophoric dissolved organic matter

Abstract

The present study demonstrates that the ratio of fluorescence integration of peak C to peak T (IC:IT) can be used as an indicator tracing the compositional dynamics of chromophoric dissolved organic matter (CDOM). CDOM absorption and fluorescence spectroscopy and stable isotope δ13C were determined on a seasonal basis in seventeen Chinese inland waters as well as in a series of mixing and photodegradation experiments in the lab. A strong positive linear correlation was recorded between IC:IT and the ratio of terrestrial humic-like C1 to tryptophan-like C4 (C1:C4) derived by parallel factor analysis. The r2 for the linear fitting between IC:IT and C1:C4 (r2=0.80) was notably higher than between C1:C4 and other indices tested, including the ratio of CDOM absorption at 250nm to 365nm, i.e. a(250):a(365) (r2=0.09), spectral slope (S275–295) (r2=0.26), spectral slope ratio (SR) (r2=0.31), the humification index (HIX) (r2=0.47), the recent autochthonous biological contribution index (BIX) (r2=0.27), and a fluorescence index (FI370) (r2=0.07). IC:IT exhibited larger variability than the remaining six indices and a closer correlation with stable isotope δ13C than that observed for a(250):a(365), S275–295, SR, FI370, and BIX during field campaigns. Confirming our field observations, significant correlations were recorded between IC:IT and the remaining six indices, and IC:IT also demonstrated notably larger variability than the six other indices during our wastewater addition experiment. Compared with HIX, eutrophic water addition and photobleaching substantially decreased IC:IT but had no pronounced effect on a(250):a(365), S275–297, SR, FI370, and BIX, further suggesting that IC:IT is the most efficient indicator of the CDOM compositional dynamics.