Photoreactivities of two distinct dissolved organic matter pools in groundwater of a subarctic island

Abstract

Abstract Groundwater is a potentially significant source of dissolved organic matter (DOM) to coastal oceans where it is subject to photochemical transformation and thus possibly influences major marine biogeochemical processes. Furthermore, groundwater DOM usually receives little prior light exposure, making it suitable for probing the photoreactivity of source organic materials. In this study we collected two DOM pools in beach and inland groundwater of the Iles-de-la-Madeleine in the Gulf of St. Lawrence, characterized them with absorbance and fluorescence spectroscopy , and compared their photoreactivities. Beach groundwater (BGW) primarily comprised old, highly colored terrestrial DOM having high molecular weight (MW), strong humification , and low protein contents, whereas inland groundwater (IGW) largely contained fresh, less colored microbial-derived DOM with low molecular weight (MW), weaker humification, and higher protein contents. For both BGW and IGW, exposure to solar-simulated radiation led to increases in the E 2/E3 quotient, biological index (BIX), and ammonium (NH4+ ) and decreases in absorbance, specific absorption coefficient at 254 nm (SUVα 254 ), fluorescence index (FI), humification index (HIX), MW, and dissolved organic carbon (DOC). The irradiation also reduced the intensities of humic-like fluorescence peaks and PARAFAC-modeled humic components. On a fractional-absorption-loss basis, the photochemically induced fractional changes in BGW were comparable to those in IGB for SUVα 254 and E2/E3, considerably larger for MW, BIX, and DOC, and substantially smaller for FI and HIX. On an absorbed-photon basis, the efficiencies of absorbance photobleaching and DOC photomineralization for DOM in BGW were 8.3 times and 2.0 times those of the respective photoprocesses for DOM in IGW, while the efficiency of photoammonification for DOM in BGW was 41% of that for DOM in IGW. Results from this study, in combination with those reported previously for surface waters, lead to a tentative paradigm: terrigenous DOM is more prone to absorbance photobleaching but less prone to photoammonification than microbial-derived DOM while the two DOM pools are comparably reactive with respect to DOC photomineralization.