Soluble Manganese(III) in the Marine Environment

Wednesday, 17 December 2014: 2:10 PM
George W Luther III1, Veronique Oldham2, Andrew Madison3, Bradley Tebo4, Matthew Jones4, Laramie Jensen5, Shannon Owings6, Alfonso Mucci7 and Bjorn Sundby7, (1)University of Delaware, Lewes, DE, United States, (2)College of Marine and Earth Studies, Lewes, DE, United States, (3)Golder Associates Inc., Geochemistry, Mt. Laurel, NJ, United States, (4)Oregon Health & Science University, Portland, OR, United States, (5)Carleton College, Chemistry, Northfield, MN, United States, (6)Georgia Institue of Technology, School of Earth and Atmospheric Sciences, Atlanta, United States, (7)McGill University, Montreal, QC, Canada
Recent field studies have confirmed the presence of soluble manganese(III), which along with Mn(II) passes through a 0.2 µm filter, in suboxic marine waters. Here we applied a spectrophotometric method using a soluble porphyrin as a competitive ligand to calculate the concentrations and kinetics of Mn(II) and Mn(III) recovery. Data will be presented from the suboxic porewaters of the Saint Lawrence estuary, the suboxic and anoxic waters of the Chesapeake Bay and the oxygenated surface waters of a coastal waterway bordered by wetlands and salt marshes in Delaware.

Soluble Mn(III) accounts for up to 100% of the dissolved Mn pool with concentrations ranging from the detection limit of 50 nM to 80 µM at the oxic/anoxic interface of the non-sulfidic porewaters from the hemipelagic sediments of the St. Lawrence Estuary. Data indicate weak-ligand complexation of Mn(III) formed from Mn(II) oxidation as well as reduction of MnO2.

Complexation of Mn(III) in the anoxic waters of Chesapeake Bay appears stronger as the porphyrin could not outcompete the natural ligands binding Mn(III). Mn(III) complexes were reduced in the presence of hydroxylamine or hydrogen sulfide and detected as Mn(II). Soluble Mn(III) comprised up to 52 % of total dissolved Mn. Profiles over the course of a five day cruise showed that high Mn(III) concentrations (7.3 μM) were observed at low H2S (4.9 μM) whereas low Mn(III) (1.1 μM) was detected at high H2S (40 μM). The presence of Mn(III) in sulfidic waters indicated that it is kinetically stabilized in situ by strong ligands so reduction to Mn(II) was incomplete. One electron reductive dissolution of solid MnO2 particles formed at the oxic-anoxic interface appear to be the source of Mn(III).

Lastly, soluble Mn(III) was detected in the oxygenated surface waters of a coastal waterway (salinity ranging from freshwater to 31) bordered by wetlands and salt marshes in Delaware. Soluble Mn(III) made up 0-49 % of the total dissolved Mn (maximum of 1.92 μM) with the highest concentrations and percentages coming from waters adjacent to salt marsh areas. The porphyrin competitive ligand could not outcompete the natural ligands, which appear to be humic material; thus, a reductant was again needed to convert the Mn(III) complexes to Mn(II) for measurement.