Examining natural attenuation and acute toxicity of petroleum-derived dissolved organic matter with optical spectroscopy

Groundwater samples containing petroleum-derived dissolved organic matter (DOM_HC) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOM_HC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm (a₂₅₄) along a transect of the DOM_HCplume indicates that a₂₅₄ can be used to quantitatively assess natural attenuation of DOM_HC. Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOM_HC beneath and adjacent to the oil body is dominated by aliphatic, low O/C compounds (“protein-like” fluorescence) and that the composition gradually evolves to aromatic, high O/C compounds (“humic-/fulvic-like” fluorescence) as a function of distance downgradient from the oil body. Finally, a direct, positive correlation between optical properties and Microtox acute toxicity assays demonstrates the utility of these combined techniques in assessing the spatial and temporal natural attenuation and toxicity of the DOM_HC in petroleum-impacted groundwater systems.