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Examining Natural Attenuation and Acute Toxicity of Petroleum-Derived Dissolved Organic Matter with Optical Spectroscopy
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Abstract
Groundwater samples containing petroleum-derived dissolved organic matter (DOMHC)
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 DOMHC 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 DOMHC plume indicates that a254
can be used to quantitatively assess natural attenuation of DOMHC. Fluorescence components,
identified by parallel factor (PARAFAC) analysis, show that the composition of the
DOMHC 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 DOMHC
in petroleum-impacted groundwater systems.