Results from natural and engineered phytoremediation systems provide strong evidencethatvegetated soils mitigate polycyclic aromatic hydrocarbon (PAH) contamination. However, the mechanisms by which PAH mitigation occurs and the impact of plant organic matter on PAH attenuation remain unclear. This study assessed the impact of plant organic matter on PAH attenuation in labile and refractory sediments fractions from a petroleum distillate waste pit that has naturally revegetated. Samples were collected in distinct zones of barren and vegetated areas to assess changes to organic matter composition and PAH content as vegetation colonized and became established in the waste pit. Sediments were fractionated into bulk sediment and humin fractions and analyzed for organic matter composition by isotope ratio mass spectrometry (delta (13)C), 13C nuclear magnetic resonance (13C NMR), delta 14C AMS (accelerator mass spectrometry), and percent organic carbon (%TOC). Gas chromatography mass spectrometry (GC/ MS) of lipid extracts of SOM fractions provided data for PAH distribution histograms, compound weathering ratios, and alkylated and nonalkylated PAH concentrations. Inputs of biogenic plant carbon, PAH weathering, and declines in PAH concentrations are most evidentfor vegetated SOM fractions, particularly humin fractions. Sequestered PAH metabolites were also observed in vegetated humin. These results show that plant organic matter does impact PAH attenuation in both labile and refractory fractions of petroleum distillate waste.
We examined polycyclic aromatic hydrocarbon (PAH) attenuation in contaminated field sediments after only 2 years of plant growth. We collected sediments from vegetated and non-vegetated areas at the Indiana Harbor Canal (IHC), an industrialized area with historic petroleum contamination of soils and sediments. PAH concentrations, PAH weathering indices, and organic matter composition in sediments colonized by Phragmites, cattails, or willow trees were compared to the same indices for non-vegetated sediments. We hypothesized that bulk sediment and humin fractions with measurable increases in plant organic matter content would show measurable changes to PAH attenuation as indicated by more weathered PAH diagnostic ratios or reduced PAH concentrations. Carbon-normalized PAH concentrations were lower in vegetated bulk sediments but higher in vegetated humin fractions relative to non-vegetated sediment fractions. Total organic carbon content was not indicative of more weathered N3/P2 ratios or reduced PAH concentrations in vegetated sediment fractions. More weathered N3/P2 ratios were observed with increased modern carbon (plant carbon) content of vegetated sediment fractions. Phragmites sediments contained more modern carbon (plant carbon) and more weathered PAH ratios [C3-naphthalenes and C2-phenanthrenes (N3/P2)] than willow, cattail, and non-vegetated sediments.
Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C(3)-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k(slow) and k(very slow). After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.
The Mystro Assembler Construction System (MACS) is a tool kit for assembler writers, based upon a parser‐generator for ambiguous attribute grammars, automatic text manipulation, and a skeletal assembler. Attention has been paid in MACS to aiding the assembler writer in employing the software methodology of iterative enhancement and in avoiding the more tedious aspects of assembler construction.
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