Chemical fingerprinting of hydrocarbon-contamination in soil.

Chemical fingerprinting analyses of 29 hydrocarbon-contaminated soils were performed to assess the soil quality and determine the main contaminant sources. The results were compared to an assessment based on concentrations of the 16 priority polycyclic aromatic hydrocarbons pointed out by the U.S. Environmental Protection Agency (EPAPAH16) and total petroleum hydrocarbon (TPH). The chemical fingerprinting strategy proposed in this study included four tiers: (i) qualitative analysis of GC-FID chromatograms, (ii) comparison of the chemical composition of both un-substituted and alkyl-substituted polycyclic aromatic compounds (PACs), (iii) diagnostic ratios of selected PACs, and (iv) multivariate data analysis of sum-normalized PAC concentrations. The assessment criteria included quantitative analysis of 19 PACs and C1-C4 alkyl-substituted homologues of naphthalene, fluorene, dibenzothiophene, phenanthrene, pyrene, and chrysene; and 13 oxygenated polycyclic aromatic compounds (O-PACs). The chemical composition of un-substituted and alkyl-substituted PACs and visual interpretation of GC-FID chromatograms were in combination successful in differentiating pyrogenic and petrogenic hydrocarbon sources and in assessing weathering trends of hydrocarbon contamination in the soils. Multivariate data analysis of sum-normalized concentrations could as a stand-alone tool distinguish between hydrocarbon sources of petrogenic and pyrogenic origin, differentiate within petrogenic sources, and detect weathering trends. Diagnostic ratios of PACs were not successful for source identification of the heavily weathered hydrocarbon sources in the soils. The fingerprinting of contaminated soils revealed an underestimation of PACs in petrogenic contaminated soils when the assessment was based solely on EPAPAH16. As alkyl-substituted PACs are dominant in petrogenic sources, the evaluation of the total load of PACs based on EPAPAH16 was not representative. Likewise, the O-PACs are not represented in soil quality assessments based on EPAPAH16 and TPH. The ∑O-PACs ranged between

Polar metabolites of polycyclic aromatic compounds from fungi are potential soil and groundwater contaminants.

This study investigated the sorption to soil of water-soluble metabolites from polycyclic aromatic compounds (PACs). The soil fungus Cunninghamella elegans was used to produce PAC metabolites from two un-substituted PACs (phenanthrene, pyrene), three alkyl-substituted PACs (2-methylnaphthalene, 1-methylphenanthrene, 1-methylpyrene), and one sulfur-containing heterocyclic PAC (dibenzothiophene). Fifty-eight metabolites were tentatively identified; metabolites from the un-substituted PACs were hydroxylated and sulfate conjugated, whereas metabolites from alkyl-substituted PACs were sulfate conjugated and either hydroxylated or oxidized to carboxylic acids at the methyl group. The metabolism of the sulfur-containing heterocyclic PAC resulted in sulfate conjugates. The sorption of the PAC metabolites to three soils was determined using a batch equilibrium method, and partition coefficients (Kd's) were calculated for fourteen representative metabolites. Sulfate conjugated metabolites displayed Kd's below 70 whereas the metabolites with both a sulfate and a carboxylic acid group had Kd's below 2.8. The low Kd's of water-soluble PAC metabolites indicate high mobility in soil and a potential for leaching to surface- and groundwaters.

The use of environmental metabolomics to determine glyphosate level of exposure in rapeseed (Brassica napus L.) seedlings.

Metabolic profiling in plants can be used to differentiate between treatments and to search for biomarkers for exposure. A methodology for processing Ultra-High-Performance Liquid Chromatography-Diode-Array-Detection data is devised. This methodology includes a scheme for selecting informative wavelengths, baseline removal, retention time alignment, selection of relevant retention times, and principal component analysis (PCA). Plant crude extracts from rapeseed seedling exposed to sublethal concentrations of glyphosate are used as a study case. Through this approach, plants exposed to concentrations down to 5 µM could be distinguished from the controls. The compounds responsible for this differentiation were partially identified and were different from those specific for high exposure samples, which suggests that two different responses to glyphosate are elicited in rapeseed depending on the level of exposure. The PCA loadings indicate that a combination of other metabolites could be more sensitive than the response of shikimate to detect glyphosate exposure.

Quantification and source identification of polycyclic aromatic hydrocarbons in sediment, soil, and water spinach from Hanoi, Vietnam.

Polycyclic aromatic hydrocarbons (PAHs) were quantified in sediment, soil, and plant material from Hanoi, Vietnam, and an aquatic production system in peri-urban Hanoi. The sum of the concentration of 16 US-EPA priority PAHs ( summation PAH16) ranged between 0.44 and 6.21 mg kg(-1) dw in sediment and between 0.26 and 1.35 mg kg(-1) dw in soil, with decreasing concentrations from the urban area to the peri-urban area, indicating contributions from urban and industrial sources. Double plots of diagnostic source ratios indicate that PAHs originate from mixed petrogenic and pyrogenic sources, the latter being predominant. The predominance of low molecular weight (LMW) PAHs in the sediment samples suggests that petrogenic sources are more prevalent in the water environment than in the soil. In contrast, high molecular weight (HMW) PAHs dominated in water spinach which probably reflects the plant's uptake of particle-bound PAHs that originate from pyrogenic sources.