Polar metabolites resulting from petroleum biodegradation are measured in groundwater samples as TPHd unless a silica gel cleanup (SGC) is used on the sample extract to isolate hydrocarbons. Even though the metabolites can be the vast majority of the dissolved organics present in groundwater, SGC has been inconsistently applied because of regulatory concern about the nature and toxicity of the metabolites. A two‐step approach was used to identify polar compounds that were measured as TPHd in groundwater extracts at five sites with biodegrading fuel sources. First, gas chromatography with mass spectrometry (GC‐MS) was used to identify and quantify 57 individual target polar metabolites. Only one of these compounds—dodecanoic acid, which has low potential human toxicity—was detected. Second, nontargeted analysis was used to identify as many polar metabolites as possible using both GC‐MS and GC×GC‐MS. The nontargeted analysis revealed that the mixture of polar metabolites identified in groundwater source areas at these five sites is composed of approximately equal average percentages of organic acids, alcohols and ketones, with few phenols and aldehydes. The mixture identified in downgradient areas at these five sites is dominated by acids, with fewer alcohols, far fewer ketones, and very few aldehydes and phenols. A ranking system consistent with systems used by USEPA and the United Nations was developed for evaluating the potential chronic oral toxicity to humans of the different classes of identified polar metabolites. The vast majority of the identified polar metabolites have a “Low” toxicity profile, and the mixture of identified polar metabolites present in groundwater extracts at these five sites is unlikely to present a significant risk to human health.

Groundwater at fuel release sites often contains nonpolar hydrocarbons that originate from both the fuel release and other environmental sources, as well as polar metabolites of petroleum biodegradation. These compounds, along with other polar artifacts, can be quantified as "total petroleum hydrocarbons" using USEPA Methods 3510/8015B, unless a silica gel cleanup step is used to separate nonpolar hydrocarbons from polar compounds prior to analysis. Only a limited number of these metabolites have been identified by traditional GC-MS methods, because they are difficult to resolve using single-column configurations. Additionally, the targeted use of derivatization limits the detection of many potential metabolites of interest. The objective of this research was to develop a nontargeted GC×GC-TOFMS approach to characterize petroleum metabolites in environmental samples gathered from fuel release sites. The method tentatively identified more than 760 unique polar compounds, including acids/esters, alcohols, phenols, ketones, and aldehydes, from 22 groundwater samples collected at five sites. Standards for 28 polar compounds indicate that effective limits of quantitation for most of these compounds in the groundwater samples range from 1 to 11 μg/L.

Abstract:In an effort to understand the nature and toxicity of petroleum hydrocarbon degradation metabolites, 2-dimensional gas chromatography linked to a time-of-flight mass spectrometer (GCÂGC-TOFMS) was used to conduct nontargeted analysis of the extracts of 61 groundwater samples collected from 10 fuel release sites. An unexpected result was the tentative identification of 197 unique esters. Although esters are known to be part of specific hydrocarbon degradative pathways, they are not commonly considered or evaluated in field studies of petroleum biodegradation. In addition to describing the compounds identified, the present study discusses the role for nontargeted analysis in environmental studies. Overall, the low toxicological profile of the identified esters, along with the limited potential for exposure, renders them unlikely to pose any significant health risk.

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This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.2008), high-resolution site characterization (USEPA 2013) among other initiatives; as ways of streamlining site assessment activities. The triad approach involves three elements: systematic project planning, dynamic work plan strategies, and real-time measurement technologies (ITRC 2007). Development of innovative field screening tools for site assessment falls into the real-time measurement technology element and also influences the dynamic work element. USEPA also recognizes that new technologies and methods need to be evaluated promptly to quickly ascertain whether the new technique is suitable for the site in terms of data quality objectives, cost and effectiveness (USEPA 2008).The increase in the use of innovative field screening tools for real-time assessment of chemical contamination for rapid vertical and horizontal source zone or dissolved plume delineation has led to less reliance on laboratory testing as evidenced by the use of direct-push tools to characterize the subsurface (membrane interface probe [MIP], laser-induced fluorescence, and others). Field screening tools bypass the wait for traditional laboratory analytical results in favor of nearly real-time results that facilitate quick decisions, for example, on monitoring well placement or areas requiring further characterization. Semi-quantitative methods, as defined by USEPA, provide order of magnitude estimations of contamination (e.g., 10s, 100s and 1000s of micrograms per liter [µg/L]); semi-quantitative methods can be used for defining the location of known types of contamination (USEPA 1997). MIP is an example of a semi-quantitative Abstract A field screening method was developed for rapid measurement of benzene and gasoline range total petroleum hydrocarbons (TPHg) concentrations in groundwater. The method is based on collecting photoionization detector (PID) measurements from vapor samples. The vapor samples are collected by bubbling air through groundwater samples (air sparging) with a constant volume, temperature and sparging rate. The level of accuracy, sensitivity, precision, and statistical significance of the estimated concentrations, derived from the screening method, are comparable to conventional laboratory analytical results at concentrations equal to or greater than 150 µg/L for benzene and greater than 50 µg/L for TPHg. The method's concentration estimations can assist in making real-time decisions regarding location of dissolved plumes and light nonaqueous phase liquid (LNAPL) source zones at many fuel release sites. The screening method was tested in the laboratory and in the field with 208 and 107 samples, respectively. The study concludes that the screening method can be used as a tool to aid in completing a site conceptual model as well as analyz...