Paul Philp

Methyl diamantane index (MDI) as a maturity parameter for Lower Palaeozoic carbonate rocks at high maturity and overmaturity

Diamantanes were identified in extracts from the Lower Ordovician Majiagou Formations (O1m5) of the central gas field, Shanganning Basin, China. At 3100‐3800 m, corresponding to Ro 1.9‐3.9%, the MDI [methyl diamantane index=4-MD/(1-MD+3-MD+4-MD)] ranges from 40 to 65% for the source rock extracts. Changes in the MDI index in the very mature sections (Ro>2.0%) are relatively small and no linear correlation between MDI and Ro ,o r MDI and depth, is noted, as previously reported, suggesting the possibility that the MDI may have limited applicability in maturity determinations. # 2000 Elsevier Science Ltd. All rights reserved.

3D-CSIA: carbon, chlorine, and hydrogen isotope fractionation in transformation of TCE to ethene by a Dehalococcoides culture.

Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc. The Cl effects (combined with an inverse H effect in TCE) suggested that dechlorination proceeded through nucleophilic reactions with cobalamin rather than by an electron transfer mechanism. Depletions of (37)Cl in daughter compounds, resulting from fractionation at positions away from the dechlorination center (secondary isotope effects), further support the nucleophilic dechlorination mechanism. Determination of C and Cl isotope ratios of the reactants and products in the reductive dechlorination chain offers a potential tool for differentiation of Dhc activity from alternative transformation mechanisms (e.g., aerobic degradation and reductive dechlorination proceeding via outer sphere mechanisms), in studies of in situ attenuation of chlorinated ethenes. Hydrogenation of the reaction products (DCE, VC, and ethene) showed a major preference for the (1)H isotope. Detection of depleted dechlorination products could provide a line of evidence in discrimination between alternative sources of TCE (e.g., evolution from DNAPL sources or from conversion of PCE).

Application of CSIA to distinguish between vapor intrusion and indoor sources of VOCs.

At buildings with potential for vapor intrusion of volatile organic chemicals (VOCs) from the subsurface, the ability to accurately distinguish between vapor intrusion and indoor sources of VOCs is needed to support accurate and efficient vapor intrusion investigations. We have developed a method for application of compound-specific stable isotope analysis (CSIA) for this purpose that uses an adsorbent sampler to obtain sufficient sample mass from the air for analysis. Application of this method to five residences near Hill Air Force Base in Utah indicates that subsurface and indoor sources of tricholorethene and tetrachloroethene often exhibit distinct carbon and chlorine isotope ratios. The differences in isotope ratios between indoor and subsurface sources can be used to identify the source of these chemicals when they are present in indoor air.

Natural attenuation/phytoremediation in the vadose zone of a former industrial sludge basin.

The natural attenuation of polyaromatic hydrocarbons (PAHs) in the vadose zone of a naturally revegetated former industrial sludge basin (0.45 ha) was examined. This was accomplished by comparing the concentration of 16 PAH contaminants present in sludge collected below the root zone of plants with contaminants present at 3 shallower depths within the root zone. Chemical analysis of 240 samples from 60 cores showed the average concentration of total and individual PAHs in the 0–30 cm, 30–60 cm, and bottom of the root zone strata were approximately 10, 20, and 50%, respectively, of the 16, 800 ppm average total PAH concentration in deep non-rooted sludge. Statistically significant differences in average PAH concentrations were observed between each strata studied and the non-rooted sludge except for the concentrations of acenaphthene and chrysene present at the bottom of the root zone in comparison to sludge values. The rooting depth of the vegetation growing in the basin was dependent on both vegetation type and plant age. Average rooting depths for trees, forbs (herbaceous non-grasses), and grasses were 90, 60, and 50 cm, respectively. The deepest root systems observed (100–120 cm) were associated with the oldest (12–14 year-old) mulberry trees. Examination of root systems and PAH concentrations at numerous locations and depths within the basin indicated that plant roots and their microbially active rhizospheres fostered PAH disappearance; including water insoluble, low volatility compounds, i.e. benzo(a)pyrene and benzo(ghi)perylene. The reduced concentration of PAHs in the upper strata of this revegetated former sludge basin indicated that natural attenuation had occurred. This observation supports the concept that through appropriate planting and management practices (phytoremediation) it will be possible to accelerate, maximize, and sustain natural processes, whereby even the most recalcitrant PAH contaminants (i.e. benzo(a)pyrene) can be remediated over time.

Demonstration of Compound-Specific Isotope Analysis of Hydrogen Isotope Ratios in Chlorinated Ethenes

High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

Carbon isotope fractionation in reactions of 1,2-dibromoethane with FeS and hydrogen sulfide.

EDB (1,2-dibromoethane) is frequently detected at sites impacted by leaded gasoline. In reducing environments, EDB is highly susceptible to abiotic degradation. A study was conducted to evaluate the potential of compound-specific isotope analysis (CSIA) in assessing abiotic degradation of EDB in sulfate-reducing environments. Water containing EDB was incubated in sealed vials with various combinations of Na(2)S (<0.7 mM) and mackinawite (FeS) (180 mM). Degradation rates in vials containing FeS exceeded those in Na(2)S-only controls. In the presence of FeS, first-order constants ranged from 0.034 ± 0.002 d(-1) at pH 6 to 0.081 ± 0.005 d(-1) at pH 8.5. In the presence of FeS, products from reductive debromination (ethylene) and from S(N)2 substitution with S(II) nucleophiles were detected (1,2-dithioethane, DTA). Relatively high yields of DTA suggested that the S(N)2 reactions were not mediated by HS(-) only but likely also included reactions mediated by FeS surface. Significant carbon isotope effects were observed for nucleophilic substitution by HS(-) (ε = -31.6 ± 3.7‰) and for a combination of reductive and substitution pathways in the presence of FeS (-30.9 ± 0.7‰), indicating good site assessment potential of CSIA. The isotope effects (KIEs) observed in the presence of FeS corroborated the predominance of S(N)2 substitution by nucleophiles combined with two-electron transfer reductive debromination.

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.