Comprehensive Two-Dimensional Gas Chromatography with Peak Tracking for Screening of Constituent Biodegradation in Petroleum UVCB Substances.

Petroleum substances, as archetypical UVCBs (substances of unknown or variable composition, complex reaction products, or biological substances), pose a challenge for chemical risk assessment as they contain hundreds to thousands of individual constituents. It is particularly challenging to determine the biodegradability of petroleum substances since each constituent behaves differently. Testing the whole substance provides an average biodegradation, but it would be effectively impossible to obtain all constituents and test them individually. To overcome this challenge, comprehensive two-dimensional gas chromatography (GC × GC) in combination with advanced data-handling algorithms was applied to track and calculate degradation half-times (DT50s) of individual constituents in two dispersed middle distillate gas oils in seawater. By tracking >1000 peaks (representing ∼53-54% of the total mass across the entire chromatographic area), known biodegradation patterns of oil constituents were confirmed and extended to include many hundreds not currently investigated by traditional one-dimensional GC methods. Approximately 95% of the total tracked peak mass biodegraded after 64 days. By tracking the microbial community evolution, a correlation between the presence of functional microbial communities and the observed progression of DT50s between chemical classes was demonstrated. This approach could be used to screen the persistence of GC × GC-amenable constituents of petroleum substance UVCBs.

Modeling the GCxGC Elution Patterns of a Hydrocarbon Structure Library To Innovate Environmental Risk Assessments of Petroleum Substances.

Comprehensive two-dimensional gas chromatography (GCxGC) offers unrivaled separation of petroleum substances, which can contain thousands of constituents or more. However, interpreting substance compositions from GCxGC data is costly and requires expertise. To facilitate environmental risk assessments, industries provide aggregated compositional information known as "hydrocarbon blocks" (HCBs), but these proprietary methods do not transparently associate the HCBs with GCxGC chromatogram data. These obstacles frustrate efforts to study the environmental risks of petroleum substances and associated environmental samples. To address this problem, we developed a GCxGC elution model for user-defined petroleum substance compositions. We calibrated the elution model to experimental GCxGC retention times of 56 known hydrocarbons by fitting three tunable model parameters to two candidate instrument methods. With the calibrated model, we simulated retention times for a library of 15,447-15,455 hydrocarbon structures (plus 40-48 predicted as chromatographically unretained) spanning 11 classes of petroleum substance constituents in the C10-C30 range. The resulting simulation data reveal that GCxGC retention times are quantitatively associated with hydrocarbon class and carbon number information throughout the GCxGC chromatogram. These innovations enable the development of transparent and efficient technical methods to investigate the chemical compositions and environmental properties of petroleum substances, including in environmental and lab-weathered samples.

Linking biodegradation kinetics, microbial composition and test temperature - Testing 40 petroleum hydrocarbons using inocula collected in winter and summer.

Many factors affect the biodegradation kinetics of chemicals in test systems and the environment. Empirical knowledge is needed on how much test temperature, inoculum, test substances and co-substrates influence the biodegradation kinetics and microbial composition in the test. Water was sampled from the Gudenaa river in winter (2.7 °C) and summer (17 °C) (microbial inoculum) and combined with an aqueous stock solution of >40 petroleum hydrocarbons prepared by passive dosing. This resulted in low-concentration test systems that were incubated for 30 days at 2.7, 12 and 20 °C. Primary biodegradation kinetics, based on substrate depletion relative to abiotic controls, were determined with automated Solid Phase Microextraction coupled to GC/MS. Biodegradation kinetics were remarkably similar for summer and winter inocula when tested at the same temperature, except when cooling summer inoculum to 2.7 °C which delayed degradation relative to winter inoculum. Amplicon sequencing was applied to determine shifts in the microbial composition between season and during incubations: (1) the microbial composition of summer and winter inocula were remarkably similar, (2) the incubation and the incubation temperature had both a clear impact on the microbial composition and (3) the effect of adding >40 petroleum hydrocarbons at low test concentrations was limited but resulted in some proliferation of the known petroleum hydrocarbon degraders Nevskia and Sulfuritalea. Overall, biodegradation kinetics and its temperature dependency were very similar for winter and summer inoculum, whereas the microbial composition was more affected by incubation and test temperature compared to the addition of test chemicals at low concentrations.

Moving persistence assessments into the 21st century: A role for weight-of-evidence and overall persistence.

Assessing the persistence of chemicals in the environment is a key element in existing regulatory frameworks to protect human health and ecosystems. Persistence in the environment depends on many fate processes, including abiotic and biotic transformations and physical partitioning, which depend on substances' physicochemical properties and environmental conditions. A main challenge in persistence assessment is that existing frameworks rely on simplistic and reductionist evaluation schemes that may lead substances to be falsely assessed as persistent or the other way around-to be falsely assessed as nonpersistent. Those evaluation schemes typically assess persistence against degradation half-lives determined in single-compartment simulation tests or against degradation levels measured in stringent screening tests. Most of the available test methods, however, do not apply to all types of substances, especially substances that are poorly soluble, complex in composition, highly sorptive, or volatile. In addition, the currently applied half-life criteria are derived mainly from a few legacy persistent organic pollutants, which do not represent the large diversity of substances entering the environment. Persistence assessment would undoubtedly benefit from the development of more flexible and holistic evaluation schemes including new concepts and methods. A weight-of-evidence (WoE) approach incorporating multiple influencing factors is needed to account for chemical fate and transformation in the whole environment so as to assess overall persistence. The present paper's aim is to begin to develop an integrated assessment framework that combines multimedia approaches to organize and interpret data using a clear WoE approach to allow for a more consistent, transparent, and thorough assessment of persistence. Integr Environ Assess Manag 2022;18:868-887. © 2021 ExxonMobil Biomedical Sciences, Inc. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Biodegradability assessment of complex, hydrophobic substances: Insights from gas-to-liquid (GTL) fuel and solvent testing.

The assessment of substances of Unknown or Variable composition, Complex reaction products or Biological materials (UVCBs) presents significant challenges when determining biodegradation potential and environmental persistence for regulatory purposes. An example of UVCBs is the gas-to-liquid (GTL) products, which are synthetic hydrocarbons produced from natural gas using a catalytic process known as the Fischer-Tropsch process. These synthetic hydrocarbons are fractionated into a wide array of products equivalent in function to their petroleum-derived analogues. Here we summarise the results of an extensive testing program to assess the biodegradability of several GTL products. This program highlights the challenges associated with UVCBs and provides a case study for the assessment of such substances that are also poorly soluble and volatile. When tested with the appropriate methods, all the GTL products assessed in this study were found to be readily biodegradable indicating they are not likely to be persistent in the environment.

Terrestrial Toxicity of Synthetic Gas-to-Liquid versus Crude Oil-Derived Drilling Fluids in Soil.

Unlike most other conventional petroleum products that are derived from crude oil, gas-to-liquids (GTLs) are petroleum products that are synthesized from natural gas (methane). This process results in GTL products having no sulfur and low aromatic content, so they should have less impact on human health and the environment compared with crude oil-derived products. The GTLs have been registered for use as nonaqueous base fluids (NABFs) in drilling muds, which aid in the process of drilling wells for oil and gas extraction; it is through these uses and others that they enter terrestrial environments. The primary objective of the present study was to determine whether GTLs were less toxic to terrestrial soil biota than conventional NABFs used for land-based drilling, such as diesel and low-toxicity mineral oil (LTMO). A second objective was to understand the fate and impact of these fluids under more realistic soil and aging conditions of a common west Texas (USA) oil-producing region (i.e., sandy loam soil with low organic matter and a hot arid climate). Acute terrestrial toxicity studies were conducted on the soft-bodied terrestrial invertebrate earthworm (Eisenia fetida) along with 3 plant species-alfalfa (Medicago stavia), thickspike wheatgrass (Elymus lanceolatus), and fourwing saltbrush (Atriplex canescens). We also assessed changes in microbial community structure of the soils following additions of NABF. Overall, the GTL NABFs had lower toxicity compared with conventional NABFs like diesel and LTMO, as measured by invertebrate toxicity, plant seed germination, and impact on the microbial community. Environ Toxicol Chem 2020;39:721-730. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.