Rebuttal to correspondence on “Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques”
No abstract available.
Environmental Science & Technology↗
Geology topics
Barbara Bekins
Publications and source records attributed to Barbara Bekins.
Natural source zone depletion of crude oil in the subsurface: Processes controlling mass losses of individual compounds
At many petroleum hydrocarbon spill sites, residual spilled product forms a long-term source of groundwater contamination. The phrase source zone natural depletion is used to refer to the mass loss rates. Overall mass lost under environmental conditions was analyzed using conservative biomarker concentrations for a 1979 oil spill in northern Minnesota, USA. After 40–41 years, an average of 50% of the mass was lost with values ranging from 22% to 57% depending on location. It is also important to understand the composition changes in the source. To understand controls on the losses of individual compounds, concentrations of volatile hydrocarbons in oil samples were compared with aqueous solubilities, and pore-space oil saturations. The results of the comparison show that losses of the oil compounds were controlled by pore-space oil saturations, solubility, and susceptibility to degradation under methanogenic conditions. Compounds that degrade under methanogenic conditions, including toluene, o -xylene, and n -alkanes are more depleted compared to benzene, ethylbenzene, and m - and p -xylene for which losses are dominated by dissolution. These rates and compound-specific behaviors form a foundation for improved modeling approaches and risk analyses.
Minnesota↗
Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques
The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.
Environmental Science and Technology↗
Reducing risk where tectonic plates collide—U.S. Geological Survey subduction zone science plan
The U.S. Geological Survey (USGS) serves the Nation by providing reliable scientific information and tools to build resilience in communities exposed to subduction zone earthquakes, tsunamis, landslides, and volcanic eruptions. Improving the application of USGS science to successfully reduce risk from these events relies on whole community efforts, with continuing partnerships among scientists and stakeholders, including researchers from universities, other government labs and private industry, land-use planners, engineers, policy-makers, emergency managers and responders, business owners, insurance providers, the media, and the general public. Motivated by recent technological advances and increased awareness of our growing vulnerability to subduction-zone hazards, the USGS is uniquely positioned to take a major step forward in the science it conducts and products it provides, building on its tradition of using long-term monitoring and research to develop effective products for hazard mitigation. This science plan provides a blueprint both for prioritizing USGS science activities and for delineating USGS interests and potential participation in subduction zone science supported by its partners. The activities in this plan address many USGS stakeholder needs: High-fidelity tools and user-tailored information that facilitate increasingly more targeted, neighborhood-scale decisions to mitigate risks more cost-effectively and ensure post-event operability. Such tools may include maps, tables, and simulated earthquake ground-motion records conveying shaking intensity and frequency. These facilitate the prioritization of retrofitting of vulnerable infrastructure; Information to guide local land-use and response planning to minimize development in likely hazardous zones (for example, databases, maps, and scenario documents to guide evacuation route planning in communities near volcanoes, along coastlines vulnerable to tsunamis, and built on landslide-prone terrain); New tools to assess the potential for cascading hazards, such as landslides, tsunamis, coastal changes, and flooding caused by earthquakes or volcanic eruptions; Geospatial models of permanent, widespread land- and sea-level changes that may occur in the immediate aftermath of great ( M ≥8.0) subduction zone earthquakes; Strong partnerships between scientists and public safety providers for effective decision making during periods of elevated hazard and risk; Accurate forecasts of far-reaching hazards (for example, ash clouds, tsunamis) to avert catastrophes and unnecessary disruptions in air and sea transportation; Aftershock forecasts to guide decisions about when and where to re-enter, repair, or rebuild buildings and infrastructure, for all types of subduction zone earthquakes.
Circular↗
Seasonal Variability in Vadose zone biodegradation at a crude oil pipeline rupture site
Understanding seasonal changes in natural attenuation processes is critical for evaluating source-zone longevity and informing management decisions. The seasonal variations of natural attenuation were investigated through measurements of surficial CO2 effluxes, shallow soil CO2 radiocarbon contents, subsurface gas concentrations, soil temperature, and volumetric water contents during a 2-yr period. Surficial CO2 effluxes varied seasonally, with peak values of total soil respiration (TSR) occurring in the late spring and summer. Efflux and radiocarbon data indicated that the fractional contributions of natural soil respiration (NSR) and contaminant soil respiration (CSR) to TSR varied seasonally. The NSR dominated in the spring and summer, and CSR dominated in the fall and winter. Subsurface gas concentrations also varied seasonally, with peak values of CO2 and CH4 occurring in the fall and winter. Vadose zone temperatures and subsurface CO2 concentrations revealed a correlation between contaminant respiration and temperature. A time lag of 5 to 7 mo between peak subsurface CO2 concentrations and peak surface efflux is consistent with travel-time estimates for subsurface gas migration. Periods of frozen soils coincided with depressed surface CO2 effluxes and elevated CO2 concentrations, pointing to the temporary presence of an ice layer that inhibited gas transport. Quantitative reactive transport simulations demonstrated aspects of the conceptual model developed from field measurements. Overall, results indicated that source-zone natural attenuation (SZNA) rates and gas transport processes varied seasonally and that the average annual SZNA rate estimated from periodic surface efflux measurements is 60% lower than rates determined from measurements during the summer.
Vadose Zone Journal↗
Coping with earthquakes induced by fluid injection
Large areas of the United States long considered geologically stable with little or no detected seismicity have recently become seismically active. The increase in earthquake activity began in the mid-continent starting in 2001 ( 1 ) and has continued to rise. In 2014, the rate of occurrence of earthquakes with magnitudes ( M ) of 3 and greater in Oklahoma exceeded that in California (see the figure). This elevated activity includes larger earthquakes, several with M > 5, that have caused significant damage ( 2 , 3 ). To a large extent, the increasing rate of earthquakes in the mid-continent is due to fluid-injection activities used in modern energy production ( 1 , 4 , 5 ). We explore potential avenues for mitigating effects of induced seismicity. Although the United States is our focus here, Canada, China, the UK, and others confront similar problems associated with oil and gas production, whereas quakes induced by geothermal activities affect Switzerland, Germany, and others.
Science↗
Heterogeneous hydrofrac ture development and accretionary fault dynamics: Reply
No abstract available
Geology↗