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Special issue "Effects of surface geology on seismic motion (ESG): General state-of-research"

To understand and predict the behaviors of strong ground motions incurred during devastating earthquakes, studies focused on the “effects of surface geology (ESG) on seismic motions” (following tradition, herein contracted as: “ESG”) have progressed steadily in the last three decades. These ESG studies typically involve in situ measurements of the wavefield and commonly apply both analytical and computational approaches. Concurrently, improvements in ESG related research can be readily attributed to the proliferation of openly accessible strong motion data, as well as advances in computational power. Nevertheless, there remain significant shortfalls in our understanding of the epistemic and aleatory uncertainties associated with the ESG as demonstrated by phenomena from recent deadly earthquake-related site effects. Thus, investigations toward addressing these deficiencies should be underscored in future earthquake related disaster mitigation efforts. This special issue of Earth, Planets, and Space (EPS) is dedicated to the ongoing efforts by the International Association of Seismology and Physics of the Earth’s Interior (IASPEI) and the International Association of Earthquake Engineering (IAEE) that champion activities promoting studies related to the ESG.

Earth, Planets and Space

Imaging of seismic discontinuities using an adjoint method

For imaging of seismic discontinuities at depth, reverse time migration (RTM) is a powerful method to apply to recordings of seismic events. It is especially powerful when an extensive receiver array, numerous seismic sources, or both, permit adequate reconstruction of incident and scattered wavefields at depth. Reconstructing either the incident or scattered wavefield at depth becomes less accurate when relatively few recordings of seismic events are available. Here we explore an inverse scattering approach to imaging discontinuities based on an adjoint method, employing sensitivity kernels (Frechet derivatives) that represent jumps in material properties across seismic-discontinuity surfaces. When combined with ray-based requirements on scattering geometry, it constitutes a powerful approach to determining the locations and amplitudes of the discontinuities, recovering only those properties that can be resolved by a spatially limited source and/or receiver distribution. This is illustrated by synthetic examples with local sources followed by a field example in a subduction zone setting

Washington

Self-guided decision support groundwater modelling with Python

The GMDSI tutorial notebooks repository provides learners with a comprehensive set of tutorials for self-guided training on decision-support groundwater modelling using Python-based tools. Although targeted at groundwater modelling, they are based around model-agnostic tools and readily transferable to other environmental modelling workflows. The tutorials are divided into three parts. The first covers fundamental theoretical concepts. These are intended as background reading for reference on an as-needed basis. Tutorials in the second part introduce learners to some of the core concepts parameter estimation in a groundwater modelling context, as well as providing a gentle introduction to the PEST, PEST++ and pyEMU software. Lastly, the third part demonstrates how to implement highly-parameterized applied decision-support modelling workflows. The tutorials aim to provide examples of both “how to use” the software as well as “how to think” about using the software. A key advantage to using notebooks in this context is that the workflows described run the same code as practitioners would run on a large-scale real- world application. Using a small synthetic model facilitates rapid progression through the workflow.

Journal of Open Source Education

Mitigating climate change by abating coal mine methane: A critical review of status and opportunities

Methane has a short atmospheric lifetime compared to carbon dioxide (CO 2 ), ∼decade versus ∼centuries, but it has a much higher global warming potential (GWP), highlighting how reducing methane emissions can slow the rate of climate change. When considering the contribution of greenhouse gas (GHG) emissions to current global warming (2010–2019) relative to the industrial revolution (1850–1900) levels, methane contributes 0.5 °C or ∼ a third of the total. The most recent post-2023 global estimates of methane emissions by bottom-up (BU) and top-down (TD) approaches for the coal mining sector are in the range of ∼41 ± 3 Tg yr −1 and 33 ± 5 Tg yr −1 , respectively. This divergence, notwithstanding overlapping confidence intervals, is a result of differences between applied TD global inversion models and BU emission inventories. Further research can help to better refine emissions from the various contributing coal mine methane (CMM) emissions sources. The coal mining sector accounts for over 10 % of global anthropogenic methane emissions. The contribution of CMM emissions to the global budget have increased since 2000, although upward and downward regional trends have been observed.

International Journal of Coal Geology

Variability and consistency in wildfire susceptibility: Insights from a national compilation

Background Wildfire risk in the United States is rising and remains a land management priority. The quantitative wildfire risk assessment (QWRA) framework integrates fuels, topography, weather and values at risk to estimate the potential change in value from wildfire. Within this, response functions (RFs) represent how values respond to fire intensity. These are often based on expert judgment, but variation across assessments is unclear. Aims This study uses data from the US Geological Survey (USGS) Wildfire Hazard and Risk Assessment Clearinghouse to characterize consistency and variation across categories and contexts. Methods We applied descriptive statistics to summarize RFs, using tables, box-and-whisker plots and heat maps stratified by highly valued resource or asset (HVRA) category and spatial scale. Key results RFs and value definitions vary, especially for ecosystem-related resources. Some functions, such as for buildings in the wildland–urban interface (WUI), translate well across contexts, while others require more input. Conclusions Some functions are broadly transferable, while others need customization. This analysis provides references and starting points for improvement to RFs in QWRAs. Interpretations Expanding the clearinghouse and dataset and building more transparency in expert elicitation can build trust among communities, agencies and end-users, and can support efficient use of limited resources to mitigate wildfire risk.

International Journal of Wildland Fire

PFAS remediation in a bioelectrochemical system inoculated with the west branch consortium (WBC-2)

Groundwater contamination by per - and polyfluoroalkyl substances (PFAS) poses a persistent environmental and public health concern. This study evaluates a two-chambered bioelectrochemical system (BES) inoculated with the West Branch Consortium (WBC-2) for PFAS remediation. Under an applied cathodic potential of −450 mV (versus Ag/AgCl), the BES with active WBC-2 achieved >99.0% perfluorooctanesulfonic acid (PFOS) removal within 21 days in deionized water with culture medium and > 98.9% removal of PFOS, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA), and perfluorohexanesulfonic acid (PFHxS) in contaminated groundwater after 102 days. Intermediate formation (e.g., PFOA, 6:2 fluorotelomer sulfonate (6:2 FTS), perfluoropropionic acid (PFPrA), perfluorobutanoic acid (PFBA)) and background-corrected fluoride release were consistent with PFOS transformation under anaerobic reducing conditions potentially involving defluorination. Following repeated PFOS spikes (100 μg/L on Days 0, 50, and 399), PFOA, PFPrA, and PFBA accumulated over 664 days. Despite being the dominant accumulated compound, PFOA accounted for <1.8% of the total spiked PFOS mass. Minimal PFOS transformation occurred in controls without active WBC-2, highlighting the importance of microbial metabolism. Biofilm analysis revealed dense colonization of rod-shaped bacteria on carbon fiber brushes. Enrichment of Bacillus , Agrobacterium , and other low-abundance taxa suggests selective adaptation to BES and PFAS conditions. These findings highlight BES driven by electrochemically stimulated microbial activity as a promising strategy for PFAS remediation.

Journal of Water Process Engineering

Constraining mean landslide occurrence rates for non-temporal landslide inventories using high-resolution elevation data

Constraining landslide occurrence rates can help to generate landslide hazard models that predict the spatial and temporal occurrence of landslides. However, most landslide inventories do not include any temporal data due to the difficulties of dating landslide deposits. Here we introduce a method for estimating the mean landslide occurrence rate of deep-seated rotational and translational slides derived solely from high-resolution (≤3 m) elevation data and globally available estimates of the diffusion coefficient for sediment flux. The method applies a linear diffusion model to the roughest landslide deposits until they reach a representative non-landslide roughness distribution. This estimates the time for a landslide deposit to be unrecognizable in high-resolution digital elevation data, which we term the mean lifetime of the landslide. Using the mean lifetime and number of landslides within an area of interest, we can estimate the mean occurrence rate of landslides over that domain. We validate this approach using a comprehensive temporal inventory of landslides in western Oregon created using age-roughness curves that are calibrated with high-resolution elevation data and radiocarbon data. We find good agreement between our diffusion method and the existing age-roughness-derived estimates, producing mean lifetimes of 4500 and 5200 years (4% difference), respectively. Hazard maps produced using the two methodologies generally agree, with the maximum differences in landslide probability reaching 0.1. Due to the relative abundance of high-resolution elevation data compared with age-dated landslides, our method could help constrain landslide occurrence rates in areas previously considered unfeasible.

Oregon

Multi-lithofacies alluvial characterization via airborne electromagnetic-borehole fusion using ordinary interval kriging and geologic constraints

Airborne electromagnetic (AEM) survey provides extensive spatial coverage and detailed resolution at the near surface and can be used to develop hydrogeological models. However, utilization of AEM data is not straightforward because AEM resistivity is an indirect measurement for inferring sediment types. This study develops an ordinary interval kriging (OIK) algorithm and a resistivity-to-multi-lithofacies (R2ML) data fusion workflow for multi-lithofacies alluvial characterization. OIK utilizes irregular interval data to construct three-dimensional (3D) resistivity fields from one-dimensional inverted AEM resistivity models. The R2ML workflow maps the resistivity field generated from OIK into a multi-facies lithological model, incorporating geologic constraints derived from well logs and geological observations. The numerical and real-world cases demonstrate that OIK is computationally efficient, accounts for 3D anisotropy, and minimizes the smoothing effect, thereby preserving resistivity contrasts and reducing interpolation uncertainty. The methodology is applied to lithologic characterization of the Mississippi River Valley alluvial aquifer (MRVA) in the Shellmound area, Mississippi, U.S. A frequency-domain AEM survey was conducted to support groundwater studies for the managed aquifer recharge (MAR) to the MRVA. The resulting lithological model, including four types of lithofacies—clay, very fine sand, fine-medium sands, and graveliferous sands, illustrates the geomorphological processes of the MRVA and implies potential MAR. The alignment between the lithological model and existing geological and hydrogeological investigations demonstrates that OIK and R2ML workflow effectively capture the subsurface architecture of the MRVA. The methods have broad applicability for characterizing alluvial aquifers through AEM-borehole data fusion, supporting sustainable groundwater management.

Mississippi

Advancing current understanding of Martian impact-generated hydrothermal systems through novel coupled modeling: Insights from Gale, Jezero, and other craters

Impact-generated hydrothermal systems are considered potentially habitable environments on Mars, Earth, and other planetary bodies for microbial life. However, there is an ongoing debate regarding what geological features on Mars provide definitive evidence for such systems. Although earlier studies have modeled hydrothermal processes in Martian craters, they often lacked integration with shock physics hydrocodes to constrain initial impact conditions. The importance of this two-code coupling was demonstrated by successfully replicating alteration signatures in the Earth's Haughton impact structure. In this study, we use a similar two-code approach, combining the iSALE hydrocode with the HYDROTHERM hydrothermal model to simulate the full evolution of impact-generated hydrothermal systems. We apply this method to craters the size of Jezero (∼50 km) and Gale (∼154 km) in diameter. Although Jezero's interior is largely buried, our results align with hypothesized hydrothermal vents and alteration minerals near central uplifts in similarly sized exposed craters, such as Toro and Auki. Furthermore, our models correspond to alteration patterns observed by the Curiosity in the lower layers of Mount Sharp, which may represent remnants of impact-driven hydrothermal activity. A key finding is that these systems may persist much longer than previously estimated. Our simulations suggest that a Jezero-sized system could remain habitable for thermophiles for approximately 720,000 years, whereas a Gale-sized system could persist for nearly 2 million years. Additionally, simulations under unsaturated crustal conditions reveal that air-dominated near-surface layers can suppress vertical fluid flow, enabling deep subsurface alteration without producing detectable mineral signatures at the surface.

Journal of Geophysical Research - Planets

Impact of gas/liquid phase change of CO2 during injection for sequestration

CO 2 sequestration in deep saline formations is an effective and important process to control the rapid rise in CO 2 emissions. The process of injecting CO 2 requires reliable predictions of the stress in the formation and the fluid pressure distributions – particularly since monitoring of the CO 2 migration is difficult – to mitigate leakage, prevent induced seismicity, and analyze wellbore stability. A key aspect of CO 2 is the gas–liquid phase transition at the temperatures and pressures of relevance to leakage and sequestration, which has been recognized as being critical for accurate predictions but has been challenging to model without ad hoc empiricisms. This paper presents a robust multiphase thermodynamics-based poromechanics model to capture the complex phase transition behavior of CO 2 and predict the stress and pressure distribution under super- and sub- critical conditions during the injection process. A finite element implementation of the model is applied to analyze the behavior of a multiphase porous system with CO 2 as it displaces the fluid brine phase. We find that if CO 2 undergoes a phase transition in the geologic reservoir, the spatial variation of the density is significantly affected, and the migration mobility of CO 2 decreases in the reservoir. A key feature of our approach is that we do not a priori assume the location of the CO 2 gas/liquid interface – or even if it occurs at all – but rather, this is a prediction of the model, along with the spatial variation of the phase of CO 2 and the change of the saturation profile due to the phase change.

Journal of the Mechanics and Physics of Solids

Concentration-discharge relations and transient metal loads reveal spatiotemporal variability in solute-generation mechanisms in a mine-affected watershed

Concentration-discharge (CQ) relations are commonly used to understand geochemical and hydrologic controls on the generation of solutes in watersheds. Despite the widespread application of CQ relations, this technique has been infrequently applied to acid mine drainage (AMD) sites, but the CQ framework may allow mechanistic understanding of remedial outcomes such as impoundment of water within underground mines. Results of CQ analyses and changes in metal loads in an AMD affected watershed in Colorado, USA indicate that dissolved loads increased at many individual locations following water impoundment within mine workings. Although increased loads were observed at most individual locations, these increases were offset by a large decrease in loading from the largest mine. A loading analysis that included data from an instream monitoring location showed a statistically significant decrease in Fe and Zn after bulkhead emplacement, indicating a net positive effect of bulkheads. Streams generally displayed dilution CQ patterns whereas mines and springs showed either flushing or chemostatic patterns prior to bulkheading, which transitioned to chemostatic patterns following bulkheading, indicating a transition from dynamic to equilibrium geochemical processes. Saturation indices for sulfide and secondary minerals indicated that mines and springs were near equilibrium for phases including schwertmannite, fluorite, and gypsum. Saturation indices vary through time for mines suggesting progressive leaching of sulfide minerals as the mass of available minerals in the mine workings decreases. Together, these diverse analyses provide an integrated understanding of the variability in solute generating processes in this watershed and may inform remediation plans for similarly affected sites by indicating the nature of mineralogic controls on water quality.

Colorado

The distribution of bromide in water in the Floridan aquifer system, Duval County, northeastern Florida

Although Duval County, Florida, has ample ground-water resources for public supply, the potential exists for a problem with excessive disinfectant by-products. These disinfectant by-products result from the treatment of raw water containing low concentrations of bromide and naturally occurring organic compounds. Because of this potential problem, the relation of bromide concentrations to aquifer tapped, well location and depth, and chemical characteristics of water in the Floridan aquifer system underlying Duval County were studied to determine if these relations could be applied to delineate water with low-bromide concentrations for future supplies. In 1992, water samples from 106 wells that tap the Floridan aquifer system were analyzed for bromide and major dissolved constituents. A comparison of bromide concentrations from the 1992 sampling with data from earlier studies (1979-80) indicates that higher bromide concentrations were detected during the earlier studies. The difference between the old and new data is probably because of a change in analytical methodology in the analysis of samples. Bromide concentrations exceeded the detection limit (0.10 milligrams per liter) in water from 28 of the 106 wells (26 percent) sampled in 1992. The maximum concentration was 0.56 milligrams per liter. There were no relations between bromide and major dissolved constituents, well depth, or aquifer tapped that would be useful for determining bromide concentrations. Areal patterns of bromide occurrence are not clearly defined, but areas with relatively high bromide concentrations tend to be located in a triangular area near the community of Sunbeam, Florida, and along the St. Johns River throughout Duval County.

Florida

Identification of representative earthquakes for probabilistic tsunami hazard analysis (PTHA) using earthquake rupture forecasts and machine learning

As probabilistic tsunami hazard analysis (PTHA) focuses more on assessments for localized, populous regions, techniques are needed to identify a subsample of representative earthquake ruptures to make the computational requirements for producing high-resolution hazard maps tractable. Moreover, the greatest epistemic uncertainty in seismic PTHA is related to source characterization, which is often poorly defined and subjective. We address these two salient issues by applying streamlined earthquake rupture forecasts (ERFs), based on combinatorial optimization methods, to an unsupervised machine learning workflow for identifying representative ruptures. ERFs determine the optimal distribution of a millennia-scale sample of earthquakes by inverting the observed slip rate on major faults. We use two previously developed combinatorial optimization ERFs, integer programming and greedy sequential, to produce the optimal location of ruptures with seismic moments sampled from a regional Gutenberg–Richter magnitude–frequency distribution. These ruptures in turn are used to calculate peak nearshore tsunami amplitude, using computationally efficient tsunami Green's functions. An unsupervised machine learning workflow is then used to identify a small subsample of the earthquakes input to ERFs for onshore PTHA analysis. We eliminate epistemic uncertainty related to source distribution under traditional PTHA analysis; in its place, a quantifiable, less subjective and generally smaller uncertainty related to the input to ERFs is included. The Nankai subduction zone is used as a test case, where previous ERFs have been conducted. Results indicate that the locations of representative earthquakes are sensitive to choice of magnitude–area relation and to whether a minimum cumulative stress objective is imposed on the fault. In general, incorporating ERFs into PTHA provide a physically self-consistent method to incorporate fault slip information in determining representative earthquakes for onshore PTHA, eliminating a major source of epistemic uncertainty.

Nankai subduction zone

Rapid seismic and infrasound assessment of large landslides: A case study from Denali National Park and Preserve (Alaska)

Large, rapid landslides are a global hazard that can occur in remote, mountainous areas. Eyewitness reports of landslides and satellite imagery can often be limited or delayed, particularly during inclement weather. However, landslide-generated seismic and infrasound (low-frequency atmospheric sound) waves can be remotely detected in near real-time. This information can significantly expedite characterization and possible landslide response activities. Here, we highlight these capabilities using a > 4 million m³ ice–rock avalanche in Denali National Park and Preserve (Alaska). This event was detected via a landslide-specific seismic location and volume estimation algorithm deployed in Alaska, and — notably — by standard earthquake monitoring systems. Following rapid detection of this event, we combined its seismic and infrasound dataset with optical, synthetic aperture radar, and oblique aerial imagery, multitemporal digital elevation models, and a numerical flow model to reconstruct its failure timeline and dynamics. We apply array processing to infrasound signals traveling > 250 km and find that two precursory events occurred minutes prior to the main failure. We use long-period seismic signals to infer the force exerted by the landslide on the Earth and constrain the rheological parameters of our numerical flow simulation with this result and deposit morphology. The main failure produced a steeply-dipping impulsive initial downward force and reached speeds exceeding 60 m/s. This impulsive force generated relatively strong seismic body waves, which contributed to the earthquake system detection. This large, remote Alaska landslide underscores the key value of seismic and infrasound analysis for rapid landslide assessment and motivates efforts to further operationalize these approaches.

Alaska

Event classification, seismicity, and eruption forecasting at Great Sitkin Volcano, Alaska: 1999–2023

The frequency content of volcanogenic seismicity is often used to classify events and their spatial and temporal progression is then used to map subsurface volcanic processes. The progression of volcano-seismic events and associated source processes also plays a critical role in eruption forecasting. Here we develop and evaluate a computerized methodology for characterizing volcano-seismic event types using Frequency Index and Average Peak Frequency. We apply and test this technique at Great Sitkin Volcano, Alaska, classifying over 9000 hypocenters between 1999 and 2023. This 24-year time span covers periods of seismic quiescence, earthquake activity on nearby tectonic (bookshelf) faults, precursory unrest from 2016 to 2021, and the explosive onset in May 2021 of the ongoing effusive eruption. We use the spatial and temporal evolution of classified event types to map the active volcanic and tectonic processes, develop a conceptual model of the subsurface magmatic system, and perform a retrospective analysis of eruption forecasts at Great Sitkin Volcano between 2016 and the present. The classification and progression of hypocenters suggests the subsurface Great Sitkin Volcano magmatic system consists of a mid- to lower- crustal source zone between 10 and 40 km depth and an upper crustal magma storage area between −1 and 10 km depth (hypocenter depth is referenced to sea level and negative depths reflect height above sea level). The earliest precursors occurred in July 2016 and consisted of deep long-period and volcano-tectonic earthquakes at mid-crustal depths suggesting the subsequent unrest and eruption were triggered by a deeper intrusion of magma. This mid-crustal seismic activity was immediately followed by the onset upper-crustal long-period events and volcano-tectonic earthquakes VTs suggesting a strong linkage between the shallow and deeper portions of the magmatic system. The upper crustal area was likely capped by the 1974 lava dome until the magmatic explosion on May 26, 2021.

Alaska

Nonstationary demographic state-space models using unreplicated counts for species undergoing environmental stressors

A fundamental task in ecological statistics is to estimate abundance and growth rate distributions from wildlife monitoring data to inform conservation management. Modeling time series of wildlife populations presents a number of challenges from both statistical and ecological perspectives, including discreteness; lack of replication; nonstationarity; and observation, demographic, and other phenomenological processes. Nonstationary dynamics are often exhibited by populations undergoing environmental stressors. Models must account for these characteristics to produce reliable estimates of abundance and trends, yet estimation can be challenging with unreplicated data. We propose nonstationary demographic state-space models using unreplicated counts for populations undergoing environmental stressors. A reduced growth rate model matches the complexity of the unreplicated count data, and a fecundity bound on growth rate distributions allows the separation of processes affecting growth rates like environmental stressors from those affecting abundance external to growth rates like migration. NDSSMs allow for the embedding of nonstationary model components, and we explore the use of changepoints, volatility clustering, and migration processes. We apply the proposed nonstationary models in case studies of herons affected by predator/competitor reestablishment and three bat species affected by a fungal pathogen causing white-nose syndrome. Nonstationary models outperform stationary models and generalized linear mixed effects models according to model scoring and visual inspection of predictions, and provide estimates more consistent with published values. Incorporating migration improves model fit universally, even with approximate one-way immigration, most likely because populations are extirpated, recolonized, and increase multiple-fold over the upper bound set by species fecundity. In addition, estimates of the timing and severity of the environmental stressor differed for models with migration. Including nonstationary and demographic components in a fecundity-bounded growth rate model improves inference and benefits interpretability of hyperparameters. In turn, this adjusts uncertainties in predictions of abundance and growth rates over time, providing the ingredients needed for informed conservation analysis and for directing future monitoring of at-risk species.

Journal of Agricultural, Biological and Environmen

Sedimentological and geochemical characterization of lacustrine deposits of the Babouri-Figuil basin, northern Cameroon: Implications for source rocks distribution and petroleum exploration

The West and Central African Rift System (WCARS) refers to the series of Cretaceous rift basins where commercial hydrocarbon accumulations have been discovered. Some of the WCARS frontier basins are currently being investigated to increase our understanding of these basins in light of new commercial discoveries. The present study was performed in the Babouri-Figuil Basin (BFB), which is genetically related to the WCARS and constitutes an area of interest in terms of petroleum prospecting, where the distribution of petroleum source rocks and potential targets for petroleum exploration across the entire basin is poorly understood. For the current study, an integrated facies analysis along with organic and inorganic geochemical techniques were applied to the basin's Cretaceous deposits with the aim of reconstructing the paleodepositional environment, assessing factors that triggered the input of organic matter, and providing a spatial overview of the organic matter accumulation in the basin based on outcrop samples. An alluvial fan-lacustrine-braided river system is inferred from the facies analysis of the stratigraphic sequence consisting of conglomerate, sandstone, siltstone, limestone, marlstone, and claystone. Bulk analysis of organic matter reveals that black shale and massive claystone are the main prospective petroleum source rocks in the basin. Inorganic geochemical analyses reveal the influence of anoxic conditions, moderate to high primary productivity, and low terrigenous inputs in organic matter enrichment. The formations rich in organic matter are predominantly concentrated in the western and eastern parts of the basin which may represent areas with depressions, characterized by high accommodation space. In terms of the regional context of the WCARS rift basins, typical hydrocarbon exploration in the BFB may target basal-conglomerate, sandstone beds situated directly above or/and interbedded with the Lower Cretaceous source rocks, and the Upper Cretaceous sandstone beds. Basement rocks (granite, granodiorite, and gneisses) and oil shale deposits may represent potential unconventional hydrocarbon exploration. The current integrated study provides an insight that should guide future hydrocarbon exploration campaigns in the basin.

Babouri-Figuil basin

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