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Humpback whales produce complex, structured songs that vary among individuals, populations, and through time. This study presents a novel method of studying changes in humpback whale song elements through time while accounting for detection probability.
In this study, we derive generic site amplification functions applicable to Northwestern Türkiye and follow guidance on site classifications established by the United States National Earthquake Hazards Reduction Program (NEHRP). We employ the one-dimensional (1-D) equivalent linear ground response analysis method and focus on recordings from a select suite of free-field strong motion (SM) stations. These particular SM stations are associated with a comprehensive geotechnical site conditions dataset comprising 76 shear-wave velocity profiles. Despite their varying resolutions and depths, this diversity allows for a more representative analysis across different site conditions, enhancing the robustness of our findings. For analyses, we utilize a robust set of global ground motion records, selected from both within and outside of Türkiye, to serve as strong and weak input bedrock motions. Site amplification is determined by propagating these bedrock records through 76 site-specific Afet ve Acil Durum Yönetimi Başkanlığı (AFAD) station profiles and calculating the spectral acceleration ratio between the ground surface and the input motion. Our analyses reveal substantial disparities between the amplification functions derived from 1-D site response analyses using strong and weak input motions. These disparities are central to our analysis and inform the subsequent comparison with site amplification functions reported in the literature. We compare the generic site amplification functions derived in this study with those reported in the literature for regions with similar geological and seismic conditions to Northwestern Türkiye. For example, site amplification functions for NEHRP Site Classes C and D have been documented for Greece and the United States utilizing frequency-dependent methods such as the quarter-wavelength approximation. Our findings reveal that the generic site amplification functions derived in this study exhibit differences in peak amplitudes and predominant frequencies compared to those in the literature, reflecting regional variations in geotechnical and seismic properties. This study represents an initial effort to formulate generic site amplification functions for Türkiye, with a particular emphasis on the Northwestern region. A thorough literature review indicated no prior studies have proposed such functions specifically for this area.
The Emigrant Gap composite pluton exposes ultramafic to silicic intrusive rocks that preserve the chemical evolution of primitive mafic arc magmas and their open-system interactions in the upper crust during mid-Jurassic growth of the Sierra Nevada batholith (California). We present field and petrographic observations and mineral and whole-rock chemistry of the ~35-km 2 ultramafic to dioritic Emigrant Gap mafic complex and an adjacent penecontemporaneous ~90-km 2 granodiorite that together make up the composite pluton. In the Emigrant Gap mafic complex, four roughly central masses of dunite, wehrlite, and olivine clinopyroxenite are surrounded by weakly layered gabbronorite and non-layered diorite. The ultramafic rocks are cumulates formed from near-liquidus minerals of primitive arc magmas that accumulated in steep feeder zones with substantial modification by melt–mush reaction as primitive liquids repeatedly transited the mush-filled conduits. The dominant gabbronoritic rocks are the variably accumulative products of more advanced crystallization–differentiation of arc tholeiitic basalts and basaltic andesites. The adjacent granodiorite intrusion originated separately and preserves field and geochemical evidence for assimilation of metasedimentary rocks. Open-system hybridization between the gabbronoritic mushes and the granodioritic magma produced an intervening body of two-pyroxene diorite. We infer that the ultramafic rocks and gabbronorite of the Emigrant Gap mafic complex crystallized from near-primitive arc basaltic to basaltic andesitic magmas at ~0.15–0.3 GPa, with estimated f O 2 of ≥FMQ +1 and dissolved H 2 O concentrations of only ~0.5–2 wt %. Notably, the Emigrant Gap composite pluton is distinct from other Mesozoic plutons in the Sierra Nevada batholith because of (1) its abundance of mafic and ultramafic rocks that crystallized from relatively primitive mafic melts and (2) the low inferred H 2 O concentrations of its parental magmas, indicated by a near absence of igneous amphibole and by the intermediate rather than calcic compositions of plagioclase. A Jurassic regional extension event probably accounts for the formation of relatively dry primitive arc magmas, as well as for their ascending to the upper crust.
A series of gold tube pyrolysis experiments (72 h, 300–550 °C, 50 MPa) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm. Organic petrology, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM) with energy dispersive spectroscopy (EDS) were combined to evaluate the thermal evolution process. The three types of graptolite periderm, namely granular, non-granular, and nodular graptolite, were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Distinct thermal evolution pathways among non-granular, granular, and nodular graptolite periderms were recorded. The evolution patterns of the Raman parameters, particularly D1 and G bands, highlight the differences in geochemical composition of the graptolite periderm types and the alteration of molecular structure with increasing thermal maturity. Raman parameters D1 (position of the D1 peak), G-FWHM (full width at half maximum of the G peak), and ratios D1-FWHM/G-FWHM (full width at half maximum of the D1 peak ratioed to G-FWHM) and A D1 /A G (ratio of D1 and G peak intensities) showed effectiveness in assessing thermal maturity. Bireflectance with increasing gold tube pyrolysis temperature followed a hierarchy: non-granular > granular > nodular, reflecting different molecular alignment intensities. Qualitative FE-SEM evaluation showed that fine-grained mineral inclusions (primarily Fe-sulfide as determined via EDS) were associated with the graptolite populations, with granular graptolite containing greater amounts of coarser-grained (e.g., ∼300–1400 nm) mineral inclusions relative to non-granular and nodular graptolite, which contain finer-grained (e.g., ∼100–200 nm) inclusions difficult to resolve with optical microscopy. These findings are investigated to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore some of the limitations of using spectroscopic parameters as thermal maturity proxies.
Forecasting water levels in complex ecosystems like wetlands can support effective water resource management, ecological conservation, and understanding surface and groundwater hydrology. Predictive models can be used to simulate the complex interactions among natural processes, hydrometeorological factors, and human activities. The Greater Everglades in the USA is a well-known example of an ecosystem where complexity has motivated adoption of machine learning algorithms in water level prediction studies. This paper aims to contribute to extending existing machine learning algorithms by integrating spatiotemporal data with deep-learning algorithms in the forecasting process. In this study, a deep-learning model is developed to predict water levels on a regional scale, covering a large area of approximately 9,138 square kilometers in the Everglades ecosystem. This model has the architecture of Convolutional Long Short-Term Memory which can deal with spatiotemporal data by capturing both spatial and temporal dependencies in the training data. The forecasting capabilities of this model (referred to as the global model) are assessed by comparing the global model to two Artificial Neural Networks developed at two different gaging stations, referred to here as local models. One local model is developed at a gaging station directly influenced by nearby water control structures, whereas the other is developed at a gaging station located farther away from these structures. By leveraging data from the Everglades Depth Estimation Network spanning from January 2002 to May 2023, the global and local models were trained to forecast water levels with a two-day lead time. Our findings suggest that both the global and local models perform with approximately the same level of accuracy, with Mean Absolute Relative Error values ranging from 0.38% to 1.4% at the selected stations. The developed global model has demonstrated strong potential as a standalone forecasting tool for the entire study area in the Everglades and could eliminate the need for developing multiple local models. This finding also highlights how machine learning can capture complex spatial and temporal relationships to generate accurate water level predictions on a regional scale.
Groundwater resources are utilized near areas of intensive oil and gas development in California’s San Joaquin Valley. In this study, we examined chemical and isotopic data to assess if thermogenic gas or saline water from oil producing formations have mixed with groundwater near the Elk Hills and North Coles Levee Oil Fields in the southwestern San Joaquin Valley. Major ion concentrations and stable isotope compositions were largely consistent with natural processes, including mixing of different recharge sources and water-rock interactions. Trace methane concentrations likely resulted from microbial rather than thermogenic sources. Trace concentrations of benzene and other dissolved hydrocarbons in three wells had uncertain sources that could occur naturally or be derived from oil and gas development activities or other anthropogenic sources. In the mid-1990s, two industrial supply wells had increasing Cl and B concentrations likely explained by mixing with up to 15 percent saline oil-field water injected for disposal in nearby injection disposal wells. Shallow groundwater along the western margin of Buena Vista Lake Bed had elevated Cl, B, and SO 4 concentrations that could be explained by accumulation of salts during natural wetting and drying cycles or, alternatively, legacy surface disposal of saline oil-field water in upgradient ephemeral drainages. This study showed that groundwater had relatively little evidence of thermogenic gas or saline water from oil and gas sources in most parts of the study area. However, the evidence for groundwater mixing with injected disposal water, and possibly legacy surface disposal water, demonstrates produced water management practices as a potential risk factor for groundwater-quality degradation near oil and gas fields. Additional studies in the San Joaquin Valley and elsewhere could improve understanding of such risks by assessing the locations, volumes, and types of produced water disposal practices used during the life of oil fields.
Groundwater seepage from underlying permeable glacial sedimentary structures, such as eskers, has been hypothesized to directly feed pools in northern peat bogs. These hypotheses directly contradict classical peat bog models for ombrogenous systems, wherein meteoric water is the sole water input to these systems. Variations in the underlying mineral sediment in contact with the peat imply that unrecognized hydrogeologic connectivity may exist with pools in northern peat bogs, particularly where high permeability materials are in contact with the peat. Seepage dynamics originating from these structural variations were investigated using a suite of thermal and hydrogeophysical methods deployed around pools in a peat bog of northeastern Maine, USA. Thermal characterization methods mapped anomalies that were confirmed as matrix seepage or preferential flow pathways (PFPs). Geochemical methods were employed at identified thermal anomalies to confirm upwelling of solute-rich groundwater. Conduits around pools were associated with surficial terminations of suspected peat pipes, based on the inference of pathways extending down into the peat, that focus flow through PFPs in the peat matrix. Discharge also occurred through the peat matrix adjacent to suspected pipe structures and matrix seepage rates were quantified using analysis of diurnal temperature signals recorded at multiple depths. Seepage rates, with a maximum of nearly 0.4 m/d, were measured at localized points around pools. Periods of synchronized temperatures paired with highly muted diurnal temperature signals, recorded in diurnal temperature with depth data, were interpreted qualitatively as activation of strong upward discharge rates through suspected peat pipes. These time periods correlated strongly with local precipitation events around the peatland. Ground-penetrating radar surveys revealed discontinuities in the low permeability glacio-marine clay at the mineral sediment-peat interface, interpreted to be regional glacial esker deposits, which were located beneath and around pools. Heat tracing, specific conductance contrasts, seepage rates, and trace metal concentrations all imply groundwater seepage originating from underlying permeable glacial esker deposits and directly sourcing pools. Preferential groundwater inputs into northern peat bogs may play a key role in developing and maintaining pool systems, with enhanced solute transport impacting peatland ecology, water resources, and carbon cycling.
The purpose of this report is to summarize various electrical sounding studies made on the Kilauea Iki lava lake and to present some of the preliminary interpretations that resulted from the measurements. The following discussion is not intended as a complete interpretation, but is intended to summarize the major points made in an invited oral presentation at the American Geophysical Union fall meeting held in San Francisco, Calif. on December 6, 1976. This paper was part of a group of papers dealing with various geophysical studies recently made on the Kilauea Iki lava lake. A general plan map of Kilauea Iki lava lake is shown in figure 1. Electromagnetic (EM) loop-loop soundings, D.C. resistivity soundings, and VLF apparent resistivity measurements were made on the lave lake surface. All of these surveys were made to determine the geoelectric structure of the lava lake and to determine parameters of the molten basaltic lens that exist in the partially solidified lava lake.
The 2018 eruption of Kīlauea volcano in its Lower East Rift Zone began with the discharge of evolved high-Ti basalt as weak lava fountains and short, slow-moving lava flows. The lavas were quickly geochemically recognized as being derived from magmas stored within the rift zone and remobilized by a new intrusion, a sequence that is common at Kīlauea. This initial phase of the 2018 eruption, referred to as phase 1a, lasted for 6 days and was followed by extrusion of mixed magma after a 3-day pause. Even though remobilization of older rift zone magmas is common within Kīlauea’s rift zones, it is difficult to determine which past intrusion(s) may have initially emplaced those stored magmas. This difficulty stems from the tendency for Kīlauea magmas to follow very similar differentiation paths without significant variations in major, minor, or even trace element chemistry. We investigate possible magma sources for the lavas erupted during phase 1a of the 2018 eruption using whole-rock, mineral, and glass major and trace element compositions from historical East Rift Zone eruptions with adjacent fissures. We consider two primary hypotheses for the phase 1a source: magmas associated with the 1955 Lower East Rift Zone eruption or the nine eruptions in the Middle and Upper East Rift Zone during the 1960s. Our results suggest that magma associated with the earliest phases of Kīlauea’s 1955 eruption was the most likely source of the 2018 phase 1a remobilized magma. We determine volatile saturation pressures from melt inclusion chemistry and find similar storage depths for the 2018 phase 1a and early 1955 magmas. The phase 1a and early 1955 lavas are nearly indistinguishable in all of the compositional criteria considered, implying that the leftover 1955 magma body barely cooled and differentiated in the 63 years between eruptions (cooling rates of ~0.1 °C/year). This study sheds light on the potential for protracted storage of eruptible magmas in rift zones at Kīlauea, and highlights some of the challenges and solutions to identifying genetic relationships between magmas at Kīlauea.
Hotter droughts have resulted in widespread tree die-off events globally, frequently leading to regeneration failure. Dry forest recovery often depends on the growth and survival of extant juvenile trees. However, it is unclear how microenvironmental changes following overstorey tree die-off affect juvenile trees, particularly in dryland systems where tree recruitment is typically limited by water availability and heat stress. We simulated an overstorey tree die-off event by girdling trees in piñon-juniper woodlands across the south-western United States. We sampled juvenile piñon pine growth from live and dead overstorey treatments across six study sites spanning a regional latitudinal gradient and local elevational gradients. We examined how juvenile branch and needle growth differed between live and dead overstorey treatments, and whether responses varied with weather conditions and juvenile tree size following overstorey mortality. We found greater juvenile branch and needle growth under dead compared with live overstorey trees for 2 years following overstorey mortality at mid- and high-elevation sites which are typically cooler and wetter than the other sites. These observed growth releases were contingent on favourable post-mortality weather conditions. Higher growth under dead overstorey occurred at sites experiencing near-average climatic water deficits compared with sites experiencing above-average climatic water deficits. Growth at all sites increased from the first to second year after overstorey mortality. Across sites, growth was unrelated to juvenile tree size. Synthesis . Our results underscore differentiation in juvenile responses to overstorey tree die-off driven by local site conditions and weather across the range of Pinus edulis . Overstorey mortality resulted in consistently higher juvenile growth only at climatically favourable sites and during favourable weather, while unmeasured microsite differences could help account for variation observed at the hottest and driest site. Results from less climatically favourable sites suggest that overstorey trees neither directly limit nor facilitate juvenile growth, though further study over longer timeframes is needed to resolve the pace and magnitude of potential recovery or decline. Overall, juvenile vigour may be promoted following overstorey mortality only in a narrow spatial (site) and temporal (weather) environmental context, suggesting additional vulnerabilities for piñon populations under more arid conditions.
The astronomical tide relates to lunar (and to a lesser extent solar) influences on rising and falling water bodies, and is a key control of many coastal processes. However, tides manifest along coastal margins in different ways to muddle application beyond Sir Isaac Newton’s first descriptions. Here, we argue that tide, or specifically “tidal,” has not been adequately defined for the coastal wetland sciences to facilitate contemporary interdisciplinary distinction for rapidly changing coastlines and future climate adaptation planning. We provide a brief history of the tidal concept, and we describe tides in a diversity of uncommonly recognized marginal coastal environments. Common astronomical tide manifestations are described through hydrographic examples, then expanded to include those tidal environments exposed additionally to fluvial, meteorological (wind), or groundwater influences. Our expanded definition of “tidal” is intended to be a forward-looking construct as environments will inevitably change with sea-level rise, water extraction, and anthropogenic flow alteration. Our definition of wetland tidal influence, which we broaden, includes those “wetlands affected by astronomic water level fluctuations within coastally restricted environments causing frequent or infrequent surface inundation or groundwater tidal variation that affects the biogeochemistry of the soil (e.g., ion exchange capacity, oxygen state, mineralization processes)”. Astronomic water level fluctuations are often amplified or dampened by non-astronomical events, such as wind. Expanding the definition of what is considered tidal by the scientific community is critical for improved understanding of coastal wetland function and the suite of ecosystem services they provide people and society, including climate mitigation opportunity, management, and adaptation.
The U.S. National Park Service stratotype inventory has systematically documented hundreds of published stratotypes across the country that represent a quintessential component of America’s geoheritage and possess significant scientific, educational, cultural, historic, and aesthetic values. As valuable geologic reference standards, stratotypes record intervals of Earth history relating to our nation’s unique geologic evolution, biological progression, cultural traditions, historical narratives, and stunning landforms. However, the general lack of awareness and knowledge regarding the scope, significance, distribution, and scale of stratotypes can result in these resources being overlooked. Consequently, stratotypes may inadvertently experience accidental alteration, damage, or destruction through both natural and anthropogenic processes. As with many American geoheritage sites, stratotypes lack specific recognition through legislation, policies, or other management strategies to ensure their preservation and protection. Through education and outreach, we hope to inform, increase awareness, and engage the public about these internationally and nationally significant geologic reference sites, unite various geoheritage communities, and promote their preservation for future generations.
Grasslands in Nebraska, USA, face threats from agricultural conversion, urban development, and woody encroachment, all of which negatively affect prairie grouse ( Tympanuchus spp.) populations. To optimize conservation planning, Nebraska wildlife agencies developed probabilistic area-based surveys for greater prairie-chicken ( T. cupido ) and sharp-tailed grouse ( T. phasianellus ) to sample landscapes across a range of environmental conditions. This design improves historical surveys and enables the development of distribution models that quantitatively define habitat associations and support scenario-based conservation planning. Using survey data collected during 2020–2022, we modeled prairie grouse occurrence and abundance as functions of land cover, topography, and climate using Bayesian logistic and zero-inflated negative binomial models with regularized horseshoe priors. We then conducted a maximum potential return-on-investment analysis of woody cover treatments, assuming sustained treatment success, relative to projected impacts of woody encroachment on prairie grouse populations by 2050. Among modeled associations were a positive association with grasslands having low woody cover and a negative association with grasslands having high woody cover. Across the 3-year period, median estimated annual populations were 142,380 for greater prairie-chicken (range of 95% CIs across years = 68,821–277,615) and 64,154 for sharp-tailed grouse (range of 95% CIs across years = 27,550–146,559). Under projected woody encroachment, mean predicted population declines were 10% for greater prairie-chicken (range of 95% CIs = 7–14%) and 6% for sharp-tailed grouse (range of 95% CIs = 5–7%). Areas with high prairie grouse density and low treatment costs in 2021, and high projected woody encroachment and population loss by 2050, offered the greatest return on investment for woody management. Return on investment was greatest in the northwestern Shortgrass Prairie ecoregion (northwestern Nebraska) for sharp-tailed grouse and the eastern Sandhills ecoregion (central Nebraska) for both species. These models underscore the value of evidence-based, quantitative approaches for prioritizing conservation actions on working lands. Scenario-based modeling could be extended to guide other treatments, such as optimizing restoration (e.g., Conservation Reserve Program) or incentivizing grassland persistence in areas with predicted climate resilience.
The increasing global demand for critical minerals to support energy and technological advancement has accelerated exploration and research efforts for these essential resources. Since 2019, the United States Geological Survey (USGS) Earth Mapping Resources Initiative (EMRI) has worked to modernize geologic mapping of the Nation to better understand its critical mineral resources. To further this initiative, the USGS has flown a series of high-resolution airborne magnetic and radiometric surveys over large areas of the southern Midcontinent. The surveys cover known critical mineral deposits and areas with the potential to host additional critical minerals based on the presence of one or more overlapping mineral systems. One aspect of EMRI emphasizes close collaboration between the USGS and the Association of American State Geologists, as well as other government and industry partners to leverage geophysical, geological, and geochemical expertise on both regional and local scales. The EMRI high-resolution airborne survey data provide new insights into the geophysical framework of the southern Midcontinent and its critical mineral endowment. Additionally, discoveries made from the data have directed new studies for critical mineral exploration.
Earth’s surface is sculpted by numerous processes that move sediment, ranging from gradual and benign to abrupt and catastrophic. Although infrequent, high-magnitude sediment mobilization events can be hazardous to people and infrastructure, leaving topographic imprints on the landscape and remarkable narratives in the historical record. Hazardous events such as fires, storms, and earthquakes accelerate erosion and sediment transport, increasing landscape sensitivity to subsequent perturbations, thus forming a cascading hazard. Although the redistribution of sediment across Earth’s landscape can result in higher risks to vulnerable populations, cascading processes are commonly unaccounted for in hazard assessments. Cascading hazards can occur almost immediately after triggering events, such as coseismic landslides, or over months, years, or even decades after an initial perturbation, such as debris flows after wildfires or flooding in channels alluviated by volcanic debris. Sediment cascades span Earth’s surface, from mountaintops to river valleys, where erosion, deposition, and aggradation can lead to a myriad of hazardous processes, including decreased river conveyance capacity, which increases the likelihood of downstream flooding. An improved understanding of the magnitude, frequency, and persistence of cascading hazards is critical given the rapid changes in the frequency and severity of storms, fires, sea-level change, and cryospheric melting, as well as the expansion of high-population-density urban footprints in regions susceptible to solid Earth hazards. Understanding the full consequences and underlying physics of Earth’s cascading land surface hazards can help minimize future human and economic losses.
Rare earth elements (REEs) are a class of critical minerals, all of which can have supply chain vulnerability that impacts economic security. These elements are widely measured in environmental matrices via inductively coupled plasma mass spectrometry (ICP-MS); however, successful quantification can require time-consuming, sample-specific optimization. While a sample-by-sample approach is appropriate for targeted quantification studies, this approach is not suitable for mineral exploration efforts where rapidly screening thousands of samples for the presence of REEs is desired. Here, we demonstrated the use of a Quick Screening Tool for Approximating REEs (Q-STAR) to detect REEs in surface water and groundwater matrices, collected as part of existing environmental studies. A mass-to-charge ratio of 144 ( m / z = 144) was added to an ICP-MS method to screen for REEs in filtered water samples submitted for metals analyses to the U.S. Geological Survey (USGS) National Water Quality Laboratory. We detected the presence of REEs above a reference threshold of 1200 counts per second in 18 % of pre-selected 6626 samples. Using this screened dataset, we mapped estimated dissolved REE concentrations across the United States in relation to ecoregions and underlying geology. Data are constrained to where sample collection took place but nevertheless show estimated aqueous dissolved REE concentrations on a geographic scale that has not yet been studied. To validate Q-STAR, REEs were measured in a USGS standard reference sample, a subset of 88 archived filtered water samples, and in fresh filtered surface water samples. Our targeted analyses demonstrated a strong linear relationship between Q-STAR predicted and measured values in all archived samples for Nd (r 2 = 0.94), and light REEs (LREEs) such as lanthanum (La) (r 2 = 0.93), praseodymium (Pr) (r 2 = 0.94) and samarium (Sm) (r 2 = 0.94). Using Q-STAR screen values, nine field sites were identified and surface water samples recollected to confirm the continued presence of Nd and LREEs. Q-STAR can be used to screen an unlimited number of water samples for the presence of REEs prior to time-intensive and costly quantitative analyses and to generate large REE datasets for further investigation.
To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.
Understanding arsenic transformations during wildfires can help better constrain the environmental impacts of increased wildfire intensity, frequency, and burned area. Previous studies have monitored the evolution of metal(loid) speciation at specific time/temperature endpoints, hampering the comprehension of the dynamic transformations of metal(loid)s during wildfires. Here, a novel approach, namely in situ time-resolved X-ray absorption near edge structure (TR-XANES) spectroscopy, was used for the first time to monitor the heat-induced redox transformations of arsenic (As) in two As-rich sediments with different characteristics. No arsenic transformations were observed in either sediment at room temperature or when the sediments were heated to a maximum temperature of 400 ºC. When heated to a maximum temperature of 600 or 700 ºC, As underwent complex, dynamic, and partially reversible redox transformations, the extent of which varied with sediment properties, initial As speciation, and heating temperature and duration. In the case of sediments initially containing As(V) and a low sulfide/sulfate ratio, the As(V) was reduced to As(III) over a short period of time, followed by immediate reoxidation of As(III) to As(V). The extent of the transient As reduction increased with increasing maximum temperature. The final As speciation at the end of the heating experiment was not substantially different from that at the beginning of the experiment. In contrast, in sediments that were best described by a more complex combination of reference compounds (As(V) coprecipitated with or adsorbed on iron oxide, arseniosiderite, arsenopyrite) with a high sulfide/sulfate ratio, As(V) phases were reduced to As(III) and As(III) was further reduced to As(-I) (at 700 ºC, only), followed by delayed reoxidation of As(-I) to As(III) (at 700 ºC, only) and reoxidation of As(III) to As(V). Approximately 9% and 26% of all As remained as As(III) ( i.e., was not reoxidized to As(V)) at the end of the experiment when heated to a maximum temperature of 600 and 700 ºC, respectively, which is higher than the relative abundance of As(III) in the native sediment. These fire-induced As transformations can potentially enhance As mobilization to surface water and groundwater, posing risks to environmental and human health.