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Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado

Geologic map of the Emmons Lake volcanic center, Alaska

Introduction The Emmons Lake volcanic center is a spatially clustered group of stratovolcanoes and calderas in the southwestern part of the Alaska Peninsula, Alaska. The volcanic center is characterized by several ice- and snow-clad stratovolcanoes located within and along the margins of a nested-caldera complex that includes Emmons Lake. A shieldlike ancestral edifice (ancestral Mount Emmons) is truncated by the caldera complex and forms a broad volcanic platform around the center. The main stratovolcanoes of the Emmons Lake volcanic center are Pavlof Sister, Pavlof Volcano, Little Pavlof, Double Crater, Mount Hague, and Mount Emmons. Several small unnamed cinder cones and vents also are located within Emmons Lake volcanic center and on the east flank of Pavlof Volcano. Many of these cones and vents have been the source of the young lava flows that mantle the floor of the caldera. Pavlof Volcano, in the northeastern part of the Emmons Lake volcanic center, is one of the most historically (that is, the past about 300 years) active volcanoes in Alaska, and eruptions from Pavlof Volcano pose the greatest hazards to the region. Volcanic rocks of the Emmons Lake volcanic center overlie continental and marine sedimentary rocks of chiefly Late Jurassic to early Tertiary age. The oldest rocks in the area are those of the Naknek Formation, consisting of volcaniclastic sandstone, siltstone, and conglomerate of Late Jurassic age. The southern part of the area includes rocks of the Belkofski Formation, a thick sequence of volcaniclastic sandstone, siltstone, and conglomerate of middle Tertiary age. Lava flows, volcanic breccia, and fluvial volcaniclastic rocks of late Miocene age, which unconformably overlie the Belkofski Formation south of the Emmons Lake volcanic center, are primarily exposed on the islands just south of the Alaska Peninsula. The Emmons Lake volcanic center was affected multiple times by glaciation associated with the glacier expansion that characterized the Quaternary. Glaciation has played a key role in shaping the present-day landscape, and much of the eruptive history of the Emmons Lake volcanic center has involved interactions with glacier ice. Thus, a brief review of the Quaternary glacial history of the area is provided to establish the physical context for Emmons Lake volcanic center eruptive activity.

Alaska

Geochemical monitoring of volcanic fluids in the twenty-first century

This chapter reviews the state-of-the-art of geochemical volcano monitoring techniques. We cover in-situ monitoring technologies that rely on sampling fluids (direct sampling) and on instrumental analysis of the composition of such fluids in real-time (remote sensing of volcanic fluids is covered elsewhere in this book). We first review key concepts and principles in the field, and then review the results of some selected case studies and applications. We cover the large variety of fluid categories emitted by volcanoes, in both the near-(crater fumaroles and lakes, and plumes) and far-(degassing soils, groundwaters) fields. Our aim is to demonstrate the utility of measuring the chemistry of fluids released by volcanoes, and how these can help characterize volcano unrest, and eventually the increased likelihood of eruption. We conclude with a brief discussion of current challenges and knowledge gaps, and on future directions in geochemical monitoring.

Book chapter

Dendroseismological investigation of redwood trees along the North Coast section of the San Andreas Fault

Sequoia sempervirens (coast redwood) tree rings have the potential to annually resolve late-Holocene earthquakes on the northern San Andreas Fault based on direct (e.g., physical damage) and indirect (e.g., co-seismic environmental change) impacts, but scarcity of suitable samples and challenges crossdating this long-lived species have limited progress. More precise dating of the pre-1906 (penultimate) earthquake can improve hazard assessment and understanding of rupture segmentation. We target old trees (maximum >815 yr) along the North Coast section of the fault (increment cores via rope-climbing, 11 living trees; plunge cuts, 23 stumps) and employ complementary disturbance detection methods including radial-growth averaging (tree- and series-level), cataloging anatomical indicators (e.g., traumatic resin ducts, TRD), and dating structural components (e.g., reiterated trunks, leans). Multi-centennial ring-width chronologies at Fort Ross (1569−2023) and Gualala (1397−2023) promote continued study with incomplete crossdating limiting utilization of some series. Growth pulses (reductions, releases) and TRD dispersed across the record reflect dynamic environments that obfuscate detection of earthquake signals. The 1906 earthquake did not leave strong signatures on most trees, and when it did, within-tree response varied from normal presentation to discoloration, TRD, and missing rings. Synchrony of indicators at both locations identified 1678−1680 (6 of 15 trees) and 1698−1700 (8 of 16 trees) as the strongest disturbances among dated rings in the time range of the penultimate earthquake, peaking at 1698 (15.7 % of possible growth and anatomical indicators), but the triggering mechanisms for these events are unknown.

California

Prioritizing resource protection and understanding potential susceptibility of springs to surficial changes in a low-temperature geothermal system

Geothermal systems are vulnerable to changes in water budget and composition, requiring science-based management. This study uses a dataset of spring water temperatures, time series of groundwater residence time tracers (tritium and carbon-14), and stable isotopes of water to understand geothermal flow in a low-temperature geothermal system in north west Colorado, United States (Steamboat Springs). The geothermal system is bisected by the Yampa River, necessitating a stream mass balance approach to quantify total discharge. Time series analysis of water temperature data provides a ranked list of features more susceptible to surficial changes, which is corroborated using time series of tritium which indicate spatially distinct patterns of mixing between modern and pre-modern groundwater. All springs contain a portion of pre-modern groundwater that is thousands to tens of thousands of years old, a period coinciding with melting of extensive Pleistocene glaciers that was likely one of the recharge sources to the geothermal system. Stream mass balance indicates that greater than 80% of the total geothermal discharge is derived from diffuse or small springs, highlighting the extensive nature of the geothermal outflow zone and the association with local geologic structures. This study provides baseline data to support management of the Steamboat Springs geothermal system and indicates the utility of these approaches in developing science-based geothermal management.

Colorado

Seismic response comparison of a historical masonry church subject to real and simulated ground motions

In recent years, advanced numerical models and high-performance computing have facilitated the utilization of ground motion time series in the assessment of the non-linear dynamic behavior of historic masonry structures. Since recorded accelerograms can be sparse for specific analysis conditions, stochastic ground motion simulations have become a viable alternative to overcome this limitation. This study simulates the recorded acceleration time series of the Central Italy 2016 earthquake event at the closest station to the town of Macerata using a site-based stochastic approach. The simulated motions are seismologically evaluated using a goodness-of-fit method in terms of various intensity measures. The simulated records, in conjunction with real records, are used to study the non-linear dynamic behavior of San Filippo Neri church located in Macerata. The church of San Filippo represents an important example of Baroque religious architecture in central Italy, which was damaged and closed off to the public after the 2016 earthquake events. The construction was investigated with a vast diagnostic campaign which included on-site testing and dynamic identification tests. The collected data is used to calibrate the dynamic response of a three-dimensional finite element model of the church. The model is finally used to compare the non-linear seismic responses under real and simulated ground motions with the site recorded damage. The results of structural responses demonstrate a strong agreement between the real and simulated records, providing evidence to support the validation of the site-based stochastic simulation.

Macerata

Use of precariously balanced rocks to constrain postglacial earthquake magnitudes in New England, United States

We use the age and fragility of 13 precariously balanced rocks (PBRs) in Massachusetts, New Hampshire, and southwestern Maine to evaluate the estimated probabilistic seismic hazard (PSH) from the U.S. Geological Survey’s National Seismic Hazard Model (NSHM), and also develop a map of maximum postglacial earthquake magnitudes in the region. The PBRs are erratic boulders left behind by the retreat of the Laurentide ice sheet between 13 and 18 ka, and published ice retreat maps are used to estimate their fragility ages. The fragilities and ages of the rocks appear to be consistent with the NSHM, in that the estimated earthquake magnitudes and resulting ground motions that would topple them are only expected on timescales longer than their fragility ages. This result, on the North American passive margin, contrasts with PBR studies at active plate boundaries, where the PBR constraints imply large reductions to estimated PSH. It may be that the PBRs are not old enough in the eastern United States to reveal the same PSH modeling issues as those revealed in the plate boundary settings. The study provides constraints on maximum magnitudes of postglacial earthquakes across much of Massachusetts, New Hampshire, and southwestern Maine, with the constraints limited to the ages of the PBRs.

Maine. Massachusetts, New Hampshire

Earthquake effects surveyed during the nineteenth century as ecological features of Chinookan tidelands

Lasting effects of a Cascadia earthquake in 1700 were documented during surveys of Chinookan tidelands near the mouth of the Columbia River between 1805 and 1868. The effects resemble estuarine consequences, near Anchorage, of the 1964 Alaska earthquake: fatal drowning of subsided meadows and forests by post-earthquake tides, rebirth of marshes and forests through post-earthquake sedimentation, and uplift. Chinookan remains of killed forests were recorded by James Graham Cooper, John J. Lowell, and Cleveland Rockwell. Cooper, attached to a railroad survey and the Smithsonian Institution, wrote of redcedar stumps and trunks standing dead in tidal marshes of Shoalwater (now Willapa) Bay. Two such snags served as bearing trees for Lowell as he platted a Shoalwater Bay township under contract with the General Land Office. Rockwell, of the US Coast Survey, flecked landward edges of tidal flats west of Astoria with symbols that evoke remains of a bygone spruce forest. The Lewis and Clark Expedition, while in that area in 1805–1806, mapped and puzzled over tideland vegetation that post-1700 succession helps explain.

Alaska, British Columbia, California, Oregon, Wash

Using visualization science to inform the design of environmental decision-support tools—A case study of the U.S. Geological Survey Waterwatch

Environmental decision-support tools are increasingly being used to serve both expert and non-expert audiences. Many existing tools are primarily expert-focused, and redesigning them can be challenging because experts and non-experts interact with tools differently, existing users may be resistant to changes, and there is little guidance on how to prioritize redesign efforts and demonstrate their efficacy. In this report, we present a case study of a user-centered redesign of an established environmental decision-support tool—the U.S. Geological Survey WaterWatch. WaterWatch supports flood, drought, and other water resource management decisions through the display of water levels at gages across the United States. Using a participatory process, we identified a functional change (replacing the existing rainbow colormap), created an alternative design, and tested the alternative’s usability through two general public surveys. The results showed that replacing the rainbow colormap with a more intuitive diverging colormap improves usability, regardless of the audience’s subjective preference for the rainbow color scheme. In addition, we demonstrated the importance of using legends to improve the audience’s understanding of the map symbols. This study demonstrates how user-centered design approaches can be used to inform the design of high-profile products and tools.

Scientific Investigations Report

Storage timescales and the crystal growth history recorded in the layered reservoir of the Unit 3 Kulanaokuaiki Tephra Member of the Uēkahuna Ash from Kīlauea volcano

The Kulanaokuaiki Tephra Unit 3 (900 C.E.) was a subplinian basaltic scoria eruption, the largest known to have occurred at Kīlauea’s summit. The initiation mechanism and cause(s) of this highly hazardous eruption remain poorly understood, particularly as this style of activity has not been observed in the modern period. We use olivine diffusion timescales from Fe-Mg and lithium zoning to assess magma storage timescales and evaluate evidence for mixing prior to eruption. Of the 200 crystals assessed, 55% are normally zoned for forsterite and 45% are non-zoned. Zoned crystals (> 1 mm) ( n = 96) have average compositions of Fo 89 cores and Fo 81 rims, while small crystals 0.5–1 mm ( n = 14) have Fo 85 cores and Fo 82 rims. Modeled Fo diffusion timescales range from < 1 to 12.6 years (median of 3.0 years). Lithium maps in 32 of the forsterite-zoned crystals reveal a variety of lithium zoning types, most of which we attribute to crystal growth. Many lithium profiles are coupled to phosphorus within the outer ~ 100 μm of the crystal ( n = 17), reflecting growth processes and precluding their use for diffusion studies. Overall, our Unit 3 olivine dataset displays no evidence of magmatic priming shortly prior to eruption, unlike prior observations for the basaltic subplinian eruption of the Keanakāko‘i Tephra Unit E (1650 C.E.). Thus, explosive eruption magmas may be stored for considerably longer than previously thought, and magmatic priming is not a necessary precursor for Kīlauea’s explosive eruptions. We hypothesize that gas-driven filter pressing from crystallization of microlites and macrocrysts in the reservoir slurry contributed to the explosivity of the Unit 3 eruption.

Hawaii

The role of alkali bicarbonate-sulfate brines in the genesis of carbonatite REE resources at the Bear Lodge Alkaline Complex, Wyoming

Rare-earth element (REE) resources in the Bear Lodge Alkaline Complex, Wyoming, are hosted in a variably leached carbonatite dike swarm spatially related to bodies of diatreme breccia. This study examines fluid inclusions in carbonatite dikes, peripheral fluorite breccias, and smoky quartz veins to reconstruct the physiochemical conditions of REE mineralization. Results reveal a multi-stage evolution of carbonatitic fluids: 1) high-temperature (330–432°C), CO 2 -rich magmatic fluids, 2) REE-enriched alkali bicarbonate-sulfate brines, and 3) low-temperature meteoric (117–182°C) or diluted magmatic fluids. Multiphase inclusions (stage-2) contain burbankite, nahcolite, and alkali sulfate daughter crystals, linking the brines to early burbankite [(Na,Ca) 3 (Sr,Ba,REE) 3 (CO 3 ) 5 ] mineralization in carbonatite. REE mobility has been linked to the stability of aqueous complexes with ligands such as Cl-, SO 4 2- , and HCO 3 - . However, light REEs were not initially transported significant distances, rather they crystallized as burbankite from brines or brine-melts associated with the carbonatite magma. Crystallization of burbankite removed Na from the system, leaving residual fluids with high K/Na ratios and promoting potassic fenitization throughout the complex. Fractionation of light and heavy REEs and involvement of low temperature (<300°C), high K/Na bicarbonate brines may have facilitated transport and formation of peripheral occurrences that are more enriched in heavy REEs at Bear Lodge.

Wyoming

Surficial geology and Quaternary fault map of the Las Vegas Valley, Clark County, Nevada

The Surficial Geology and Quaternary Fault Map of the Las Vegas Valley, Clark County, Nevada is a 1:50,000-scale compilation of published 1:24,000-scale geologic maps integrated with new field and desktop mapping. This geologic map compilation and GIS database are part of a broader study on the Quaternary faults in the Las Vegas Valley, the results of which are summarized in this report. The map compilation utilized a variety of digital base maps to evaluate the characteristics of surficial deposits and Quaternary fault scarps including lidar data in undeveloped parts of the valley and orthorectified historical aerial photos in the urbanized center of the valley. The map distinguishes twenty surficial map units including alluvial-fan and ephemeral-wash deposits, groundwater discharge deposits of the Las Vegas Formation, and alluvium deposits of Las Vegas Wash. Quaternary faults include the Quaternary Las Vegas Valley fault system in the center of the valley and the Frenchman Mountain fault system along the eastern margin. All Quaternary fault traces in the valley were evaluated, and the previously published fault mapping was modified as needed. The new mapping and uniform correlation of surficial deposits displaced by Quaternary faults yields a consistent valley-wide characterization of the recency of fault activity. The map and GIS database include a Quaternary geochronology compilation of 119 previously published surficial deposit ages of various types, 35 new luminescence ages, and 3 new radiocarbon ages. The new age data further bracket the ages of the Las Vegas basin Quaternary stratigraphy and provide new constraints on the timing of Quaternary fault activity.

Nevada

Estimated hydrogeologic, spatial, and temporal distribution of self-supplied domestic groundwater withdrawals for aquifers of the Virginia Coastal Plain

Water use from private-domestic wells accounts for nearly 40 percent of total groundwater withdrawals in the Virginia Coastal Plain Physiographic Province (henceforth called the Virginia Coastal Plain). However, because self-supplied domestic water use generally falls below the Virginia Department of Environmental Quality (VDEQ) reporting and management threshold of 300,000 gallons per month, quantifying these withdrawals is challenging. This report builds upon the foundation of previous U.S. Geological Survey investigations by providing revised techniques to improve estimates of the aquifer source, spatial distribution, and monthly magnitude of these groundwater withdrawals. The aquifer sources of private-domestic wells in the Virginia Coastal Plain were estimated by cross-referencing 8,264 well records from the VDEQ and the Virginia Department of Health to a digital model of the Virginia Coastal Plain hydrogeologic framework. This analysis highlights the regional importance of the Yorktown-Eastover, Potomac, and surficial aquifers. Collectively, these three aquifers account for 80 percent of self-supplied domestic groundwater withdrawals. The population using self-supplied domestic water was estimated using census blocks, well-use ratios, building footprints, and land-use and land-cover data to produce a high-resolution, disaggregated, raster-based dataset. This approach improves upon previous models at the census-block or road-network scale by reducing the low-density spread of the self-supplied domestic population across undeveloped areas and concentrating the population and its corresponding water use in the areas where it is most likely to occur. Results show that an estimated 475,332 people comprise the 2020 self-supplied domestic population of the Virginia Coastal Plain, an increase of 5.7 percent since 2010, and the greatest concentrations of self-supplied domestic population surround large cities. Estimates could be further refined with the addition of current and complete spatial data on public water-system service areas. The quantity of water used by the self-supplied domestic population was estimated by modifying published state per-capita water-use coefficients with the corresponding monthly variability assessed from Virginia Coastal Plain public water-system withdrawal data. This analysis estimates an average increase of 12 percent from June through August and an average decrease of 8 percent from December through March from the baseline annual average of 80 gallons per day per capita, which generally matches similar studies in the eastern United States. The application of these revised methodologies for the estimation of private-domestic wells and the self-supplied domestic population improves understanding of domestic groundwater use in the Virginia Coastal Plain across hydrogeologic, spatial, and temporal scales. These revisions help better inform water-resource managers and decision makers and support higher resolution groundwater modeling. Furthermore, these methods are transferrable to other areas where self-supplied domestic water withdrawals are important to the overall water budget.

Virginia

Divisions of geologic time—Major chronostratigraphic and geochronologic units

Effective communication in the geosciences requires consistent uses of stratigraphic nomenclature, especially divisions of geologic time. A geologic time scale is composed of standard stratigraphic divisions based on rock sequences and calibrated in years. Over the years, the development of new dating methods and refinement of previous ones have stimulated revisions to geologic time scales. Since the mid-1990s, geologists from the U.S. Geological Survey (USGS), State geological surveys, academia, and other organizations have sought a consistent time scale to be used in communicating ages of geologic units in the United States. Many international debates have occurred over names and boundaries of units, and various time scales have been used by the geoscience community. For consistency purposes, the USGS Geologic Names Committee and the Association of American State Geologists developed Divisions of Geologic Time .

Fact Sheet

Tungsten skarn quantitative mineral resource assessment and gold, rare earth elements, graphite, and uranium qualitative assessments of the Kuldjuktau and Auminzatau Ranges, in the central Kyzylkum region, Uzbekistan

A new quantitative mineral resource assessment for tungsten skarn was conducted for the Auminzatau and Kuldjuktau mountain ranges in Central Uzbekistan, along with qualitative assessments of orogenic gold, rare earth elements (REEs), amorphous graphite, and uranium. By integrating a variety of geological, geochemical, geophysical, and remote sensing data sets, estimates of undiscovered tungsten skarn deposits in permissive tracts are combined with grade and tonnage distributions of known deposits to generate probabilistic estimates of undiscovered resources. Undiscovered deposits in Auminzatau are estimated to contain median resources of 98 thousand metric tons (kt) of WO 3 with a 70 percent (%) probability of at least 28 kt and a 10% probability of at least 468 kt, of which 16 kt to 293 kt may be economic to extract. In Kuldjuktau, the undiscovered deposits are estimated to contain median resources of 27 kt of WO 3 with a 60% probability of at least 12 kt and a 10% probability of at least 208 kt, of which 5 kt to 132 kt may be economic to extract. Our results suggest that the Auminzatau–Kuldjuktau Mountains area is highly prospective for additional discovery of significant Au and U resources and has low prospectivity for discovery of significant REE and graphite resources.

Minerals

Hydrogeology of stratified drift in Farmington, Connecticut: Available data and future needs

The purpose of this report is twofold. The first is to update hydrogeologic information on the major stratified-drift deposits that underlie much of Farmington. The second is to outline data requirements for future ground-water evaluation and management. The scope of the report is limited to the stratified drift, as it is the only aquifer capable of sustaining large withdrawals for public or industrial supply. This aquifer is composed of interbedded layers of gravel, sand, silt and clay. Most of this material was deposited by glacial meltwaters, but locally the aquifer contains some unconsolidated deposits of nonglacial origin. The most extensive stratified-drift deposits are in the valleys of the Farmington and Pequabuck Rivers.(See plate B.) A few small areas of stratified drift near East Farmington Heights and Oakland Gardens are not discussed in this report as their potential for large-scale development is slight.

Connecticut

Tracking diagenetic alteration of magnetic susceptibility in thrust ridge and slope basin sediments of the Cascadia margin (ODP Sites 1249 and 1252; IODP Site U1325)

We investigated sediment core records from the Cascadia Margin (Ocean Drilling Program Sites 1249 and 1252 at Hydrate Ridge; Integrated Ocean Drilling Program Site U1325 offshore Vancouver Island) using a Zr/Rb heavy mineral proxy from X-ray fluorescence (XRF) core scanning to identify intervals of primary detrital magnetic susceptibility (κ) and predict intervals where diagenesis caused magnetite dissolution by hydrogen sulfide. We also measured total sulfur (TS) content, grain size distributions, total organic carbon (TOC) content, and the magnetic mineral assemblage to further constrain the role of diagenesis on κ. Understanding how κ can be used to better characterize the varied effects of detrital and diagenetic signals in marine settings is important for understanding biogeochemical cycling and records of paleoenvironmental change. The upper 100 m of slope basin Site 1252 contains multiple intervals (> 90 m total) of decreased κ correlated with elevated TS content, consistent with dissolution of magnetite and precipitation of pyrite, iron monosulfides, and/or elemental sulfur. Similarly at the other slope basin site, Site U1325, κ is lower and TS is elevated in the interval between 24 and 51 mbsf, due to sulfide formation. At both slope basin sites, these low κ intervals correspond with high TOC, suggesting the possibility that organoclastic sulfate reduction (OSR) is likely a major driver of diagenetic alteration of κ at these sites. High TS:TOC ratios at Site U1325 suggests anaerobic oxidation of methane (AOM) during sulfate-methane transition zone (SMTZ) migration may have contributed to alteration of κ. In contrast, within the upper 90 m of Site 1249, a methane seep site at the summit of Hydrate Ridge, κ is almost entirely altered by diagenetic processes, with much of the low κ explained by a high degree of iron sulfide formation, while some intervals are affected by precipitation of magnetic iron sulfides that maintain or even increase κ. The presence of abundant methane seepage and gas hydrate as well as chemosynthetic seafloor fauna at this site, suggests that sulfide is released to the water column and AOM, rather than OSR, drives diagenetic alteration of κ at this site. Overall, the slope basin sites show episodic variation of κ that is influenced by TOC content, likely driven by changes in marine primary productivity and sedimentation rate, while the seep site shows consistently altered κ with lower TS content and no correlation with TOC. Methane seep environments likely experience loss of hydrogen sulfide to the water column and oxidation of hydrogen sulfide by seafloor seep fauna, which limits the amount of solid phase sulfur (pyrite, iron monosulfides, elemental sulfur) that can be precipitated within the sediments. In contrast, the migration of a buried SMTZ at slope basin sites results in enhanced sulfur precipitation within the sediments. This integrated magnetic and geochemical approach reveals the diagenetic production pathway and residence time of sulfide with the sediment column ultimately controls the style and degree of diagenetic loss of κ in marine sediments. This approach works best in environments with unaltered reference intervals/sites, consistent magnetic mineralogy, and clay-to-silt grain sizes.

Cascadia margin, Pacific Ocean

Hydroacoustic observations reveal drivers of mixing and salinization of a karst subterranean estuary during intense precipitation

Karst subterranean estuaries within globally ubiquitous carbonate aquifers are coastal groundwater ecosystems that provide an essential water resource for human populations. To understand the drivers of salinization within a coastal aquifer in the Yucatan Peninsula (Mexico), we employed hydroacoustics in flooded caves to observe how oceanic and atmospheric events facilitate mixing between the meteoric lens (fresh-brackish groundwater) and the saline groundwater on tidal and episodic timescales. Precipitation during Tropical Storm Carlotta increased the flow and salinity of the meteoric lens without evidence for vertical mixing across the halocline. We postulate that vertical migration of haloclines in the conduit relative to those within the rock matrix during precipitation creates lateral density gradients that drive mixing, and ultimately creates a brackish layer within the meteoric lens. These results provide a mechanistic explanation for vertical and lateral exchange in a coastal carbonate aquifer, which has implications for groundwater response to future climatic change.

Ox Bel Ha cave system, Yucatan peninsula