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Guidelines for producing integrated 210Pb and 14C age-models

Accurate reconstructions of past environmental changes are crucial in paleoecological research and require reliable chronologies of sedimentary archives. Establishing robust age-models and obtaining the most appropriate proxies for analysis is a complex scientific endeavor, requiring extensive resources and collaboration among specialists, including radiochronologists. Radiometric dating methods, such as 210 Pb and radiocarbon ( 14 C), are frequently employed to establish chronologies in aquatic sedimentary deposits and peat bogs. In this study, we review key aspects of sampling, analysis, and the principles underlying 210 Pb and 14 C age-models, focusing on methods for developing robust joint chronologies for paleoenvironmental research. Drawing largely from the authors' experiences and group discussions during and after a scientific workshop in 2022, we discuss important considerations for site selection, sampling strategies, and radiometric dating to construct integrated 210 Pb and 14 C age-models. Using expert consensus, this group – called Paleostats – aims to provide a set of best practices for other geochronologists with this methods paper. Among our conclusions, we emphasize the importance of accounting for site-specific factors such as prior information on sedimentation rates to establish appropriate sampling and analytical strategies. The use of appropriate coring devices can minimize disturbance to sediments and ensure the core surface remains intact and preserved until sectioning. Where excess 210 Pb is expected, sectioning at intervals of ≤1 cm provides an adequate sampling resolution for 210 Pb dating. Exceptions are possible, allowing for ~2–3 cm sections in areas with confirmed high sedimentation rates (e.g., > 1 cm yr −1 ). Recovering deeper core sections for 14 C dating with sufficient overlap allows for accounting errors in depth estimates made in the field. Special attention is advised during time intervals where validation proxies, such as the human-made radionuclides 137 Cs or post-bomb 14 C, are expected, and to determine the depth of secular equilibrium between 210 Pb and 226 Ra. Radiocarbon analyses are commonly performed by accelerator mass spectrometry, and age models are constructed mainly using Bayesian statistics with Markov Chain Monte Carlo techniques (e.g., Bacon ). A Bayesian approach ( Plum ) is now available for producing 210 Pb age-models, which infers the 210 Pb ex flux, eliminates the need for selecting an equilibrium depth, and allows dating cores with incomplete 210 Pb ex inventory. Plum offers improved chronologies by integrating raw 210 Pb and 14 C data, and these age-models can be enriched with other dating methodologies, such as identifying tephras and other well-recorded historical events. Harmonized reporting would contribute to making radiometric age-models reproducible, which would benefit from an international effort. Using 210 Pb and 14 C to produce integrated age-models may yield better insights into the interplay between natural and recent anthropogenic forcings on ecosystems. This can enhance our understanding of environmental processes and their impacts on climate change, ultimately supporting science-based assessments and decisions.

Earth-Science Reviews

Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain

VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey's (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite . Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.

Texas

Three-dimensional temperature maps of the Williston Basin, USA: Implications for deep hot sedimentary and enhanced geothermal resources

As part of U.S. Geological Survey's (USGS) efforts to identify and assess geothermal energy resources of the US, a three-dimensional (3D) geologic and thermal model has been constructed for the Williston Basin, USA. The geologic model consists of all sedimentary units above the Proterozoic and Archean crystalline rock (called basement herein), with a total sedimentary thickness of up to 5 km near the basin center. Twenty-nine geologic units were mapped from interpreted formation tops from 16,465 wells. A 3D temperature model was constructed to a depth of 7 km by constructing a 3D heat flow model for the sedimentary units, followed by estimating underlying temperature using a one-dimensional (1D) analytic solution for heat flow within the underlying crystalline basement. Using the sedimentary basin model, heat flow was simulated in 3D and was calibrated using three temperature datasets: 1) 24 high-confidence static temperature logs (equilibrium thermal profiles), 2) more than15,000 drill stem test (DST) measurements from >7,000 wells, and 3) more than 45,000 bottomhole temperature (BHT) measurements from >14,000 wells. The DST and BHT datasets provide broad spatial coverage, but are lower confidence, primarily because measurements were made prior to attaining thermal equilibrium. DST and BHT measurements were binned regionally to develop representative thermal profiles that generally agree with these lower quality data (hereafter called pseudowell temperature profiles). Layer properties (primarily thermal conductivity and compaction curves) were set to best estimate values, then the heat flow model was calibrated to fit pseudowell and static temperature logs primarily by adjusting basal heat flow to approximate the overall temperature profile. Minor adjustments to thermal conductivity allowed adjusting changes in slope at lithologic contacts. Resulting maps include 3D temperature and basal (bottom of sedimentary units) heat flow estimates, which are used as input for the temperature model of the basement. The crystalline basement temperature model uses an analytic 1D solution to the heat flow equation that requires estimates of heat flow and temperature at the upper boundary (i.e., the sediment/basement contact), radiogenic heat production within the crystalline basement, and reference thermal conductivity (i.e., uncorrected for temperature). Two regions of high heat flow are identified: 1) in western North Dakota along the North American Central Plains Conductivity Anomaly and 2) in eastern Montana near the Poplar dome. Within the sedimentary column in the center of the basin of the basin, an area of approximately 100,000 km2 is predicted to have moderate- to high-temperature geothermal resources (>90 °C) under the thickest sequences of sediments. Where thick insulation and high heat flow coincide, electric-grade resources can be less than 4 km deep. Assuming a maximum feasible drilling depth of 7 km, temperatures are predicted to be as high as 175 °C. The geologic model may be used to identify strata at sufficient temperatures that may have natural permeability or that may have conditions that favor development of enhanced/engineered geothermal systems resources.

Montana, North Dakota, South Dakota

Formation of vertical columnar seismic structures and seafloor depressions by groundwater discharge in the drowned Miami Terrace platform and overlying deep-water carbonates, southeastern Florida

The presence of vertical cross-formational fluid migration passageways within sedimentary basins can profoundly impact aquifer and reservoir fluid-flow and their identification is fundamental to informing management of subsurface fluid resources (groundwater, oil, gas). In an onshore and offshore southeastern part of Florida, 2D/3D seismic-reflection and bathymetry data document ∼153 vertical columnar structures composed of reflection disruptions up to 790 m in the height and averaging 360 m in diameter, and ∼219 subcircular to circular seafloor depressions up to 1334 m wide. Our study focuses on these features found within the offshore shallow-marine carbonate Miami Terrace platform, which drowned approximately at the end of the middle Miocene, and within overlying Plio-Quaternary deep-water carbonate slope and drift deposits. Most columnar structures are rooted in stratiform aquifers of the Miami Terrace platform and associated with faults or fault intersections produced by Eocene and circa late Miocene tectonics. The columns commonly terminate within the platform or as subcircular depressions along an amalgamated karstic and drowning unconformity at the platform top. The columns typically stretch upwards from a zone of deep karst cavity collapse through the Miami Terrace platform with upward decreasing sag on internal reflections. Following drowning and Plio-Quaternary partial burial of the Miami Terrace platform by deep-water deposits, the subcircular depressions and faults along the platform top were points of origin for a second phase of column growth upward into the deep-water deposits. The continuation of deep platform cavity collapse and column evolution produced pockmarks along paleo-seafloors within the deep-water deposits and at the present-day sea floor. The Plio-Quaternary pockmarks formed at water depths too deep to suggest an origin related to meteoric karst above or near sea level, but rather their formation is suggested to be related to cyclic sea level falls that drove increased groundwater head and density gradients, and seafloor discharge of offshore freshened groundwater sourced from the underlying platform. Plausibly, mixing of freshened groundwater and seawater at the seafloor discharge sites drove dissolution of the host deep-water deposits, which together with erosion by groundwater venting and current scouring formed the pockmarks. Seaward of the Plio-Quaternary seafloor pockmarks, at the late-middle Miocene upper slope of the Miami Terrace platform and along the regional karst/drowning unconformity is a slope-parallel band of ∼189 densely distributed subcircular seafloor depressions with diameters up to 1334 m at water depths up to ∼660 m. It is plausible that along the upper slope, faults and fractures produced by gravity-driven slope instability and possibly tectonics formed a dense network of fluid passageways that promoted upward artesian freshened groundwater flow to sites of discharge where mixing with seawater generated limestone dissolution and the depressions. But tectonic uplift may have forced emersion and initial meteoric sinkhole formation circa late Miocene with later enhancement by freshened groundwater discharge and bottom current erosion.

Florida

Rapid emplacement of the Keaiwa Lava Flow of 1823 from the Great Crack in the Southwest Rift Zone of Kilauea volcano

The Keaīwa Lava Flow of 1823 in the Southwest Rift Zone of Kīlauea volcano is unusual for its expansive pāhoehoe sheet flow morphology and lack of constructive vent topography, despite having a similar tholeiitic basalt composition to other lavas erupted from Kīlauea. This lava flow issued from a ∼10-km-long continuous fissure now known as the Great Crack, and has an unusually thin sheet flow morphology with margin thicknesses of ∼15–110 cm (average of 42 cm). Based on field observations of the lava flow at its fissure vent (e.g., drain-back features), we propose that the Great Crack formed, or at least significantly widened, just prior to and syn-eruptively with this 1823 eruption. The absence of pyroclastic cones or spatter ramparts indicates that the eruption consisted of a rapid outpouring of relatively degassed lava as the fissure unzipped. The rapidly moving lava flow overtopped pre-existing tumuli and scoria cones (e.g., Lava Plastered Cones) up to ∼10 m tall. Glass and whole-rock chemistry yield homogeneous compositions for the lavas erupted from the Great Crack, with glass compositions of 6.40 ± 0.10 wt% MgO and whole-rock compositions of 7.39 ± 0.07 wt% MgO. Lava pads erupted from a short western fissure system are richer in mafic minerals (e.g., olivine and clinopyroxene), and show slightly more MgO-rich whole-rock compositions (7.79 ± 0.05 wt%). MgO-in-glass thermometry on juvenile spatter yield eruption temperatures of 1153 ± 13°C that are typical of Kīlauea lavas. Thus, the extensive sheet-like lava flow morphology is not a direct consequence of unusual magmatic or rheological conditions (i.e., low viscosity). Instead, the flow morphology is associated with high effusion rates caused by sudden drainage of uprift magma as it erupted from the Great Crack. Lava flow modeling on a 2-m-resolution digital elevation model indicates that a minimum bulk effusion rate of ∼5800 m 3 /s (∼3500 m 3 /s dense rock equivalent) and a minimum flow velocity of ∼11 m/s are required for the lava flow to overcome the topography of the Lava Plastered Cones. This effusion rate is among the highest inferred for eruptions in Hawaiʻi and around the world. This study highlights a less frequent eruption style at Hawaiian volcanoes characterized by a sudden outpouring of lava from an unusual fissure system. Local eyewitness accounts indicate that the 1823 eruption was preceded by seismicity. Given the complex magmatic-volcanic-tectonic relations across Kīlauea, we speculate that the south flank could have slipped over one or more events that ultimately triggered unzipping of the Great Crack and passive release of briefly stored uprift magma. An eruption similar to 1823 at Kīlauea or Mauna Loa, with an eruptive timeframe that could be as short as an hour, with high effusion rates and rapid flow front velocities, would not easily allow for a timely response.

Hawaii

Diel temperature signals track seasonal shifts in localized groundwater contributions to headwater streamflow generation at network scale

Groundwater contributions to streamflow sustain aquatic ecosystem resilience; streams without significant groundwater inputs often have well-coupled air and water temperatures that degrade cold-water habitat during warm low flow periods. Widespread uncertainty in stream-groundwater connectivity across space and time has created disparate predictions of energy and nutrient fluxes across headwater networks, hindering predictions of cold-water habitat resilience under climate change scenarios. Recently, annual paired air and water temperature signals have been harnessed to indicate stream water thermal sensitivity and the dominance of deep versus shallow groundwater influence, although the utility of diel air–water temperature signal metrics for hydrologic inference has remained unexplored. Here we analyzed two consecutive years of locally paired, air–water temperature data from 47 headwater stream sites in the Catskill Mountains, New York, USA, and discovered characteristic seasonal patterns in diel temperature signal sinusoid metrics (amplitude ratio, phase lag, and mean ratio) driven by shifts in streamflow generation mechanisms and stream network position. Hydrologic interpretations of observed patterns were supported by stream heat budget model scenarios and additional analysis of paired air–water temperature data from two streams in Shenandoah National Park, Virginia, USA, with well characterized stream-groundwater connectivity. We found that within smaller tributaries, streamflow generation transitions from runoff to groundwater dominance were driven by hillslope drying during seasonal periods of lower precipitation. This was evidenced by significant correlations (p < 0.01) between daily water:air temperature signal amplitudes (non-linear decreases of ∼ 50 %) and derived base-flow index at 22 of the 28 sites, indicating enhanced local groundwater influence on streamflow promotes decoupling of diel air–water temperature signals. Additionally, ratios between daily water:air temperature signal means were lower in tributaries (∼0.68) when compared to main-stem (∼0.8) sites, increasing linearly throughout the observational period. In conceptual stream heat budget models, groundwater inflow had minimal effects on daily phase lags (∼0.2 hr), but increases in fractional groundwater discharge (0–50 %) depressed daily amplitude (∼20 % to 50 %) and mean ratios (∼15 %), supporting the sensitivity of daily metrics to interpreted changes in seasonal groundwater contributions to streamflow. During observational periods (i.e., April through October 2021 and 2022), significant differences (p < 0.01) between tributary and main-stem air–water metrics occurred when base-flow contributions were highest (∼0.93 vs. ∼ 0.68), as sites lower in the network had daily temperature metrics dominated by stream channel thermal inertia, rather than local groundwater connectivity, showing enhanced air–water diel signal coupling during warmer, drier periods. Divergent air temperature coupling across the network was interpreted as being driven by distance from local groundwater source zones, additional lateral groundwater inflows do not contribute a meaningful fraction to channel discharge lower in the network. Given the growing footprint of stream temperature observations, diel air–water temperature signals can provide distributed metrics sensitive to upstream groundwater discharge. Consequently, these metrics can support ongoing efforts by resource managers and researchers seeking to forecast the resilience of cold-water habitat to climate warming and changing precipitation regimes in mountain headwater streams.

New York, Virginia

Cancer risk and estimated lithium exposure in drinking groundwater in the US

Importance Lithium is a naturally occurring element in drinking water and is commonly used as a mood-stabilizing medication. Although clinical studies have reported associations between receiving lithium treatment and reduced cancer risk among patients with bipolar disorder, to our knowledge, the association between environmental lithium exposure and cancer risk has never been studied in the general population. Objectives To evaluate the association between exposure to lithium in drinking groundwater and cancer risk in the general population. Design, Setting, and Participants This cohort study included participants with electronic health record and residential address information but without cancer history at baseline from the All of Us Research Program between May 31, 2017, and June 30, 2022. Participants were followed up until February 15, 2023. Statistical analysis was performed from September 2023 through October 2024. Exposure Lithium concentration in groundwater, based on kriging interpolation of publicly available US Geological Survey data on lithium concentration for 4700 wells across the contiguous US between May 12, 1999, and November 6, 2018. Main Outcome and Measures The main outcome was cancer diagnosis or condition, obtained from electronic health records. Stratified Cox proportional hazards regression models were used to estimate the hazard ratios (HRs) and 95% CIs for risk of cancer overall and individual cancer types for increasing quintiles of the estimated lithium exposure in drinking groundwater, adjusting for socioeconomic, behavioral, and neighborhood-level variables. The analysis was further conducted in the western and eastern halves of the US and restricted to long-term residents living at their current address for at least 3 years. Results A total of 252 178 participants were included (median age, 52 years [IQR, 36-64 years]; 60.1% female). The median follow-up time was 3.6 years (IQR, 3.0-4.3 years), and 7573 incident cancer cases were identified. Higher estimated lithium exposure was consistently associated with reduced cancer risk. Compared with the first (lowest) quintile of lithium exposure, the HR for all cancers was 0.49 (95% CI, 0.31-0.78) for the fourth quintile and 0.29 (95% CI, 0.15-0.55) for the fifth quintile. These associations were found for all cancer types investigated in both females and males, among long-term residents, and in both western and eastern states. For example, for the fifth vs first quintile of lithium exposure for all cancers, the HR was 0.17 (95% CI, 0.07-0.42) in females and 0.13 (95% CI, 0.04-0.38) in males; for long-term residents, the HR was 0.32 (95% CI, 0.15-0.66) in females and 0.24 (95% CI, 0.11-0.52) in males; and the HR was 0.01 (95% CI, 0.00-0.09) in western states and 0.34 (95% CI, 0.21-0.57) in eastern states. Conclusions and Relevance In this cohort study of 252 178 participants, estimated lithium exposure in drinking groundwater was associated with reduced cancer risk. Given the sparse evidence and unknown mechanisms of this association, follow-up investigation is warranted.

contiguous United States

Lunar analog study using portable gamma-ray neutron detector: Radiochemical mapping of silicic-to-basaltic volcanic terrains in the San Francisco Volcanic Field, Arizona

Studying lunar silicic volcanism provides key insights into the Moon’s crustal evolution, magmatic processes, and volcanic history. The Lunar-VISE (Lunar Vulkan Imaging and Spectroscopy Explorer) mission will investigate the Gruithuisen domes, a unique lunar region hypothesized to have formed through silicic volcanism. Using instruments on a Firefly Aerospace lander and a Honeybee Robotics rover, Lunar-VISE will analyze mineralogy, geochemistry, and surface properties to determine the origin and evolution of the domes, with a gamma-ray and neutron spectrometer (LV-GRNS) among its payload instruments. In preparation for this mission, we conducted preliminary fieldwork using a handheld gamma-ray neutron detector with NaI(Tl) and Cs LiYCl :Ce (CLYC) scintillators. This study focuses on various rhyolitic and basaltic volcanic centers in the San Francisco Volcanic Field (SFVF) near Flagstaff, Arizona—specifically Sugarloaf Peak, Bonito Lava Flow, and Robinson Mountain, a region containing several well-characterized lunar analog sites. The SFVF was selected for this study due to its broad compositional diversity spanning basaltic to rhyolitic compositions, its well-preserved volcanic morphologies, and its extensive use in previous NASA field campaigns and astronaut training exercises, making it an ideal terrestrial laboratory for testing planetary exploration techniques. We measured natural radioactivity, specifically from potassium (K), thorium (Th), and uranium (U) and other elements in their decay chains, which serve as diagnostic tracers of magmatic differentiation and crustal evolution processes, to assess geochemical variability across compositionally diverse terrains. The detector’s sensitivity was assessed across varying concentration levels. Regionally averaged concentrations of radioisotopes were determined by gamma-ray spectroscopy at selected sites. Our measurements reveal significant compositional variations between sites, with Sugarloaf Peak (rhyolitic, silicic dome) exhibiting the highest average radioisotope concentrations (K: 3.29 ± 0.24 wt%, U: 14.35 ± 1.81 ppm, Th: 27.14 ± 2.43 ppm), while Bonito Lava Flow (K: 1.13 ± 0.08 wt%, U: 3.86 ± 0.52 ppm, Th: 7.52 ± 1.02 ppm), and Robinson Mountain (K: 1.46 ± 0.16 wt%, U: 5.59 ± 1.06 ppm, Th: 11.75 ± 1.98 ppm) show lower concentrations aligned with basaltic compositions. Gamma-ray fluxes were elevated by a factor of approximately three to four at Sugarloaf Peak relative to nearby basaltic terrains, consistent with expected geochemical differentiation patterns. Furthermore, at meter scales, proximity to geological features significantly affects measurements. Th concentrations adjacent to a cliff face at Sugarloaf’s base were 28% higher than values measured 3-5 meters away from the same feature, demonstrating localized compositional heterogeneity. Analysis of station-by-station measurements reveals that K, U, and Th concentrations show an elevation trend at Robinson Mountain and generally higher concentrations near Sugarloaf Peak’s summit, suggesting progressive magmatic differentiation and/or the presence of more evolved lithologies at higher elevations. By mapping these elements on Earth using GRNS, we aim to optimize measurement techniques for Lunar-VISE and similar rover-borne missions by demonstrating the applicability of portable GRNS instruments for planetary surface exploration in an analog environment.

Arizona

Upper crustal seismic velocity structure of the Hayward fault zone, San Francisco Bay, California, USA: Results from the 2016 East Bay Seismic Experiment (EBSI-16)

We developed Vp, Vs, Vp / Vs ratio, and Poisson’s ratio models of the uppermost crust (<4 km depth) from the eastern San Francisco (SF) Bay (California, USA) to near the Calaveras fault along a 15-km-long, linear profile. Upper crustal velocities are highly variable beneath, west, and well east of the Hayward fault. We observe eight notable features, from west to east: (1) Near San Francisco Bay, there is an ~2-km-wide structure with high Vp / Vs ratios (up to 5) and Poisson’s ratios (up to 0.48) extending from the surface to the base of our model, which we suggest the structure is a near-vertical fault that lies along a straight-line projection between the Silver Creek fault to the south and the Point Richmond fault to the north. The structure may be part of an ~90-km-long fault along the eastern SF Bay. (2) The western East Bay Plain, the lower lying area between the bay and the hills, includes up to 800 m of low-velocity sediments ( Vp ~1600–3000 m/s, Vs ~500 m/s to ~1000 m/s), underlain by higher velocity basement rocks ( Vp ~3000–5800 m/s; Vs ~1000–1500 m/s). (3) Between ~1 km and 3 km east of the Bay shoreline, sediments thin in a series of steps (likely faults) toward the Hayward fault. (4) Between ~3 km west and ~1 km east of the Hayward fault (at the East Chabot fault) at depths greater than 1 km, basement Vp (up to 6000 m/s) and Vs (up to 2800 m/s) are high, and Vp / Vs ratios (<2) and Poisson’s ratios (<0.3) are low, suggesting crystalline rocks. Furthermore, a near-vertical zone of low Vp / Vs ratios and Poisson’s ratios is between near-surface traces of the Hayward and East Chabot faults, likely corresponding to the San Leandro Gabbro of Ponce et al. (2003) . (5) Eastward of the East Chabot fault in the upper 1.5 km, basement Vp (~3000 m/s to ~4200 m/s) and Vs (~1200–2000 m/s) are lower than those west of the fault. (6) In the eastern Hayward/Oakland Hills, there are zones of laterally varying, high- and low-velocity ( Vp ~2500–3000 m/s) Jurassic–Cretaceous and Tertiary sediments in the shallow subsurface that likely extend much deeper than imaged. (7) Seismic energy that propagates westward from sources east of the Hayward fault (HF) appear weaker than energy that propagates eastward from sources west of the HF, suggesting that the HF acts as a partial barrier to shallow seismic energy propagation into the more populated eastern SF Bay area. (8) Unlike many fault zones, it appears that the active trace of the Hayward fault (in our study area) is not cored by a prominent, low-velocity zone relative to rocks to the east and west of the active trace. However, the active trace does mark a prominent change from relatively higher velocities to the west and lower velocities to the east.

California

Stratigraphic notes—Volume 1, 2022

This is the first volume in the U.S. Geological Survey (USGS) series of reports on stratigraphy entitled “Stratigraphic Notes,” which consists of short papers that highlight stratigraphic studies, changes in stratigraphic nomenclature, and explanations of stratigraphic names and concepts used on published geologic maps. “Stratigraphic Notes” is a long-term (multiyear), multivolume publication containing articles that address updates or revisions to stratigraphic nomenclature (and whose content ultimately will be incorporated by National Geologic Map Database personnel into Geolex, https://ngmdb.usgs.gov/Geolex/ ). We welcome papers for the “Stratigraphic Notes” series from geoscientists of the USGS, of State Geological Surveys, and from academicians. Papers can be submitted for publication in “Stratigraphic Notes” by contacting the USGS Geologic Names Committee ( gnc@usgs.gov ). As new “Stratigraphic Notes” volumes are published, links to the volumes will be posted at https://doi.org/10.3133/pp1879 . This first volume ("Stratigraphic notes—Volume 1, 2022") includes articles that provide guidance for those who wish to submit papers to “Stratigraphic Notes,” as well as information on how to make your manuscripts compliant for geologic names reviews and how to organize your paper’s content to facilitate inclusion of new or revised names in Geolex. This volume also includes some specific guidance on conducting geologic names reviews of geologic and hydrogeologic reports.

Professional Paper

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

Refining the earthquake history of south-central Alaska through lake records

The Alaska–Aleutian subduction zone (AASZ) is one of the world's most seismically active plate boundaries and the source of the 1964 M w 9.2 Great Alaska earthquake–the second largest instrumentally recorded earthquake in the world. Understanding the nature and frequency of such earthquakes is necessary for seismic and tsunami hazard assessment, but instrumental and historical records that span less than 150 years are too short to allow a statistically reliable analysis of earthquake recurrence times. This calls for studies of evidence of past earthquakes, extending the earthquake catalog further back in time. Subduction-zone paleoseismology in south-central Alaska is predominantly based on coastal evidence of land-level changes and tsunamis generated by megathrust earthquakes and preserved in the geological record. A complementary approach is lacustrine paleoseismology, which is still a relatively young discipline in Alaska. However, globally, lake basins are well-established high-resolution and continuous recorders of paleoseismic activity along subduction zones, relying on the identification of underwater landslide deposits and turbidites generated by seismic shaking. As a result, lake basins not only register ground shaking from megathrust earthquakes, but also from intraslab and crustal earthquakes, which are typically not accompanied by significant land-level changes. In this review paper, we combine coastal and lacustrine paleoseismology approaches to refine the south-central Alaskan earthquake history by comparing the paleoseismic records from two lakes (i.e., Eklutna Lake, located in the Chugach Mountain Range, and Skilak Lake, situated on the Kenai Peninsula) with the coastal and crustal earthquake catalog in Alaska. The resulting age ranges of all known megathrust earthquakes involving the Alaskan megathrust between the Kodiak and Prince William Sound (PWS) sections are more precise and accurate for the last 1.3 kyrs BP than the previously published age ranges from coastal records. As a result, this study supports the following key conclusions: (1) The 1964 CE earthquake was an exceptionally strong and unique event in the last 2000 years, rupturing the PWS, Kenai, Barren Islands, and Kodiak sections simultaneously. (2) The high-resolution and seasonal markings of the varved lake records now disentangle for the first time closely timed earthquakes, which was not possible based on the coastal evidence alone. (3) No persistent megathrust rupture boundaries exist. So, the possibility of a full rupture of the entire eastern AASZ, from PWS to Semidi cannot be excluded. (4) The rupture pattern in the eastern AASZ reveals superimposed cycles of multi-asperity ruptures (1964 earthquake) and clustered complementary partial ruptures, or rupture cascades. (5) The PWS section hosts the largest asperity in the eastern AASZ. (6) The shaking record of megathrust earthquakes indicates a time-dependent (quasiperiodic) behavior for the study area, but the observation of complementary clusters means that the hazards will not drop to zero but instead may even increase for a neighboring section. (7) The time-independent behavior of intraplate earthquakes implies that the intraslab hazard did not decrease following the 2016 and 2018 earthquakes. This study utilizes an integrated approach for subduction zone paleoseismology as a solution for unraveling recurrence and rupture patterns in Alaska, which can be applied worldwide.

Alaska

Foundational uncertainties in terminal Ediacaran chronostratigraphy revealed by high-precision zircon U-Pb geochronology of the Nama Group, Namibia

The Nama Group of southern Namibia and northwestern South Africa hosts the best-dated mixed carbonate-siliciclastic foreland basin succession of the terminal Ediacaran [ca. 551 million years (Ma) ago to <538 Ma] and is key for resolving the chronology of early metazoan evolution. Numerous silicified volcanic tuff interbeds are present, but differing interpretations regarding the fidelity of their ages lead to different regional stratigraphic correlations, especially for the Urusis Formation of the Schwarzrand Subgroup. An expanded record of the Urusis Formation is found in the Swartpunt area of southern Namibia, which has yielded an important metazoan biota. But the succession in this area is preserved as a series of thrusts at the leading edge of the Gariep orogenic belt and zircon U-Pb data show systematic age repetition. We use regional stratigraphic and structural mapping, integrated with carbonate carbon isotope (δ 13 C carb ) chemostratigraphy and high-precision radioisotope U-Pb zircon geochronology from outcrop and recently acquired drill core to develop a temporally calibrated basin-wide depositional model. This integrated dataset either reflects complex zircon reworking, inheritance, or potential analytical biases (Scenario 1) or the presence of a Gariep-related cryptic décollement within the Spitskop Member that has resulted in stratigraphic repetition (Scenario 2). We investigate the evidence for and against both scenarios and consider their implications for stratigraphic and δ 13 C carb correlations between the Swartpunt area and coeval exposures along the Orange River border with South Africa. Given that these issues are in an area that hosts numerous silicified ash beds and extensive exposure, an inability to confidently discount either scenario highlights a level of compounding uncertainty in zircon U-Pb geochronology that must be considered when attempting to build global chronostratigraphic frameworks. Scenario 1 implies that some of the weighted mean ages and Bayesian eruption ages from the Swartpunt area may be >1 Myr older than the depositional age of their respective ash beds when assuming existing stratigraphic correlations. If this scenario is preferred, then a cautious approach would be to consider all weighted mean zircon U-Pb ages from ash beds to reflect maximum depositional ages. Both scenarios support deposition of the Huns Member >540 Ma in the Swartpunt area if the oldest weighted mean age reported here represents a near-depositional age, which has significant implications for the temporal calibration of important terminal Ediacaran ichnofossil assemblages and future cyclostratigraphic studies. Stratigraphic correlations common to both scenarios allow us to temporally calibrate a basin evolution model for the Nama Group. Temporal trends in initial hafnium isotope (εHf) compositions of zircon grains from ash beds throughout the succession may support progressive crustal thickening associated with underplating of the Damara orogenic belt along the northern periphery of the Kalahari craton from ca. 547 Ma to ca. 538 Ma. The compilation of new and published zircon U-Pb ages may also imply that the locus of carbonate platform development migrated from north to south (present co-ordinates), tracking the migration of foredeep subsidence.

Earth-Science Reviews

Understanding the resource potential of natural hydrogen on Earth: Scientific gaps, uncertainties and recommendations

A comprehensive scientific research roadmap is essential to bridge knowledge gaps and deepen the understanding of key geological, geochemical, and geophysical aspects of natural hydrogen (H 2 ) as a potential new energy resource. This paper reviews major scientific uncertainties on natural H 2 , suggesting research priorities, as a guide for defining exploration strategies, techniques, and data interpretation. The uncertainties concern all phases of the natural H 2 cycle, from generation (source rocks) through migration (advection and diffusion) and accumulation (reservoir and cap rocks) to the application and interpretation of subsurface and surface geochemical and geophysical exploration techniques. Understanding H 2 sources and generation rates (the amount of H 2 generated by a given volume of rock over time) is crucial for determining whether a geological H 2 system operates as a short-term dynamic system with rapid H 2 production and release, or as a conventional gas system with long-term accumulations, analogous to petroleum reservoirs. Preliminary estimates for serpentinisation, radiolysis, and organic matter degradation suggest that H 2 generation is not inherently fast, especially for non-hydrothermal continental systems (crystalline basement of shields, ophiolites, peridotite massifs, sedimentary basins), and long-term accumulations, like those of fossil natural gas systems, represent the most likely scenario. The mechanisms of H 2 migration through geological formations require application of fundamental principles of fluid-flow physics, distinguishing advection and diffusion, as well as their forms (from gas-phase, bubble flows to aqueous solutions). Additional studies of H 2 accumulation and retention in subsurface reservoirs could improve understanding of mechanisms of H 2 migration by focusing on the rock fluid-bearing properties and the factors affecting H 2 preservation, such as the presence of cap rocks impermeable to H 2 , pressure conditions, residence times, and microbial or abiotic consumption. Advanced techniques, including reservoir modelling, flow simulations, 3D imaging (micro-CT) of H 2 -bearing rocks, and extraction and analysis of gas occluded in rocks, can provide insights into the stability and potential recoverability of H 2 accumulations. The interpretation of surface exploration techniques, including gas geochemistry, geophysics, and remote sensing, long employed in mineral and energy resource exploration, is now being adapted for natural H 2 studies, but challenges remain in the data interpretation. Distinguishing H 2 seepage due to geological degassing from H 2 produced near the surface by modern microbial processes or artificial sources, such as hammering or drilling for soil-gas sampling, drilling into aquifers, and corrosion in boreholes, is an essential step in exploration. The simple detection of H 2 in soils, even in morphological structures like sub-circular depressions or “fairy circles”, cannot be cursorily interpreted as a signal of natural H 2 seepage from a deep source. A holistic geochemical approach, including isotopic analyses of gases associated with H 2 , is recommended to distinguish among the variety of possible H 2 origins. Observations of H 2 in wells should be interrogated to rule out possible artifacts such as corrosion and drill bit metamorphism. The integration of multiple geophysical methods, including seismic, gravimetric, magnetic, and electro-magnetic surveys, is recommended to mitigate interpretation ambiguities regarding the structure of a subsurface H 2 system (source and reservoir rocks, including fluid and gas storage), due to the non-uniqueness of rock-specific physical properties.

Earth-Science Reviews

Timing and geometry of the Chemehuevi Formation reveal a late Pleistocene sediment pulse into the Lower Colorado River

The Chemehuevi Formation is a distinctive 50−150-m-thick wedge-shaped Pleistocene sedimentary unit deposited by the Colorado River. It lines the perimeters of the river’s floodplains and bedrock canyons for more than 600 km between the mouth of the Grand Canyon and the delta region in the Gulf of California. The formation is composed of a basal tan to light-yellowish-brown and pale-orange mud-dominated facies overlain and interbedded by a light-yellow-brown sand-dominated facies. The unit is one of two extensively exposed aggradational packages in the Lower Colorado River corridor, in addition to a series of other smaller alluvial terrace deposits. The Chemehuevi Formation appears to represent the response of a fully integrated Colorado River system to a significant perturbation, in contrast to the Bullhead Alluvium, which is likely a unique result of Pliocene river integration. The aggradation of the Chemehuevi Formation in the Lower Colorado River corridor may be similarly due to a unique event in the Colorado River system, or it may instead be a well-preserved sedimentary sequence recording typical behavior of the Colorado River below the Grand Canyon in the late Pleistocene. As such, multiple causal mechanisms have been proposed, but no study to date has conclusively explained the Chemehuevi Formation. To help resolve its timing, duration, and origin, we applied post-infrared infrared stimulated luminescence, carbonate U-Th series, and zircon sensitive high-resolution ion microprobe U-Th series geochronology to determine the ages of key exposures of the unit over a wide spatial area. These new data demonstrate that the Chemehuevi Formation was deposited ca. 110−90 ka. The depositional ages collectively overlap, suggesting that deposition occurred rapidly relative to the resolution of the geochronometers. The new depositional timing coincides with a shift from glacial to interglacial conditions after the marine isotope stage 5-6 transition. This observation is consistent with a climate-induced sediment pulse as a causal mechanism, yet correlations with similar deposits in the Colorado River headwaters or in neighboring catchments appear elusive. Potentially, climate transitions between glacial and interglacial periods induced a sediment pulse from hillslopes of the Colorado River system that resulted in the Chemehuevi Formation. An alternative or additional explanation is that the Chemehuevi Formation represents release of lava dam−impounded sediment in the Grand Canyon. The surface geometry of the Chemehuevi Formation projects upstream to the approximate location of lava dams, and the largest possible lava dam impoundment (the Upper Prospect dam) is comparable in volume to the formation. The lava dam hypothesis appears to be a possible explanation for the Chemehuevi Formation. However, tying deposition to a specific lava dam or series of lava dams remains challenging due to discrepancies in timing and volume. The combined effects of a series of lava dams may have led to the Chemehuevi Formation, as the last Pleistocene lava dam eruption coincides with the onset of deposition. Alternatively, the formation may result from the combined effects of both regional climate transitions and the lava dams that created a transient reservoir to compound a climate transition−driven sediment pulse. The geochronologic data presented here do not allow us to distinguish between the lava dam or climate transition hypotheses but will need to be reconciled with any future proposed depositional model.

Arizona, California, Nevada

Melt generation sources and conditions in the wake of a migrating slab window: Geochemistry and petrology of the million-year history of primitive volcanism at Clear Lake volcanic field, California

Clear Lake volcanic field (CLVF) is the northernmost and youngest (~2.2 Ma to 8 ka) of the volcanic centers distributed along the San Andreas transform fault in western California. The initial phase of CLVF volcanism (interval one) occurred between ~2.2 and 1.3 Ma and extends ~35 km southeast of Clear Lake, forming a semi-continuous upland plateau capped by lava flows, with isolated volcanic remnants on the periphery. This volcanism is broadly characterized by geochemically primitive compositions that reflect three source compositions and conditions of melt generation. (1) Partial melting of upwelling asthenospheric mantle lherzolite at moderate pressures (1.2–1.4 GPa) and temperatures (1297–1329 °C) produced high-CaO (9.8–11.3 wt %) basalts with high Al 2 O 3 (16.8–17.6 wt %), Mg#s (66–70), MgO (8–10 wt %), Ni (103–262 μg/g), and Cr (284–609 μg/g). These high-CaO basalts contain olivine (Fo 87–91 ) phenocrysts with Cr-spinel inclusions ± subordinate plagioclase and crop out only in the southern part of the CLVF. (2) Partial melting of depleted sub-continental lithospheric mantle harzburgite at variable pressures (0.7–1.5 GPa) and temperatures (1097–1299 °C) produced a compositional continuum of med-K 2 O, calc-alkaline, high-MgO basalts through high-MgO andesites with high Mg#s (67–77), MgO (8–14 wt %) and high Ni and Cr abundances (154–439 and 340–1124 μg/g, respectively). Mineral assemblages are olivine (Fo 88–93 ) with Cr-spinel inclusions ± subordinate clinopyroxene, orthopyroxene and plagioclase. Small (<2.5 cm) mantle harzburgite xenoliths and mantle olivine xenocrysts are also found in several of these samples. These high-MgO basalts through andesites represent the largest volume of primitive compositions and have erupted predominantly along the main, fault-controlled northwest-southeast trending axis of volcanism with peripheral outcrops to the north, west, and east. (3) Partial melting of the Gorda eclogite slab edge produced adakitic silicic slab melts with strong depletion in the heavy rare earth elements (Yb = 0.6 μg/g). Subsequent reaction of those melts with depleted ultramafic rocks during ascent imprinted the adakitic dacites with high Mg#s (65–78) and elevated Ni (117–210 μg/g) and Cr (191–283 μg/g). Phenocrysts of orthopyroxene (En 87–94 ) with spinel inclusions (Cr# = 80–88) and extremely Ni-rich (9483 μg/g) olivine cores (Fo 84–93 ) record those reactions. Small-volume outcrops of the adakites on the eastern periphery of the CLVF track the passing slab edge. The trio of melting sources recorded by early CLVF magmatism reflect the tectonically complex environment and the hot (1097–1329 °C), shallow (0.7–1.5 GPa) melting conditions for these primitive compositions and provide estimates of the heat delivered to the crust. Over time, this flux led to maturation of the CLVF magmatic system toward the more voluminous and silicic volcanism that characterizes the balance of its subsequent volcanic history and maintains the present-day anomalously high heat flow in the region. The current interval (interval four) of volcanic activity at CLVF is characterized by low-volume, fault-controlled eruptions of basaltic andesite and andesite suggestive of mantle magma and heat delivery to the crust, similar to interval one. This analogous activity provides motivation for the current study and begs the question of whether the system is undergoing thermal priming for renewed silicic volcanism.

California

Depth of magma crystallization and fluid exsolution beneath the porphyry-skarn Cu deposits at Santa Rita and Hanover-Fierro, New Mexico, USA

The depth level at which porphyry Cu–forming magmas fractionated and exsolved mineralizing fluids is actively debated. In the classic model, extensive magma fractionation occurs in large, upper crustal magma chambers, and concomitant fluid exsolution leads to forceful expulsion of residual magmas in the form of porphyry dikes, stocks, and breccia pipes, which subsequently serve as pathways for the mineralizing fluids. In contrast, some recent studies highlighting the role of deep crustal magma fractionation in the production of fertile magmas essentially deny the existence of upper crustal magma chambers at the time of mineralization. To address this, we conducted a detailed thermobarometric investigation of 13 intermediate to felsic, porphyritic intrusive rocks related to porphyry-skarn Cu mineralization at Santa Rita and Hanover-Fierro, New Mexico, United States, representing two premineralization magmas (61–60 Ma), seven synmineralization magmas (60–58 Ma), and four late- to postmineralization magmas (58–57 Ma). For each sample, the pressure of last magma crystallization before final magma ascent to the current exposure level was reconstructed based on Al-in-hornblende barometry of small hornblende inclusions trapped within quartz phenocrysts and through titanium-in-quartz (TitaniQ) thermobarometry of the host quartz phenocrysts themselves. Since quartz is one of the last crystallizing magmatic minerals, and no significant phenocryst growth could have occurred in small dikes and stocks after final magma emplacement, quartz phenocrysts and their contained hornblende inclusions record the depth of last magma crystallization before final magma ascent. When present, hornblende phenocrysts and hornblende inclusions within other major phenocrysts were also analyzed. Both quartz and hornblende barometers return consistent average pressures of 3.2 ± 0.4 kbar for the entire suite of pre- to postmineralization magmas, corresponding to depths of 11 to 14 km. The synmineralization magmas return even more consistent average pressures of 3.1 ± 0.2 kbar, corresponding to a depth of 12 ± 1 km. The volume of the mineralizing porphyry dikes and stocks at the emplacement level is far too small to have provided all the fluids and metals required to form the observed ore deposits. Therefore, the majority of the ore-forming fluids must have originated from the magmas that crystallized at 12 ± 1 km depth. The ore deposits, conversely, formed at ~5-km paleodepth. This implies that most of the mineralizing fluids traveled an average vertical distance of ~7 km from their magmatic source to the eventual site of ore precipitation. The relatively unaltered nature and low veining degree of deeper parts of mineralized porphyry dikes and stocks suggest that the fluid transport through these intrusive bodies occurred mostly at near-solidus conditions by means of fluid percolation along grain boundaries. In summary, our results suggest that (1) a large, upper crustal pluton exists ~7 km beneath the Santa Rita and Hanover-Fierro deposits; (2) abundant phenocryst crystallization occurred at this depth level; and (3) this pluton was the main source for the exsolution of ore-forming fluids. However, the investigated rocks have elevated whole-rock Sr/Y ratios, indicating magma fractionation at deep crustal levels. As a result, our preferred model is a combination of the two end-member models introduced above, with most magma fractionation having occurred in the deep crust and with residual, intermediate to felsic melts having ascended and accumulated at 11 to 14 km paleodepth, where they continued to crystallize with comparatively little crystal-liquid separation, before some of these magmas ascended further to shallow levels and quenched to porphyries.

New Mexico

Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru

The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T- f S 2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (log f O 2 < − 30 atm). The low f O 2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu + + In 3+ ↔ 2 Zn 2+ and (Sn, Ge) 4+ + (Ga, In) 3+ + (Cu + Ag) + ↔ 4 Zn 2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.

Pasco