Widespread six degrees Celsius cooling on land during the Last Glacial Maximum.

The magnitude of global cooling during the Last Glacial Maximum (LGM, the coldest multimillennial interval of the last glacial period) is an important constraint for evaluating estimates of Earth's climate sensitivity1,2. Reliable LGM temperatures come from high-latitude ice cores3,4, but substantial disagreement exists between proxy records in the low latitudes1,5-8, where quantitative low-elevation records on land are scarce. Filling this data gap, noble gases in ancient groundwater record past land surface temperatures through a direct physical relationship that is rooted in their temperature-dependent solubility in water9,10. Dissolved noble gases are suitable tracers of LGM temperature because of their complete insensitivity to biological and chemical processes and the ubiquity of LGM-aged groundwater around the globe11,12. However, although several individual noble gas studies have found substantial tropical LGM cooling13-16, they have used different methodologies and provide limited spatial coverage. Here we use noble gases in groundwater to show that the low-altitude, low-to-mid-latitude land surface (45 degrees south to 35 degrees north) cooled by 5.8 ± 0.6 degrees Celsius (mean ± 95% confidence interval) during the LGM. Our analysis includes four decades of groundwater noble gas data from six continents, along with new records from the tropics, all of which were interpreted using the same physical framework. Our land-based result broadly supports a recent reconstruction based on marine proxy data assimilation1 that suggested greater climate sensitivity than previous estimates5-7.

High 3He/4He in central Panama reveals a distal connection to the Galápagos plume.

It is well established that mantle plumes are the main conduits for upwelling geochemically enriched material from Earth's deep interior. The fashion and extent to which lateral flow processes at shallow depths may disperse enriched mantle material far (>1,000 km) from vertical plume conduits, however, remain poorly constrained. Here, we report He and C isotope data from 65 hydrothermal fluids from the southern Central America Margin (CAM) which reveal strikingly high 3He/4He (up to 8.9RA) in low-temperature (≤50 °C) geothermal springs of central Panama that are not associated with active volcanism. Following radiogenic correction, these data imply a mantle source 3He/4He >10.3RA (and potentially up to 26RA, similar to Galápagos hotspot lavas) markedly greater than the upper mantle range (8 ± 1RA). Lava geochemistry (Pb isotopes, Nb/U, and Ce/Pb) and geophysical constraints show that high 3He/4He values in central Panama are likely derived from the infiltration of a Galápagos plume-like mantle through a slab window that opened ∼8 Mya. Two potential transport mechanisms can explain the connection between the Galápagos plume and the slab window: 1) sublithospheric transport of Galápagos plume material channeled by lithosphere thinning along the Panama Fracture Zone or 2) active upwelling of Galápagos plume material blown by a "mantle wind" toward the CAM. We present a model of global mantle flow that supports the second mechanism, whereby most of the eastward transport of Galápagos plume material occurs in the shallow asthenosphere. These findings underscore the potential for lateral mantle flow to transport mantle geochemical heterogeneities thousands of kilometers away from plume conduits.

Occurrence and Sources of Radium in Groundwater Associated with Oil Fields in the Southern San Joaquin Valley, California.

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range = <0.005-18.5 mg/L), and pH (p < 0.001, ρ = -0.67, range = 6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

A novel high-frequency groundwater quality monitoring system.

High-frequency, long-term monitoring of water quality has revolutionized the study of surface waters in recent years. However, application of these techniques to groundwater has been limited by the ability to remotely pump and analyze groundwater. This paper describes a novel autonomous groundwater quality monitoring system which samples multiple wells to evaluate temporal changes and identify trends in groundwater chemistry. The system, deployed near Fresno, California, USA, collects and transmits high-frequency data, including water temperature, specific conductance, pH, dissolved oxygen, and nitrate, from supply and monitoring wells, in real-time. The system consists of a water quality sonde and optical nitrate sensor, manifold, submersible three-phase pump, variable frequency drive, data collection platform, solar panels, and rechargeable battery bank. The manifold directs water from three wells to a single set of sensors, thereby reducing setup and operation costs associated with multi-sensor networks. Sampling multiple wells at high frequency for several years provided a means of monitoring the vertical distribution and transport of solutes in the aquifer. Initial results show short period variability of nitrate, specific conductivity, and dissolved oxygen in the shallow aquifer, while the deeper portion of the aquifer remains unchanged-observations that may be missed with traditional discrete sampling approaches. In this aquifer system, nitrate and specific conductance are increasing in the shallow aquifer, while invariant changes in deep groundwater chemistry likely reflect relatively slow groundwater flow. In contrast, systems with high groundwater velocity, such as karst aquifers, have been shown to exhibit higher-frequency groundwater chemistry changes. The stability of the deeper aquifer over the monitoring period was leveraged to develop estimates of measurement system uncertainty, which were typically lower than the manufacturer's stated specifications, enabling the identification of subtle variability in water chemistry that may have otherwise been missed.

Assessing California groundwater susceptibility using trace concentrations of halogenated volatile organic compounds.

Twenty-four halogenated volatile organic compounds (hVOCs) and SF6 were measured in groundwater samples collected from 312 wells across California at concentrations as low as 10⁻¹² grams per kilogram groundwater. The hVOCs detected are predominately anthropogenic (i.e., "ahVOCs") and as such their distribution delineates where groundwaters are impacted and susceptible to human activity. ahVOC detections were broadly consistent with air-saturated water concentrations in equilibrium with a combination of industrial-era global and regional hVOC atmospheric abundances. However, detection of ahVOCs in nearly all of the samples collected, including ancient groundwaters, suggests the presence of a sampling or analytical artifact that confounds interpretation of the very-low concentration ahVOC data. To increase our confidence in ahVOC detections we establish screening levels based on ahVOC concentrations in deep wells drawing ancient groundwater in Owens Valley. Concentrations of ahVOCs below the Owens Valley screening levels account for a large number of the detections in prenuclear groundwater across California without significant loss of ahVOC detections in shallow, recently recharged groundwaters. Over 80% of the groundwaters in this study contain at least one ahVOC after screening, indicating that the footprint of human industry is nearly ubiquitous and that most California groundwaters are vulnerable to contamination from land-surface activities.

Small atoll fresh groundwater lenses respond to a combination of natural climatic cycles and human modified geology.

Freshwater lenses underlying small ocean islands exhibit spatial variability and temporal fluctuations in volume, influencing ecologic management. For example, The Palmyra Atoll National Wildlife Refuge harbors one of the few surviving native stands of Pisonia grandis in the central Pacific Ocean, yet these trees face pressure from groundwater salinization, with little basic groundwater data to guide decision making. Adding to natural complexity, the geology of Palmyra was heavily altered by dredge and fill activities. Our study based at this atoll combines geophysical and hydrological field measurements from 2008 to 2019 with groundwater modeling to study the drivers of observed freshwater lens dynamics. Electromagnetic induction (EMI) field data were collected on the main atoll islands over repeat transects in 2008 following 'strong' La Niña conditions (wet) and in 2016 during 'very strong' El Niño conditions (dry). Shallow monitoring wells were installed adjacent to the geophysical transects in 2013 and screened within the fresh/saline groundwater transition zone. Temporal EMI and monitoring well data showed a strong contraction of the freshwater lens in response to El Niño conditions, and indicated a thicker lens toward the ocean side, an opposite spatial pattern to that observed for many other Pacific islands. On an outer islet where a stand of mature Pisonia trees exist, EMI surveys revealed only a thin (<3 m from land surface) layer of brackish groundwater during El Niño. Numerical groundwater simulations were performed for a range of permeability distributions and climate conditions at Palmyra. Results revealed that the observed atypical lens asymmetry is likely due to more efficient submarine groundwater discharge on the lagoon side as a result of lagoon dredging and filling with high-permeability material. Simulations also predict large decreases (40%) in freshwater lens volume during dry cycles and highlight threats to the Pisonia trees, yielding insight for atoll ecosystem management worldwide.

Groundwater Quality of Aquifers Overlying the Oxnard Oil Field, Ventura County, California.

Groundwater samples collected from irrigation, monitoring, and municipal supply wells near the Oxnard Oil Field were analyzed for chemical and isotopic tracers to evaluate if thermogenic gas or water from hydrocarbon-bearing formations have mixed with surrounding groundwater. New and historical data show no evidence of water from hydrocarbon-bearing formations in groundwater overlying the field. However, thermogenic gas mixed with microbial methane was detected in 5 wells at concentrations ranging from 0.011-9.1 mg/L. The presence of these gases at concentrations <10 mg/L do not indicate degraded water quality posing a known health risk. Analysis of carbon isotopes (δ13C-CH4) and hydrogen isotopes (δ2H-CH4) of methane and ratios of methane to heavier hydrocarbon gases were used to differentiate sources of methane between a) microbial, b) thermogenic or c) mixed sources. Results indicate that microbial-sourced methane is widespread in the study area, and concentrations overlap with those from thermogenic sources. The highest concentrations of thermogenic gas were observed in proximity to relatively high density of oil wells, large injection volumes of water disposal and cyclic steam, shallow oil development, and hydrocarbon shows in sediments overlying the producing oil reservoirs. Depths of water wells containing thermogenic gas were within approximately 200 m of the top of the Vaca Tar Sand production zone (approximately 600 m below land surface). Due to the limited sampling density, the source and pathways of thermogenic gas detected in groundwater could not be conclusively determined. Thermogenic gas detected in the absence of co-occurring water from hydrocarbon-bearing formations may result from natural gas migration over geologic time from the Vaca Tar Sand or deeper formations, hydrocarbon shows in sediments overlying producing zones, and/or gas leaking from oil-field infrastructure. Denser sampling of groundwater, potential end-members, and pressure monitoring could help better distinguish pathways of thermogenic gases.

Groundwater residence time estimates obscured by anthropogenic carbonate.

Groundwater is an important source of drinking and irrigation water. Dating groundwater informs its vulnerability to contamination and aids in calibrating flow models. Here, we report measurements of multiple age tracers (14C, 3H, 39Ar, and 85Kr) and parameters relevant to dissolved inorganic carbon (DIC) from 17 wells in California's San Joaquin Valley (SJV), an agricultural region that is heavily reliant on groundwater. We find evidence for a major mid-20th century shift in groundwater DIC input from mostly closed- to mostly open-system carbonate dissolution, which we suggest is driven by input of anthropogenic carbonate soil amendments. Crucially, enhanced open-system dissolution, in which DIC equilibrates with soil CO2, fundamentally affects the initial 14C activity of recently recharged groundwater. Conventional 14C dating of deeper SJV groundwater, assuming an open system, substantially overestimates residence time and thereby underestimates susceptibility to modern contamination. Because carbonate soil amendments are ubiquitous, other groundwater-reliant agricultural regions may be similarly affected.

Deglacial water-table decline in Southern California recorded by noble gas isotopes.

Constraining the magnitude of past hydrological change may improve understanding and predictions of future shifts in water availability. Here we demonstrate that water-table depth, a sensitive indicator of hydroclimate, can be quantitatively reconstructed using Kr and Xe isotopes in groundwater. We present the first-ever measurements of these dissolved noble gas isotopes in groundwater at high precision (≤0.005‰ amu-1; 1σ), which reveal depth-proportional signals set by gravitational settling in soil air at the time of recharge. Analyses of California groundwater successfully reproduce modern groundwater levels and indicate a 17.9 ± 1.3 m (±1 SE) decline in water-table depth in Southern California during the last deglaciation. This hydroclimatic transition from the wetter glacial period to more arid Holocene accompanies a surface warming of 6.2 ± 0.6 °C (±1 SE). This new hydroclimate proxy builds upon an existing paleo-temperature application of noble gases and may identify regions prone to future hydrological change.

Geostatistical analysis of tritium, groundwater age and other noble gas derived parameters in California.

Key characteristics of California groundwater systems related to aquifer vulnerability, sustainability, recharge locations and mechanisms, and anthropogenic impact on recharge are revealed in a spatial geostatistical analysis of a unique data set of tritium, noble gases and other isotopic analyses unprecedented in size at nearly 4000 samples. The correlation length of key groundwater residence time parameters varies between tens of kilometers ((3)H; age) to the order of a hundred kilometers ((4)Heter; (14)C; (3)Hetrit). The correlation length of parameters related to climate, topography and atmospheric processes is on the order of several hundred kilometers (recharge temperature; δ(18)O). Young groundwater ages that highlight regional recharge areas are located in the eastern San Joaquin Valley, in the southern Santa Clara Valley Basin, in the upper LA basin and along unlined canals carrying Colorado River water, showing that much of the recent recharge in central and southern California is dominated by river recharge and managed aquifer recharge. Modern groundwater is found in wells with the top open intervals below 60 m depth in the southeastern San Joaquin Valley, Santa Clara Valley and Los Angeles basin, as the result of intensive pumping and/or managed aquifer recharge operations.

Simulation of fluid, heat transport to estimate desert stream infiltration.

In semiarid regions, the contribution of infiltration from intermittent streamflow to ground water recharge may be quantified by comparing simulations of fluid and heat transport beneath stream channels to observed ground temperatures. In addition to quantifying natural recharge, streamflow infiltration estimates provide a means to characterize the physical properties of stream channel sediments and to identify suitable locations for artificial recharge sites. Rates of winter streamflow infiltration along stream channels are estimated based on the cooling effect of infiltrated water on streambed sediments, combined with the simulation of two-dimensional fluid and heat transport using the computer program VS2DH. The cooling effect of ground water is determined by measuring ground temperatures at regular intervals beneath stream channels and nearby channel banks in order to calculate temperature-depth profiles. Additional data inputs included the physical, hydraulic, and thermal properties of unsaturated alluvium, and monthly ground temperatures measurements over an annual cycle. Observed temperatures and simulation results can provide estimates of the minimum threshold for deep infiltration, the variability of infiltration along stream channels, and also the frequency of infiltration events.