Estimating Lithium Concentrations in Groundwater Used as Drinking Water for the Conterminous United States.

Lithium (Li) concentrations in drinking-water supplies are not regulated in the United States; however, Li is included in the 2022 U.S. Environmental Protection Agency list of unregulated contaminants for monitoring by public water systems. Li is used pharmaceutically to treat bipolar disorder, and studies have linked its occurrence in drinking water to human-health outcomes. An extreme gradient boosting model was developed to estimate geogenic Li in drinking-water supply wells throughout the conterminous United States. The model was trained using Li measurements from ∼13,500 wells and predictor variables related to its natural occurrence in groundwater. The model predicts the probability of Li in four concentration classifications, ≤4 µg/L, >4 to ≤10 µg/L, >10 to ≤30 µg/L, and >30 µg/L. Model predictions were evaluated using wells held out from model training and with new data and have an accuracy of 47-65%. Important predictor variables include average annual precipitation, well depth, and soil geochemistry. Model predictions were mapped at a spatial resolution of 1 km2 and represent well depths associated with public- and private-supply wells. This model was developed by hydrologists and public-health researchers to estimate Li exposure from drinking water and compare to national-scale human-health data for a better understanding of dose-response to low (<30 µg/L) concentrations of Li.

Polymer Characterization of Submerged Plastic Litter from Lake Tahoe, United States.

Monitoring plastic litter in the environment is critical to understanding the amount, sources, transport, fate, and environmental impact of this pollutant. However, few studies have monitored plastic litter on lakebeds which are potentially important environments for determining the fate and transport of plastic litter in freshwater basins. In this study, a self-contained underwater breathing apparatus was used for litter collection at the lakebed along five transects in Lake Tahoe, United States. Litter was brought to the surface and characterized by litter type. Plastic litter was subsampled, and polymer composition was determined using attenuated total reflection Fourier transform infrared spectroscopy. The average plastic litter from the lakebed for the five dive transects was 83 ± 49 items per kilometer. The top plastic litter categories were other plastic litter (plastic litter that did not fall in another category), followed by food containers, bottles <2 L, plastic bags, and toys. These results are in line with prior studies on submerged litter, and intervention approaches or ongoing education are needed. The six polymers most frequently detected in the subsamples were polyvinyl chloride, polystyrene/expanded polystyrene, polyethylene terephthalate/polyester, polyethylene, polypropylene, and polyamide. These observations reflect global plastic production and microplastic studies from lake surface water and sediments. We found that some litter subcategories were primarily comprised of a single polymer type, therefore, in studies where the polymer type cannot be measured but litter is categorized, these results could provide an estimate of the total polymer composition for select litter categories.

Predictions of Arsenic in Domestic Well Water Sourced from Alluvial Aquifers of the Western Great Basin, USA.

Chronic exposure to high levels of arsenic in drinking water can have wide-ranging health effects and is a global health concern. The domestic well population of the western Great Basin (WGB) is at increased risk of exposure to arsenic due to the hydrologic, geologic, and climatic setting of the region. A logistic regression (LR) model was developed to predict the probability of elevated arsenic (≥5 µg/L) in alluvial aquifers and assess the potential geologic hazard level posed to domestic well populations. Alluvial aquifers are susceptible to arsenic contamination, which is a concern because they are the primary source of water for domestic well users of the WGB. The probability of elevated arsenic at a domestic well is strongly influenced by tectonic and geothermal variables, including the total Quaternary fault length in the hydrographic basin and the distance between the sampled well and a geothermal system. The model had an overall accuracy of 81%, sensitivity of 92%, and specificity of 55%. Results show a >50% probability of elevated arsenic in untreated well water for approximately 49 thousand (64%) alluvial-aquifer domestic well users in northern Nevada, northeastern California, and western Utah.

Naturally occurring metals in unregulated domestic wells in Nevada, USA.

The dominant source of drinking water in rural Nevada, United States, is privately-owned domestic wells. Because the water from these wells is unregulated with respect to government guidelines, it is the owner's responsibility to test their groundwater for heavy metals and other contaminants. Arsenic, lead, cadmium, and uranium have been previously measured at concentrations above Environmental Protection Agency (EPA) guidelines in Nevada groundwater. This is a public health concern because elevated levels of these metals are known to have negative health effects. We recruited individuals through a population health study, the Healthy Nevada Project, to submit drinking water samples from domestic wells for testing. Water samples were returned from 174 households with private wells. We found 22 % had arsenic concentrations exceeding the EPA maximum contaminant level (MCL) of 10 µg/L. Additionally, federal, state, or health-based guidelines were exceeded for 8 % of the households for uranium and iron, 6 % for lithium and manganese, 4 % for molybdenum, and 1 % for lead. The maximum observed concentrations of arsenic, uranium, and lead were ∼80, ∼5, and ∼1.5 times the EPA guideline values, respectively. 41 % of households had a treatment system and submitted both pre- and post-treatment water samples from their well. The household treatments were shown to reduce metal concentrations, but concentrations above guideline values were still observed. Many treatment systems cannot reduce the concentration below guideline values because of water chemistry, treatment failure, or improper treatment techniques. These results show the pressing need for continued education and outreach on regular testing of domestic well waters, proper treatment types, and health effects of metal contamination. These findings are potentially applicable to other arid areas where groundwater contamination of naturally occurring heavy metals occurs.

Improved estimates of preindustrial biomass burning reduce the magnitude of aerosol climate forcing in the Southern Hemisphere.

Fire plays a pivotal role in shaping terrestrial ecosystems and the chemical composition of the atmosphere and thus influences Earth's climate. The trend and magnitude of fire activity over the past few centuries are controversial, which hinders understanding of preindustrial to present-day aerosol radiative forcing. Here, we present evidence from records of 14 Antarctic ice cores and 1 central Andean ice core, suggesting that historical fire activity in the Southern Hemisphere (SH) exceeded present-day levels. To understand this observation, we use a global fire model to show that overall SH fire emissions could have declined by 30% over the 20th century, possibly because of the rapid expansion of land use for agriculture and animal production in middle to high latitudes. Radiative forcing calculations suggest that the decreasing trend in SH fire emissions over the past century largely compensates for the cooling effect of increasing aerosols from fossil fuel and biofuel sources.

Comparison of co-located ice-core and tree-ring mercury records indicates potential radial translocation of mercury in whitebark pine.

Tree-ring records are a potential archive for reconstructing long-term historical trends in atmospheric mercury (Hg) concentrations. Although Hg preserved in tree rings has been shown to be derived largely from the atmosphere, quantitative relationships linking atmospheric concentrations to those in tree rings are limited. In addition, few tree-ring-based Hg records have been evaluated against co-located proxies of atmospheric Hg deposition or direct atmospheric measurements. Here we develop long-term Hg records extending from 1800 to 2018 CE using cores collected from two stands of whitebark pine located near the Upper Fremont Glacier in the Wind River Range, Wyoming, where a long-term record of atmospheric Hg deposition previously was developed from an ice core. The tree ring record showed that Hg concentrations increased beginning in 1800 CE to a broad peak centered at ~1960 CE, before decreasing to present, generally paralleling the ice-core record of Hg deposition. The exact timing and magnitude of the Hg increases in the trees, however, is offset earlier relative to the ice-core record. These discrepancies potentially arise from biotic processes that impact Hg uptake and preservation in whitebark pine, and results from an advection-diffusion model indicate that the temporal differences are consistent with radial movement of Hg within the trees. The forms of atmospheric Hg and seasonality may also impact the Hg record preserved by each archive, but are less likely to affect long-term trends. Further work is needed to assess radial Hg translocation in more controlled studies with larger sample sizes.

Pervasive Arctic lead pollution suggests substantial growth in medieval silver production modulated by plague, climate, and conflict.

Lead pollution in Arctic ice reflects large-scale historical changes in midlatitude industrial activities such as ancient lead/silver production and recent fossil fuel burning. Here we used measurements in a broad array of 13 accurately dated ice cores from Greenland and Severnaya Zemlya to document spatial and temporal changes in Arctic lead pollution from 200 BCE to 2010 CE, with interpretation focused on 500 to 2010 CE. Atmospheric transport modeling indicates that Arctic lead pollution was primarily from European emissions before the 19th-century Industrial Revolution. Temporal variability was surprisingly similar across the large swath of the Arctic represented by the array, with 250- to 300-fold increases in lead pollution observed from the Early Middle Ages to the 1970s industrial peak. Superimposed on these exponential changes were pronounced, multiannual to multidecadal variations, marked by increases coincident with exploitation of new mining regions, improved technologies, and periods of economic prosperity; and decreases coincident with climate disruptions, famines, major wars, and plagues. Results suggest substantial overall growth in lead/silver mining and smelting emissions-and so silver production-from the Early through High Middle Ages, particularly in northern Europe, with lower growth during the Late Middle Ages into the Early Modern Period. Near the end of the second plague pandemic (1348 to ∼1700 CE), lead pollution increased sharply through the Industrial Revolution. North American and European pollution abatement policies have reduced Arctic lead pollution by >80% since the 1970s, but recent levels remain ∼60-fold higher than at the start of the Middle Ages.

Four-fold increase in solar forcing on snow in western U.S. burned forests since 1999.

Forest fires are increasing across the American West due to climate warming and fire suppression. Accelerated snow melt occurs in burned forests due to increased light transmission through the canopy and decreased snow albedo from deposition of light-absorbing impurities. Using satellite observations, we document up to an annual 9% growth in western forests burned since 1984, and 5 day earlier snow disappearance persisting for >10 years following fire. Here, we show that black carbon and burned woody debris darkens the snowpack and lowers snow albedo for 15 winters following fire, using measurements of snow collected from seven forested sites that burned between 2002 and 2016. We estimate a 372 to 443% increase in solar energy absorbed by snowpacks occurred beneath charred forests over the past two decades, with enhanced post-fire radiative forcing in 2018 causing earlier melt and snow disappearance in > 11% of forests in the western seasonal snow zone.

Method for Correcting Continuous Ice-Core Elemental Measurements for Under-Recovery.

Measurement of elemental concentrations in ice cores are critical for determining atmospheric aerosol variations. For such measurements, acidified ice-core meltwater typically is analyzed continuously (<5 min after acidification) or discretely (∼3 months after acidification). The reduced acidification time during continuous analysis may result in a measured elemental concentration that is lower than the concentration of discrete analysis if particulates are not fully dissolved. To evaluate this, sections of three ice cores from Greenland and Antarctica were measured both continuously (4.5 min after acidification) and discretely (repeatedly from 1 to 151 days after continuous measurements), with discrete samples collected from the meltwater sample stream prior to continuous measurement. We show that elements such as Na, Sr, and S dissolved readily and therefore were fully recovered during continuous measurements. Average recovery for other elements was between 70 to 100% for Cd, Gd, Mg, Mn, U, and Yb, 50 to 90% for Ca, Ce, Sm, and V, and less than 50% for Al, Fe, and La. Given the advantages of continuous measurements, we conclude that the preferred method for ice-core measurements is continuous analysis with simultaneous discrete sample collection, followed by adjustment of the continuous measurements based on discrete sample analysis at least 3 months after acidification.

Alpine ice evidence of a three-fold increase in atmospheric iodine deposition since 1950 in Europe due to increasing oceanic emissions.

Iodine is an important nutrient and a significant sink of tropospheric ozone, a climate-forcing gas and air pollutant. Ozone interacts with seawater iodide, leading to volatile inorganic iodine release that likely represents the largest source of atmospheric iodine. Increasing ozone concentrations since the preindustrial period imply that iodine chemistry and its associated ozone destruction is now substantially more active. However, the lack of historical observations of ozone and iodine means that such estimates rely primarily on model calculations. Here we use seasonally resolved records from an Alpine ice core to investigate 20th century changes in atmospheric iodine. After carefully considering possible postdepositional changes in the ice core record, we conclude that iodine deposition over the Alps increased by at least a factor of 3 from 1950 to the 1990s in the summer months, with smaller increases during the winter months. We reproduce these general trends using a chemical transport model and show that they are due to increased oceanic iodine emissions, coupled to a change in iodine speciation over Europe from enhanced nitrogen oxide emissions. The model underestimates the increase in iodine deposition by a factor of 2, however, which may be due to an underestimate in the 20th century ozone increase. Our results suggest that iodine's impact on the Northern Hemisphere atmosphere accelerated over the 20th century and show a coupling between anthropogenic pollution and the availability of iodine as an essential nutrient to the terrestrial biosphere.

Lead pollution recorded in Greenland ice indicates European emissions tracked plagues, wars, and imperial expansion during antiquity.

Lead pollution in Arctic ice reflects midlatitude emissions from ancient lead-silver mining and smelting. The few reported measurements have been extrapolated to infer the performance of ancient economies, including comparisons of economic productivity and growth during the Roman Republican and Imperial periods. These studies were based on sparse sampling and inaccurate dating, limiting understanding of trends and specific linkages. Here we show, using a precisely dated record of estimated lead emissions between 1100 BCE and 800 CE derived from subannually resolved measurements in Greenland ice and detailed atmospheric transport modeling, that annual European lead emissions closely varied with historical events, including imperial expansion, wars, and major plagues. Emissions rose coeval with Phoenician expansion, accelerated during expanded Carthaginian and Roman mining primarily in the Iberian Peninsula, and reached a maximum under the Roman Empire. Emissions fluctuated synchronously with wars and political instability particularly during the Roman Republic, and plunged coincident with two major plagues in the second and third centuries, remaining low for >500 years. Bullion in silver coinage declined in parallel, reflecting the importance of lead-silver mining in ancient economies. Our results indicate sustained economic growth during the first two centuries of the Roman Empire, terminated by the second-century Antonine plague.

Synchronous volcanic eruptions and abrupt climate change ∼17.7 ka plausibly linked by stratospheric ozone depletion.

Glacial-state greenhouse gas concentrations and Southern Hemisphere climate conditions persisted until ∼17.7 ka, when a nearly synchronous acceleration in deglaciation was recorded in paleoclimate proxies in large parts of the Southern Hemisphere, with many changes ascribed to a sudden poleward shift in the Southern Hemisphere westerlies and subsequent climate impacts. We used high-resolution chemical measurements in the West Antarctic Ice Sheet Divide, Byrd, and other ice cores to document a unique, ∼192-y series of halogen-rich volcanic eruptions exactly at the start of accelerated deglaciation, with tephra identifying the nearby Mount Takahe volcano as the source. Extensive fallout from these massive eruptions has been found >2,800 km from Mount Takahe. Sulfur isotope anomalies and marked decreases in ice core bromine consistent with increased surface UV radiation indicate that the eruptions led to stratospheric ozone depletion. Rather than a highly improbable coincidence, circulation and climate changes extending from the Antarctic Peninsula to the subtropics-similar to those associated with modern stratospheric ozone depletion over Antarctica-plausibly link the Mount Takahe eruptions to the onset of accelerated Southern Hemisphere deglaciation ∼17.7 ka.

Reassessment of the Upper Fremont Glacier Ice-Core Chronologies by Synchronizing of Ice-Core-Water Isotopes to a Nearby Tree-Ring Chronology.

The Upper Fremont Glacier (UFG), Wyoming, is one of the few continental glaciers in the contiguous United States known to preserve environmental and climate records spanning recent centuries. A pair of ice cores taken from UFG have been studied extensively to document changes in climate and industrial pollution (most notably, mid-19th century increases in mercury pollution). Fundamental to these studies is the chronology used to map ice-core depth to age. Here, we present a revised chronology for the UFG ice cores based on new measurements and using a novel dating approach of synchronizing continuous water isotope measurements to a nearby tree-ring chronology. While consistent with the few unambiguous age controls underpinning the previous UFG chronologies, the new interpretation suggests a very different time scale for the UFG cores with changes of up to 80 years. Mercury increases previously associated with the mid-19th century Gold Rush now coincide with early-20th century industrial emissions, aligning the UFG record with other North American mercury records from ice and lake sediment cores. Additionally, new UFG records of industrial pollutants parallel changes documented in ice cores from southern Greenland, further validating the new UFG chronologies while documenting the extent of late 19th and early 20th century pollution in remote North America.

Measurement of δ18O and δ2H values of fluid inclusion water in speleothems using cavity ring-down spectroscopy compared with isotope ratio mass spectrometry.

RATIONALE: The hydrogen and oxygen isotopic analyses (δ(2)H and δ(18)O values) of water trapped within speleothem carbonate (fluid inclusions) have traditionally been conducted utilizing dual-inlet isotope ratio mass spectrometry (IRMS) or continuous-flow (CF)-IRMS methods. The application of cavity ring-down spectroscopy (CRDS) to the δ(2)H and δ(18)O analysis of water in fluid inclusions has been investigated at the University of Miami as an alternative method to CF-IRMS. METHODS: An extraction line was developed to recover water from the fluid inclusions consisting of a crusher, sample injection port and an expansion volume (either 100 or 50 cm(3)) directly connected to the CRDS instrument. Tests were conducted to determine the reproducibility of standard water injections and crushes. In order to compare results with conventional analytical methods, samples were analyzed both at the University of Miami (CRDS method) and at the Vrije Universiteit Amsterdam (CF-IRMS method). RESULTS: The analytical reproducibility of speleothem samples crushed on the Miami Device demonstrates an average external standard deviation of 0.5 and 2.0 ‰ for δ(18)O and δ(2)H values, respectively. Sample data are shown to fall near the global meteoric water line, supporting the validity of the method. Three different samples were analyzed at Vrije Universiteit Amsterdam and the University of Miami in order to compare the performance of each laboratory. The average offset between the two laboratories is 0.7 ‰ for δ(18)O and 2.5 ‰ for δ(2)H. CONCLUSIONS: The advantage of CRDS is that the system is a low-cost alternative to CF-IRMS for fluid inclusion isotope analysis. The CRDS method demonstrates acceptable precision and good agreement with results from the CF-IRMS method. These are promising results for the future application of CRDS to fluid inclusion isotope analysis.