Despite the hypothesized importance of the tropics in the global climate system, few tropical paleoclimatic records extend to periods earlier than the last glacial maximum (LGM), about 20,000 years before present. We present a well-dated 170,000-year time series of hydrologic variation from the southern hemisphere tropics of South America that extends from modern times through most of the penultimate glacial period. Alternating mud and salt units in a core from Salar de Uyuni, Bolivia reflect alternations between wet and dry periods. The most striking feature of the sequence is that the duration of paleolakes increased in the late Quaternary. This change may reflect increased precipitation, geomorphic or tectonic processes that affected basin hydrology, or some combination of both. The dominance of salt between 170,000 and 140,000 yr ago indicates that much of the penultimate glacial period was dry, in contrast to wet conditions in the LGM. Our analyses also suggest that the relative influence of insolation forcing on regional moisture budgets may have been stronger during the past 50,000 years than in earlier times.

International audience[1] Thirteen laboratories from the USA and Europe participated in an intercomparison study of Mg/Ca and Sr/Ca measurements in foraminifera. The study included five planktonic species from surface sediments from different geographical regions and water depths. Each of the laboratories followed their own cleaning and analytical procedures and had no specific information about the samples. Analysis of solutions of known Mg/Ca and Sr/Ca ratios showed that the intralaboratory instrumental precision is better than 0.5% for both Mg/Ca and Sr/Ca measurements, regardless whether ICP-OES or ICP-MS is used. The interlaboratory precision on the analysis of standard solutions was about 1.5% and 0.9% for Mg/Ca and Sr/Ca measurements, respectively. These are equivalent to Mg/Ca-based temperature repeatability and reproducibility on the analysis of solutions of +/- 0.2 degreesC and +/- 0.5 degreesC, respectively. The analysis of foraminifera suggests an interlaboratory variance of about +/-8% (%RSD) for Mg/Ca measurements, which translates to reproducibility of about +/- 2 - 3 degreesC. The relatively large range in the reproducibility of foraminiferal analysis is primarily due to relatively poor intralaboratory repeatability (about +/- 1 - 2 degreesC) and a bias (about 1 degreesC) due to the application of different cleaning methods by different laboratories. Improving the consistency of cleaning methods among laboratories will, therefore, likely lead to better reproducibility. Even more importantly, the results of this study highlight the need for standards calibration among laboratories as a first step toward improving interlaboratory compatibility

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Rare earth elements (REEs) are critical and strategic materials in the defense, energy, electronics, and automotive industries. The reclamation of REEs from coal combustion fly ash has been proposed as a way to supplement REE mining. However, the typical REE contents in coal fly ash, particularly in the United States, have not been comprehensively documented or compared among the major types of coal feedstocks that determine fly ash composition. The objective of this study was to characterize a broad selection of U.S. fly ashes of varied geological origin in order to rank their potential for REE recovery. The total and nitric acid-extractable REE content for more than 100 ash samples were correlated with characteristics such as the major element content and coal basin to elucidate trends in REE enrichment. Average total REE content (defined as the sum of the lanthanides, yttrium, and scandium) for ashes derived from Appalachian sources was 591 mg kg(-1) and significantly greater than in ashes from Illinois and Powder River basin coals (403 and 337 mg kg(-1), respectively). The fraction of critical REEs (Nd, Eu, Tb, Dy, Y, and Er) in the fly ashes was 34-38% of the total and considerably higher than in conventional ores (typically less than 15%). Powder River Basin ashes had the highest extractable REE content, with 70% of the total REE recovered by heated nitric acid digestion. This is likely due to the higher calcium content of Powder River Basin ashes, which enhances their solubility in nitric acid. Sc, Nd, and Dy were the major contributors to the total REE value in fly ash, based on their contents and recent market prices. Overall, this study shows that coal fly ash production could provide a substantial domestic supply of REEs, but the feasibility of recovery depends on the development of extraction technologies that could be tailored to the major mineral content and origins of the feed coal for the ash.

We present paleoclimate evidence for rapid ( < 100 years) shifts of f 2-4 jC in Chesapeake Bay (CB) temperature f2100, 1600, 950, 650, 400 and 150 years before present (years BP) reconstructed from magnesium/calcium (Mg/Ca) paleothermometry. These include large temperature excursions during the Little Ice Age (f1400 -1900 AD) and the Medieval Warm Period (f800 -1300 AD) possibly related to changes in the strength of North Atlantic thermohaline circulation (THC). Evidence is presented for a long period of sustained regional and North Atlantic-wide warmth with low-amplitude temperature variability between f450 and 1000 AD. In addition to centennial-scale temperature shifts, the existence of numerous temperature maxima between 2200 and 250 years BP (average f70 years) suggests that multi-decadal processes typical of the North Atlantic Oscillation (NAO) are an inherent feature of late Holocene climate. However, late 19th and 20th century temperature extremes in Chesapeake Bay associated with NAO climate variability exceeded those of the prior 2000 years, including the interval 450 -1000 AD, by 2 -3 jC, suggesting anomalous recent behavior of the climate system. D

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

An investigation of the potential environmental and health impacts in the immediate aftermath of one of the largest coal ash spills in U.S. history at the Tennessee Valley Authority (TVA) Kingston coal-burning power plant has revealed three major findings. First, the surface release of coal ash with high levels of toxic elements (As = 75 mg/kg; Hg = 150 μg/kg) and radioactivity (226Ra + 228Ra = 8 pCi/g) to the environment has the potential to generate resuspended ambient fine particles (<10 μm) containing these toxics into the atmosphere that may pose a health risk to local communities. Second, leaching of contaminants from the coal ash caused contamination of surface waters in areas of restricted water exchange, but only trace levels were found in the downstream Emory and Clinch Rivers due to river dilution. Third, the accumulation of Hg- and As-rich coal ash in river sediments has the potential to have an impact on the ecological system in the downstream rivers by fish poisoning and methylmercury formation in anaerobic river sediments.

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