A carbon-rich black layer, dating to Ϸ12.9 ka, has been previously identified at Ϸ50 Clovis-age sites across North America and appears contemporaneous with the abrupt onset of Younger Dryas (YD) cooling. The in situ bones of extinct Pleistocene megafauna, along with Clovis tool assemblages, occur below this black layer but not within or above it. Causes for the extinctions, YD cooling, and termination of Clovis culture have long been controversial. In this paper, we provide evidence for an extraterrestrial (ET) impact event at Х12.9 ka, which we hypothesize caused abrupt environmental changes that contributed to YD cooling, major ecological reorganization, broad-scale extinctions, and rapid human behavioral shifts at the end of the Clovis Period. Clovis-age sites in North American are overlain by a thin, discrete layer with varying peak abundances of (i) magnetic grains with iridium, (ii) magnetic microspherules, (iii) charcoal, (iv) soot, (v) carbon spherules, (vi) glass-like carbon containing nanodiamonds, and (vii) fullerenes with ET helium, all of which are evidence for an ET impact and associated biomass burning at Ϸ12.9 ka. This layer also extends throughout at least 15 Carolina Bays, which are unique, elliptical depressions, oriented to the northwest across the Atlantic Coastal Plain. We propose that one or more large, low-density ET objects exploded over northern North America, partially destabilizing the Laurentide Ice Sheet and triggering YD cooling. The shock wave, thermal pulse, and event-related environmental effects (e.g., extensive biomass burning and food limitations) contributed to end-Pleistocene megafaunal extinctions and adaptive shifts among PaleoAmericans in North America.comet ͉ iridium ͉ micrometeorites ͉ nanodiamonds ͉ spherules

Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (δ 13 C-CH 4 , δ 13 C-C 2 H 6 , and δ 2 H-CH 4 ), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas 4 He to CH 4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living <1 km from gas wells have drinking water contaminated with stray gases.carbon, hydrogen, and helium isotopes | groundwater contamination | geochemical fingerprinting | fracking | hydrology and ecology

Horizontal drilling and hydraulic fracturing have enhanced energy production but raised concerns about drinking-water contamination and other environmental impacts. Identifying the sources and mechanisms of contamination can help improve the environmental and economic sustainability of shale-gas extraction. We analyzed 113 and 20 samples from drinking-water wells overlying the Marcellus and Barnett Shales, respectively, examining hydrocarbon abundance and isotopic compositions (e.g., C 2 H 6 /CH 4 , δ 13 C-CH 4 ) and providing, to our knowledge, the first comprehensive analyses of noble gases and their isotopes (e.g., 4 He, 20 Ne, 36 Ar) in groundwater near shale-gas wells. We addressed two questions. (i) Are elevated levels of hydrocarbon gases in drinking-water aquifers near gas wells natural or anthropogenic? (ii) If fugitive gas contamination exists, what mechanisms cause it? Against a backdrop of naturally occurring salt-and gas-rich groundwater, we identified eight discrete clusters of fugitive gas contamination, seven in Pennsylvania and one in Texas that showed increased contamination through time. Where fugitive gas contamination occurred, the relative proportions of thermogenic hydrocarbon gas (e.g., CH 4 , 4 He) were significantly higher (P < 0.01) and the proportions of atmospheric gases (air-saturated water; e.g., N 2 , 36 Ar) were significantly lower (P < 0.01) relative to background groundwater. Noble gas isotope and hydrocarbon data link four contamination clusters to gas leakage from intermediate-depth strata through failures of annulus cement, three to target production gases that seem to implicate faulty production casings, and one to an underground gas well failure. Noble gas data appear to rule out gas contamination by upward migration from depth through overlying geological strata triggered by horizontal drilling or hydraulic fracturing. noble gas geochemistry | groundwater contamination | methane | water quality | isotopic tracers

It is demonstrated that fullerenes, prepared via the standard method (an arc between graphite electrodes in a partial pressure of helium), on heating to high temperatures release (4)He and (3)He. The amount corresponds to one (4)He for every 880,000 fullerene molecules. The (3)He/(4)He isotopic ratio is that of tank helium rather than that of atmospheric helium. These results convincingly show that the helium is inside and that there is no exchange with the atmosphere. The amount found corresponds with a prediction from a simple model based on the expected volume of the cavity. In addition, the temperature dependence for the release of helium implies a barrier about 80 kilocalories per mole. This is much lower than the barrier expected from theory for helium passing through one of the rings in the intact structure. Amechanism involving reversibly breaking one or more bonds to temporarily open a "window" in the cage is proposed. A predicted consequence of this mechanism is the incorporation of other gases while the "window" is open. This was demonstrated through the incorporation of (3)He and neon by heating fullerene in their presence.

The Tagish Lake meteorite fell last year on a frozen lake in Canada and may provide the most pristine material of its kind. Analyses have now shown this carbonaceous chondrite to contain a suite of soluble organic compounds (approximately 100 parts per million) that includes mono- and dicarboxylic acids, dicarboximides, pyridine carboxylic acids, a sulfonic acid, and both aliphatic and aromatic hydrocarbons. The insoluble carbon exhibits exclusive aromatic character, deuterium enrichment, and fullerenes containing "planetary" helium and argon. The findings provide insight into an outcome of early solar chemical evolution that differs from any seen so far in meteorites.

In their first paper on Buckminsterfullerene,1 Kroto and Smalley et al. proposed a hollow structure. Interest in theinclusion of atoms into the cavity to form "endohedral complexesn has continued. Early work concentrated on incorporating metals? but noble gas atoms were obvious possibilities. Several studies reported that collisions of fullerene cation radicals with helium and neon in a mass spectrometer led to addition of the mass of the noble gas atoms to the ions.S7 Many theoretical studiesB-15 have appeared with estimates of the energies of fullerenes containing noble gas atoms, the dynamics of motion inside the cavity, and spectroscopic properties, even though none of these substances has been prepared in quantity.We have recently shown16 that fullerene prepared in the standard manner (a graphite arc in a low pressure of helium17) contains helium in about one in a million molecules. Heating fullerenes in several atmospheres of 3He or neon at 600 "C led to inclusion of these atoms at similar levels. We proposed that (1) Kroto, H. W.; Heath, J. R.; OBrien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985, 318, 162-163. (2) Heath, J. R.; OBrien, S. C.; Zhang, Q.; Liu, Y.; Curl, R. F.; Kroto, H. W.; Smalley, R. E. J. Am. Chem. Soc. 1985,107,7779-7780. (3) Weiske, T.; Bdhme, D. K.; HruUk, J.; KrHtchmer, K.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1991, 30, 884-886. (4) Schwarz, H.; Weiskc, T.; Bdhme, D. K.; HruUk, J. In Euckminrterfullerenes; Billups, W. E., Ciufolini, M. A,, Eds.; VCH Publishers: New (5) Ross, M. M.; Callahan, J. H. (7) Caldwcll, K. A.; Giblin, D. E.; Hsu, C. S.; Cox, D.; Gross, M. L. J. Am. (8) Breton, J.; Gonzalez-Platas, J.; Girardet, G. (IS) Cardini, 0.; Procacci, P.; Salvi, P. R.; Schettino, V. Chem. Phys. (16) Saunders, M.; JimCnez-Vhzqucz. H. A,; Cross, R. J.; Poreda, R. J. (17) KrHtchmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. 3734. 8362. 8741. 1864-7869.this process takes place by the reversible breaking of one or more bonds, opening a "window" large enough for entry of atoms. The noble gases were detected by heating samples in the modified mass spectrometer operated by one of us (R.J.P.). 16 We have now incorporated krypton using -15 atm at 600 OC for 2 h. An 18.5-mg sample of the resulting fullerene yielded 1.6 X 1 V cm3 of 84Kr on heating (1 atom in 410 OOO molecules), with a release pattern similar to that reported for helium and neon. Since several theoretical papers predicted that krypton and xenon would not fit into CM, we wanted to try to incorporate xenon.To investigate the spectroscopic and other properties of these interesting noble gas compounds, it is necessary to increase the fraction of fullerene molecules occupied. We have done this by carrying out the incorporation step at high pressures of the gas. One of us (S.M.) operates a facility with high-pressure steel vessels that can be heated behind appropriate shielding. Usually, a pump is employed to compress the gas into the vessel. Using expensive gases (e.g., 3He), this is a disadvantage since large amounts o...

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We find anomalously high gadolinium (Gd) concentrations in the femoral head bones of patients exposed to chelated Gd, commonly used as a contrast agent for medical imaging. Gd is introduced in chelated form to protect patients from exposure to toxic free Gd(3+), a calcium antagonist which disrupts cellular processes. Recent studies suggest Gd chelates break down in vivo, and Gd accumulation in tissue is linked to medical conditions such as nephrogenic systemic fibrosis (NSF), acute kidney failure, and in some cases death. We measure Gd and other rare earth element (REE) concentrations in 35 femoral heads by solution based ICP-MS. Gd concentrations in patients with documented exposure to Gd-based contrast agents (n = 13: Gd DTPA-BMA (Omniscan) n = 6; Gd HP-DO3A (Prohance) n = 5; unknown type n = 4) are significantly higher (p < 0.001) than the control group (n = 17). We use our control group to establish the 'natural' background level of Gd in human bone (cortical 95% CI: 0.023, 0.041 nmol/g; trabecular 95% CI: 0.054, 0.107 nmol/g). A control group outlier reveals the occurrence of individuals with high concentrations of all REEs, including Gd. Because of this, we calculate Gd anomalies from the concentrations of adjacent REEs and normalize to the control group mean to isolate Gd input from contrast agents. Normalized Gd anomalies, (Gd/Gd*)(N), for exposed patients range up to >800 times the 'natural' level (95% CI: 124, 460). Our data confirm that Gd, introduced in chelated form, incorporates into bone and is retained for more than 8 years. No difference was observed in bone Gd concentrations and anomalies between patients dosed with Gd DTPA-BMA (Omniscan; n = 6) and Gd HP-DO3A (Prohance; n = 5). Osteoporotic fracture patients exposed to Gd have significantly lower Gd concentrations than osteoarthritis patients (p < 0.001). This indicates different mechanisms of metal incorporation and/or retention in osteoporotic bone tissues, and may signal an increased risk of endogenous Gd release for patients with increased rates of bone resorption (e.g. osteoporosis patients and menopausal, pregnant, and lactating women) who are exposed to Gd-based contrast agents.