Deformation properties of lead isotopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolokonnikov, S. V.; Borzov, I. N.; Lutostansky, Yu. S.

2016-01-15

The deformation properties of a long lead isotopic chain up to the neutron drip line are analyzed on the basis of the energy density functional (EDF) in the FaNDF{sup 0} Fayans form. The question of whether the ground state of neutron-deficient lead isotopes can have a stable deformation is studied in detail. The prediction of this deformation is contained in the results obtained on the basis of the HFB-17 and HFB-27 Skyrme EDF versions and reported on Internet. The present analysis reveals that this is at odds with experimental data on charge radii and magnetic moments of odd lead isotopes.more » The Fayans EDF version predicts a spherical ground state for all light lead isotopes, but some of them (for example, {sup 180}Pb and {sup 184}Pb) prove to be very soft—that is, close to the point of a phase transition to a deformed state. Also, the results obtained in our present study are compared with the predictions of some other Skyrme EDF versions, including SKM*, SLy4, SLy6, and UNE1. By and large, their predictions are closer to the results arising upon the application of the Fayans functional. For example, the SLy4 functional predicts, in just the same way as the FaNDF{sup 0} functional, a spherical shape for all nuclei of this region. The remaining three Skyrme EDF versions lead to a deformation of some light lead isotopes, but their number is substantially smaller than that in the case of the HFB-17 and HFB-27 functionals. Moreover, the respective deformation energy is substantially lower, which gives grounds to hope for the restoration of a spherical shape upon going beyond the mean-field approximation, which we use here. Also, the deformation properties of neutron-rich lead isotopes are studied up to the neutron drip line. Here, the results obtained with the FaNDF{sup 0} functional are compared with the predictions of the HFB-17, HFB-27, SKM*, and SLy4 Skyrme EDF versions. All of the EDF versions considered here predict the existence of a region where

Archean Pb Isotope Evolution: Implications for the Early Earth.

NASA Astrophysics Data System (ADS)

Vervoort, J. D.; Thorpe, R.; Albarede, F.; Blichert-Toft, J.

2008-12-01

The U-Pb isotope system provides us with a powerful tool for understanding the chemical evolution of the Earth. Pb isotopes in Archean rocks, however, have not been widely utilized because U mobility makes initial Pb isotope ratios from old silicate rocks difficult, if not impossible, to determine. Galenas in syngenetic volcanogenic massive sulfide (VMS) deposits, however, provide snapshots of initial Pb ratios because their Pb isotopic composition is time invariant at their formation (U/Pb=0). The Pb isotopic record from galenas from rocks of all age have been utilized for over 70 years to answer a wide range of scientific problems beginning with Al Nier's pioneering work analyzing Pb isotopes in the 1930's but are no longer widely used by the isotopic community because they have been produced by older TIMS techniques. We have begun a re-examination of Archean Pb by an extensive analysis of over 100 galena samples from Archean VMS deposits throughout the Superior and Slave Provinces in Canada as well as from other VMS deposits in Finland, South Africa and Western Australia. The goal of this work is to provide modern, high precision measurements and update an old, but venerable, Pb isotopic data set. We feel these data provide important constraints on not only the Pb isotopic evolution of the Earth, but planetary differentiation and recycling processes operating in the first 2 b.y. of Earth's history. Our analytical techniques include dissolving the Pb sulfide minerals, purifying them with ion chromatography, and analyzing them using MC-ICPMS at both Washington State University (Neptune) and Ecole Normale Superieure in Lyon, France (Nu). All Pb solutions are doped with Tl in order to correct for mass fractionation. In this abstract we report preliminary galena Pb isotope data from 6 VMS deposits in the Abitibi greenstone belt: Chibougamu, Matagami, Noranda, Normetal, Timmins, and Val d"Or. These deposits are all approximately 2.7 Ga in age but in detail vary from 2

Stable lead isotopic analyses of historic and contemporary lead contamination of San Francisco Bay estuary

USGS Publications Warehouse

Ritson, P.I.; Bouse, R.M.; Flegal, A.R.; Luoma, S.N.

1999-01-01

Variations in stable lead isotopic composition (240Pb, 206Pb, 207Pb, 208Pb) in three sediment cores from the San Francisco Bay estuary document temporal changes in sources of lead during the past two centuries. Sediment, with lead from natural geologic sources, and relatively homogeneous lead isotopic compositions are overlain by sediments whose isotopic compositions indicate change in the sources of lead associated with anthropogenic modification of the estuary. The first perturbations of lead isotopic composition in the cores occur in the late 1800s concordant with the beginning of industrialization around the estuary. Large isotopic shifts, toward lower 206Pb/207Pb, occur after the turn of the century in both Richardson and San Pablo Bays. A similar relationship among lead isotopic compositions and lead concentrations in both Bays suggest contamination from the same source (a lead smelter). The uppermost sediments (post 1980) of all cores also have a relatively homogenous lead isotopic composition distinct from pre-anthropogenic and recent aerosol signatures. Lead isotopic compositions of leachates from fourteen surface sediments and five marsh samples from the estuary were also analyzed. These analyses suggest that the lead isotopic signature identified in the upper horizons of the cores is spatially homogeneous among recently deposited sediments throughout the estuary. Current aerosol lead isotopic compositions [Smith, D.R., Niemeyer, S., Flegal, A.R., 1992. Lead sources to California sea otters: industrial inputs circumvent natural lead biodepletion mechanisms. Environmental Research 57, 163-175] are distinct from the isotopic compositions of the surface sediments, suggesting that the major source of lead is cycling of historically contaminated sediments back through the water column. Both the upper core sediments and surface sediments apparently derive their lead predominantly from sources internal to the estuary. These results support the idea that

Lead isotope compositions as guides to early gold mineralization: The North Amethyst vein system, Creede district, Colorado

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

1994-01-01

Pb isotope compositions from the late stage of the North Amethyst vein system and from the Bondholder and central and southern Creede mining districts are more radiogenic than the host volcanic rocks of the central cluster of the San Juan volcanic field. Our Pb isotope results indicate that early Au mineralization of the North Amethyst area may represent the product of an older and relatively local hydrothermal system distinct from that of the younger base metal and Ag mineralization found throughout the region. Fluids that deposited Au minerals may have derived their Pb isotope composition by a greater degree of interaction with shallow, relatively less radiogenic volcanic wall rocks. The younger, base metal and Ag-rich mineralization that overprints the Au mineralization in the North Amethyst area clearly has a more radiogenic isotopic signature, which implies that the later mineralization derived a greater component of its Pb from Proterozoic source rocks, or sediments derived from them.Paragenetically early sulfide-rich vein assemblages have the least radiogenic galenas and generally also have the highest Au contents. Thus, identification of paragenetically early vein assemblages with relatively unradiogenic Pb isotope compositions similar to those of the North Amethyst area provides an additional exploration tool for Au in the central San Juan Mountains area.

Ore genesis of the Wusihe carbonate-hosted Zn-Pb deposit in the Dadu River Valley district, Yangtze Block, SW China: evidence from ore geology, S-Pb isotopes, and sphalerite Rb-Sr dating

NASA Astrophysics Data System (ADS)

Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping

2018-01-01

The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

The identification of lead ammunition as a source of lead exposure in First Nations: the use of lead isotope ratios.

PubMed

Tsuji, Leonard J S; Wainman, Bruce C; Martin, Ian D; Sutherland, Celine; Weber, Jean-Philippe; Dumas, Pierre; Nieboer, Evert

2008-04-15

The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of (206)Pb/(204)Pb and (206)Pb/(207)Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (p<0.05) positive correlations for (206)Pb/(204)Pb and (206)Pb/(207)Pb, and a significant negative correlation for (208)Pb/(206)Pb, as predicted if leaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.

Stable lead isotopes reveal a natural source of high lead concentrations to gasoline-contaminated groundwater

USGS Publications Warehouse

Landmeyer, J.E.; Bradley, P.M.; Bullen, T.D.

2003-01-01

Concentrations of total lead as high as 1,600 ??g/L were detected in gasoline-contaminated and uncontaminated groundwater at three gasoline-release sites in South Carolina. Total lead concentrations were highest in turbid groundwater samples from gasoline-contaminated and uncontaminated wells, whereas lower turbidity groundwater samples (collected using low-flow methods) had lower total lead concentrations. Dissolved lead concentrations in all wells sampled, however, were less than 15 ??g total lead/L, the current United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL). Because many total lead concentrations exceeded the MCL, the source of lead to the groundwater system at two of the three sites was investigated using a stable lead isotope ratio approach. Plots of the stable isotope ratios of lead (Pb) in groundwater as 207Pb/206Pb versus 208Pb/206Pb, and 208Pb/204Pb versus 206Pb/204Pb were similar to ratios characteristic of lead-based minerals in local rocks of the southeastern US, and were not similar to the stable lead isotopes ratios characteristic of distant lead ore deposits such as Broken Hill, Australia, used to produce tetraethyl lead in gasoline products prior to its phase-out and ban in the United States. Moreover, the isotopic composition of dissolved lead was equivalent to the isotopic composition of total lead in turbid samples collected from the same well, suggesting that the majority of the lead detected in the groundwater samples was associated with sediment particulates of indigenous aquifer material, rather than lead associated with spilled leaded gasoline. The results of this investigation indicate that (1) lead detected at some gasoline-release sites may be derived from the local aquifer material, rather than the gasoline release, and consequently may affect site-specific remediation goals; (2) non-low flow groundwater sampling methods, such as a disposable bailer, may result in turbid groundwater samples and

Source of lead and mineralizing brines for rossie-type Pb-Zn veins in the Frontenac axis area, New York ( USA).

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora K.; Brown, C. Erwin

1987-01-01

The present study of fluid inclusions and lead isotopes was done to understand better the nature and possible source of the mineralizing solutions for both vertical and gash veins and the possible origin of the lead and zinc mineralization. Large deposits of essentially syngenetic sphalerite with minor to trace galena occur in the Proterozoic rocks of this region (e.g., Balmat-Edwards, New York). Although none of these deposits are known in the immediate vicinity of Rossie veins, the possibility that Rossie veins contain remobilized metals from these older deposits was considered.

Correlation of Surface Adsorption and Oxidation with a Floatability Difference of Galena and Pyrite in High-Alkaline Lime Systems.

PubMed

Niu, Xiaopeng; Ruan, Renman; Xia, Liuyin; Li, Li; Sun, Heyun; Jia, Yan; Tan, Qiaoyi

2018-02-27

When it comes to Pb-Zn ores with high amounts of pyrite, the major problem encountered is the low separation efficiency between galena and pyrite. By virtue of high dosage of lime and collector sodium diethyl dithiocarbamate (DDTC), pyrite and zinc minerals are depressed, allowing the galena to be floated. However, there have been significant conflicting reports on the flotation behavior of galena at high pH. In this context, correlation of the surface adsorption and oxidation with the floatability difference of galena and pyrite in high-alkaline lime systems would be a key issue for process optimization. Captive bubble contact angle measurements were performed on freshly polished mineral surfaces in situ exposed to lime solutions of varying pH as a function of immersion time. Furthermore, single mineral microflotation tests were conducted. Both tests indicated that the degree of hydrophobicity on the surfaces of galena and pyrite increased in the presence of DDTC at natural or mild pulp pH. While in a saturated lime solution, at pH 12.5, DDTC only worked for galena, but not for pyrite. Surface chemistry analysis by time-of-flight secondary ion mass spectrometry (Tof-SIMS) confirmed the preference of DDTC on the galena surface at pH 12.5, which contributed to a merit recovery. Further important evidence through measurements of Tof-SIMS, ion chromatography, and high-performance liquid chromatography indicated that in high-alkaline lime systems, the merit floatability of galena could exclude the insignificant contribution of elemental sulfur (S 8 ) and was dominantly attributed by the strong adsorption of DDTC. In contrast, the poor flotation response of pyrite at high pH was due to the prevailing adsorption of CaOH + species. This study provides an important surface chemistry evidence for a better understanding of the mechanism on the better selectivity in the galena-pyrite separation adopting high-alkaline lime systems.

Lead isotopes reveal different sources of lead in balsamic and other vinegars.

PubMed

Ndung'u, Kuria; Hibdon, Sharon; Véron, Alain; Flegal, A Russell

2011-06-15

Fifty-eight brands of balsamic vinegars were analyzed for lead concentrations and isotopic compositions ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) to test the findings of a previous study indicating relatively high levels of lead contamination in some of those vinegars--more than two thirds (70%) of them exceeded California's State Maximum Level (34 μg/L) based on consumption rates ≥0.5 μg Pb per day. The lead isotopic fingerprints of all those vinegars with high lead concentrations were then found to be primarily anthropogenic. This isotopic analysis unquestionably reveals multiple contamination sources including atmospheric pollutant Pb and an unidentified contamination source, likely occurring after grape harvest. Organically grown grape vinegars display the same Pb content and isotopic signatures as other vinegars. This implies that pesticides might not be a significant source of pollutant Pb in vinegars. A significant post-harvest contamination would be inherited from chemicals added during production and/or material used during transport, processing or storage of these vinegars. This is consistent with the highest Pb levels being found in aged vinegars (112±112 μg/L) in contrast to other vinegars (41.6±28.9 μg/L) suggesting contamination during storage. It is, therefore, projected that lead levels in most vinegars, especially aged balsamic and wine vinegars, will decrease with improvements in their manufacture and storage processes consequential to recent concerns of elevated levels of lead in some vinegars. Copyright © 2011 Elsevier B.V. All rights reserved.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides

Flow-Meter and Passive Diffusion Bag Tests and Potential Influences on the Vertical Distribution of Contaminants in Wells at Galena Airport, Galena, Alaska, August to October 2002

USGS Publications Warehouse

Vroblesky, Don A.; Peterson, J.E.

2004-01-01

Past activities at Galena Airport, a U.S. Air Force Base in Galena, Alaska, have resulted in ground-water contamination by volatile organic compounds. The primary contaminants are petroleum hydrocarbons and chlorinated aliphatic hydrocarbons. The U.S. Geological Survey and Earth Tech, in cooperation with the Air Force Center for Environmental Excellence, conducted investigations at Galena Airport from August to October 2002 using polyethylene diffusion bag samplers and borehole flow-meter testing to examine the vertical distribution of ground-water contamination in selected wells. This investigation was limited to the vicinity of building 1845 and to the area between building 1845 and the Yukon River. In addition, the U.S. Geological Survey was asked to determine whether additional wells are needed to more clearly define the nature and extent of the ground-water contamination at the Air Force Base. Little or no vertical water movement occurred under ambient conditions in the wells tested at Galena Airport, Alaska, in August 2002. All of the ambient vertical flows detected in wells were at rates less than the quantitative limit of the borehole flow meter (0.03 gallons per minute). In wells 06-MW-07 and 10-MW-01, no vertical flow was detected. In wells where ambient flow was detected, the direction of flow was downward. In general, concentrations of volatile organic compounds detected in the low-flow samples from wells at Galena Airport were approximately the same concentrations detected in the closest polyethylene diffusion bag sample for a wide variety of volatile organic compounds. The data indicate that the polyethylene diffusion bag sample results are consistent with the low-flow sample results. Vertical profiling of selected wells using polyethylene diffusion bag samplers at Galena Airport showed that from September 30 to October 1, 2002, little vertical change occurred in volatile organic compound concentrations along the screen length despite the fact that

Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: a review.

PubMed

Cheng, Hefa; Hu, Yuanan

2010-05-01

As the most widely scattered toxic metal in the world, the sources of lead (Pb) observed in contamination investigation are often difficult to identify. This review presents an overview of the principles, analysis, and applications of Pb isotopic fingerprinting in tracing the origins and transport pathways of Pb in the environment. It also summarizes the history and current status of lead pollution in China, and illustrates the power of Pb isotopic fingerprinting with examples of its recent applications in investigating the effectiveness of leaded gasoline phase-out on atmospheric lead pollution, and the sources of Pb found in various environmental media (plants, sediments, and aquatic organisms) in China. The limitations of Pb isotopic fingerprinting technique are discussed and a perspective on its development is also presented. Further methodological developments and more widespread instrument availability are expected to make isotopic fingerprinting one of the key tools in lead pollution investigation. Copyright 2009 Elsevier Ltd. All rights reserved.

Lead isotope determinations from sulfide mineral occurrences--Russian Far East

USGS Publications Warehouse

Church, Stan E.; Goryachev, Nikolai A.; Shpikerman, Vladimir I.

2013-01-01

The lead isotope database for sulfide deposits and occurrences in the Russian Far East was funded by the Mineral Resources Program, U.S. Geological Survey (USGS) in conjunction with the collaborative studies of mineral resources by the Russian Academy of Sciences and the U. S. Geological Survey (Nokleberg and others, 1996). Comparisons of these data with similar lead isotope data from Alaska published in Church, Delevaux, and others (1987) and Gaccetta and Church (1989) provide a basis for the following three-fold project objectives: 1. To utilize lead isotope signatures, in conjunction with regional mapping, to assess the relative ages and to categorize the types of mineral deposits studied, 2. To relate the lead isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and 3. To use the lead isotope data to correlate lithotectonic terranes within the northern Cordillera (Alaska, Yukon Territories and British Columbia in Canada, and the western Cordillera of the United States). The report by Church, Gray, and others (1987) shows how this fingerprinting methodology can be applied to trace the offset of lithotectonic (or lithostratigraphic as labeled by some authors) terranes.The lead isotope data presented in table 1 represent the work completed on sulfide mineral deposits located in the Russian Far East from 1993 to 1995, when this study was terminated due to lack of funding. The lead isotope data are reported here for use by investigators who may find them of value in mineral exploration. No attempt is made to summarize the voluminous literature on these mineral deposits.

Lead isotopes in the western North Atlantic: Transient tracers of pollutant lead inputs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veron, A.J.; Church, T.M.; Flegal, A.R.

1998-08-01

In the early 1980s, Patterson and colleagues demonstrated that most lead in oceanic surface waters had an anthropogenic origin. Their discovery occurred during the phasing out of leaded gasoline in North America initiated in the previous decade. The corresponding decrease in anthropogenic lead emissions, verified by Pb/{sup 210}Pb ratios, accounted for the systematic decline in lead concentrations in surface waters of the western Sargasso Sea. Subsequent changes in anthropogenic lead inputs to the western Sargasso Sea surface waters have been documented by measurements of lead concentrations, isotopic compositions ({sup 206}Pb/{sup 207}Pb, {sup 208}Pb/{sup 206}Pb), and Pb/{sup 210}Pb ratios in precipitationmore » and seawater for the period of 1981 to 1994. These data indicate the easterly trade winds are now the primary source of atmospheric lead in Bermuda, and they confirm that the decline of lead concentrations in the North Atlantic is associated with the phasing out of leaded gasoline in North America and western Europe over the past decade. Moreover, temporal variations in the relative contribution of industrial lead inputs from the two sides of the North Atlantic over that period can be quantified based on differences in their isotopic composition. The transient character of those isotopic signatures also allows calculations of pollutant lead penetration rates into the mixed layer and upper thermocline of the western Sargasso Sea.« less

Microbially induced selective flotation of sphalerite from galena using mineral-adapted strains of Bacillus megaterium.

PubMed

Vasanthakumar, B; Ravishankar, H; Subramanian, S

2013-12-01

The selective flotation of sphalerite from a sphalerite-galena mineral mixture has been achieved using cells and extracellular secretions of Bacillus megaterium after adaptation to the chosen minerals. The extracellular secretions obtained after thermolysis of bacterial cells adapted to sphalerite yield the highest flotation recovery of sphalerite with a selectivity index value of 24.5, in comparison to the other cellular and extra-cellular bio-reagents studied. The protein profile for the unadapted and mineral-adapted cells has been found to differ distinctly, attesting to variation in the yield and nature of extra-cellular polymeric substances (EPS). The changes induced in the bacterial cell wall components after adaptation to sphalerite or galena with respect to the contents of phosphate, uronic acid and acetylated sugars of B. megaterium have been quantified. The role of the dissolved metal ions from the minerals as well as that of the constituents of extracellular secretions in modulating the surface charge of the bacterial cells as well as the minerals under study has been confirmed using various enzymatic treatments of the bacterial cells. It has been demonstrated that the induction of additional molecular weight protein fractions as well as the higher amount of extracellular proteins and phosphate secreted after adaptation to sphalerite vis-à-vis galena are contributory factors for the selective separation of sphalerite from galena. Copyright © 2013 Elsevier B.V. All rights reserved.

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

NASA Astrophysics Data System (ADS)

Jimenez, A.

2012-04-01

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls

Monitoring steel bridge renovation using lead isotopic tracing.

PubMed

Salome, Fred; Gulson, Brian; Chiaradia, Massimo; Davis, Jeffrey; Morris, Howard

2017-05-01

Monitoring removal of lead (Pb) paint from steel structures usually involves analysis of environmental samples for total lead and determination of blood Pb levels of employees involved in the Pb paint removal. We used high precision Pb isotopic tracing for a bridge undergoing Pb paint removal to determine if Pb in the environmental and blood samples originated from the bridge paint. The paint system on the bridge consisted of an anti-corrosive red Pb primer top-coated with a Micaceous Iron Oxide (MIO) alkyd. Analysis of the red Pb primer gave uniform isotopic ratios indicative of Pb from the geologically-ancient Broken Hill mines in western New South Wales, Australia. Likewise waste abrasive material, as anticipated, had the same isotopic composition as the paint. The isotopic ratios for other samples lay on 2 separate linear arrays on a 207 Pb/ 204 Pb versus 206 Pb/ 204 Pb diagram, one largely defined by gasoline and the majority of the ambient air data, and the other by data for one sample each of gasoline and ambient air and underwater sediments. Isotopic ratios in background ambient air samples for the project were characteristic of leaded gasoline. Air sampling during paint removal showed a contribution of paint Pb ranging from about 20 to 40%. Isotopic ratios in the blood of 8 employees prior to the commencement of work showed that 6 of these had been previously exposed to the Broken Hill Pb possibly from earlier bridge paint removal projects. One subject appeared to have increased exposure to Pb probably from the paint renovations. Copyright © 2017 Elsevier Ltd. All rights reserved.

The isotopic composition of ore lead of the Creede mining district and vicinity, San Juan Mountains, Colorado: Text of a talk presented at the San Juan Mountains symposium to honor Thomas A. Steven; Rocky Mountain Section meeting of the Geological Society of America, May 2, 1987, Boulder, Colorado

USGS Publications Warehouse

Foley, N.K.; Barton, P.B.; Bethke, P.M.; Doe, B.R.

1988-01-01

Recent work allows us to extend the results of Doe et al. and to consider alternative processes to explain the widespread homogeneity and radiogenic nature of the ore lead: 1) David Matty (pers. commun., 1986) has shown that some minor volcanic units in the area have unusually radiogneic lead values; magmas comparable in composition to the units are a possible, though improbable, source of the ore lead. 2) The uniformity of the isotopic values of galenas may have resulted from homogenization during an extensive potassium-metasomatic event that predated the ores; this possibility is being tested in an on-going study of feldspars from metasomatized and unmetasomatized rocks. 3) Recent regional studies suggest the possibility of a prevolcanic, NNW-trending graben system filled by clastic sediments derived from the Precambrian basement, a process that would have an homogenizing effect on the lead isotopes. This interpretation implies importation, deep within the Creede hydrologic system, of fluids from remote sources. These alternatives show that the Pbisotope systematics may have a profound impact on the interpretation of the Creede hydrothermal system, and that further study is warranted.

The potential source of lead in the Permian Kupferschiefer bed of Europe and some selected Paleozoic mineral deposits in the Federal Republic of Germany

USGS Publications Warehouse

Wedepohl, K.H.; Delevaux, M.H.; Doe, B.R.

1978-01-01

New lead isotopic compositions have been measured for Paleozoic bedded and vein ore deposits of Europe by the high precision thermal emission (triple filament) technique. Eleven samples have been analyzed from the Upper Permian Kupferschiefer bed with representatives from Poland to England, three samples from the Middle Devonian Rammelsberg deposit and one from the Middle Devonian Meggen deposit, both of which are conformable ore lenses and are in the Federal Republic of Germany (FRG); and also two vein deposits from the FRG were analyzed, from Ramsbeck in Devonian host rocks and from Grund in Carboniferous host rocks. For Kupferschiefer bed samples from Germany, the mineralization is of variable lead isotopic composition and appears to have been derived about 250 m.y. ago from 1700 m.y. old sources, or detritus of this age, in Paleozoic sedimentary rocks. Samples from England, Holland, and Poland have different isotopic characteristics from the German samples, indicative of significantly different source material (perhaps older). The isotopic variability of the samples from the Kupferschiefer bed in Germany probably favors the lead containing waters coming from shoreward (where poor mixing is to be expected) rather than basinward (where better mixing is likely) directions. The data thus support the interpretation of the metal source already given by Wedepohl in 1964. Data on samples from Rammelsberg and Meggen tend to be slightly less radiogenic than for the Kupferschiefer, about the amount expected if the leads were all derived from the same source material but 100 to 150 m.y. apart in time. The vein galena from Ramsbeck is similar to that from Rammelsberg conformable ore lenses, both in rocks of Devonian age; vein galena from Grund in Upper Carboniferous country rocks is similar to some bedded Kupferschiefer mineralization in Permian rocks, as if the lead composition was formed at about the same time and from similar source material as the bedded deposits

Human exposure to lead and other potentially harmful elements associated with galena mining at New Zurak, central Nigeria

NASA Astrophysics Data System (ADS)

Lar, U. A.; Ngozi-Chika, C. S.; Ashano, E. C.

2013-08-01

Galena mining in New Zurak, central Nigeria is currently increasing in intensity, with widespread artisanal mining taking place alongside mechanised mining. These activities are causing immeasurable damage to the environment. The prolonged human exposure and ingestion of Pb and other potentially harmful elements (PHEs) such as U, Cd, Se, Zn and As that are released from ores during these (mining) activities is a cause of great concern to populations that live in the vicinity of these mine fields. Many of the communities make their living from subsistence farming, growing food from the surroundings, and obtaining drinking water from nearby surface and sub-surface water resources. An overall assessment of the degree of contamination or toxicity of Pb and other PHEs was carried out using the indices of geoaccumulation (Igeo) and contamination factors (CFs), in the different media sampled - farmland soils, uncultivated lands, mine tailings/dumps, natural waters and vegetables. Results reveal that the mine tailings and dumps are highly contaminated with Pb and other PHEs followed in decreasing degree of contamination by the uncultivated lands, farmlands and natural waters. These findings suggest that release of Pb and other PHEs from the galena mining activity has contributed significantly to the enrichment of these elements in the surrounding environment, including the natural water bodies, and are disposed to subsequent entry into the human body through the food chain. As such these PHE accumulations pose significant risks to the environment and human health, especially of children and pregnant women who are the most vulnerable groups in the area. In order to forestall a reoccurrence of the Zamfara Pb poisoning episode in northwestern Nigeria in 2010, where more than 400 children died, the authorities concerned should ensure that mining in New Zurak is done in a more environmentally friendly manner, ensuring the maintenance of an environmental quality adequate for

Lead Isotope Characterization of Petroleum Fuels in Taipei, Taiwan

PubMed Central

Yao, Pei-Hsuan; Shyu, Guey-Shin; Chang, Ying-Fang; Chou, Yu-Chen; Shen, Chuan-Chou; Chou, Chi-Su; Chang, Tsun-Kuo

2015-01-01

Leaded gasoline in Taiwan was gradually phased out from 1983 to 2000. However, it is unclear whether unleaded gasoline still contributes to atmospheric lead (Pb) exposure in urban areas. In this study, Pb isotopic compositions of unleaded gasolines, with octane numbers of 92, 95, 98, and diesel from two local suppliers in Taipei were determined by multi-collector inductively coupled plasma mass spectrometry with a two-sigma uncertainty of ± 0.02 %. Lead isotopic ratios of vehicle exhaust (208Pb/207Pb: 2.427, 206Pb/207Pb: 1.148, as estimated from petroleum fuels) overlap with the reported aerosol data. This agreement indicates that local unleaded petroleum fuels, containing 10–45 ng·Pb·g−1, are merely one contributor among various sources to urban aerosol Pb. Additionally, the distinction between the products of the two companies is statistically significant in their individual 208Pb/206Pb ratios (p-value < 0.001, t test). Lead isotopic characterization appears to be applicable as a “fingerprinting” tool for tracing the sources of Pb pollution. PMID:25918913

Fluid inclusion and sulphur isotope evidence for syntectonic mineralisation at the Elura mine, southeastern Australia

NASA Astrophysics Data System (ADS)

Seccombe, P. K.

1990-10-01

Fluid inclusion and sulphur isotope data for the discordant, metasediment-hosted massive sulphide deposit at Elura are consistent with a syntectonic origin of the orebodies. Thermometric and laser Raman microprobe analyses indicate that two-phase, primary fluid inclusions are low salinity and H2O-CO2-CH4 types. Inclusion fluids from quartz in ore yield homogenisation temperatures (Th) ranging from 298 ° to 354 °C (mean 320 °C). They are likely to have been trapped close to the solvus of the H2O-CO2-(CH4-NaCl) system and thus should give temperatures of the mineralising fluid. An additional, low Th population of later fluid inclusions is recognised in quartz from ore and syntectonic extension veins in the adjacent wallrock. Th's for these low CO2bearing inclusions range from 150 to 231 °C (mean 190 °C), and should be considerably lower than true trapping temperatures. Sulphur isotopic composition (δ34S) of pyrite, sphalerite, pyrrhotite and galena ranges from 4.7 to 12.6% and indicates a sulphur source from underlying Cobar Supergroup metasediments. An average temperature of 275 °C from the sphalerite-galena sulphur isotopic thermometer suggests isotopic re-equilibration below peak metamorphic temperatures.

Origin of the mysterious Yin-Shang bronzes in China indicated by lead isotopes.

PubMed

Sun, Wei-dong; Zhang, Li-peng; Guo, Jia; Li, Cong-ying; Jiang, Yu-hang; Zartman, Robert E; Zhang, Zhao-feng

2016-03-18

Fine Yin-Shang bronzes containing lead with puzzlingly highly radiogenic isotopic compositions appeared suddenly in the alluvial plain of the Yellow River around 1400 BC. The Tongkuangyu copper deposit in central China is known to have lead isotopic compositions even more radiogenic and scattered than those of the Yin-Shang bronzes. Most of the Yin-Shang bronzes are tin-copper alloys with high lead contents. The low lead and tin concentrations, together with the less radiogenic lead isotopes of bronzes in an ancient smelting site nearby, however, exclude Tongkuangyu as the sole supplier of the Yin-Shang bronzes. Interestingly, tin ingots/prills and bronzes found in Africa also have highly radiogenic lead isotopes, but it remains mysterious as to how such African bronzes may have been transported to China. Nevertheless, these African bronzes are the only bronzes outside China so far reported that have lead isotopes similar to those of the Yin-Shang bronzes. All these radiogenic lead isotopes plot along ~2.0-2.5 Ga isochron lines, implying that deposits around Archean cratons are the most likely candidates for the sources. African cratons along the Nile and even micro-cratons in the Sahara desert may have similar lead signatures. These places were probably accessible by ancient civilizations, and thus are the most favorable suppliers of the bronzes.

Origin of the mysterious Yin-Shang bronzes in China indicated by lead isotopes

PubMed Central

Sun, Wei-dong; Zhang, Li-peng; Guo, Jia; Li, Cong-ying; Jiang, Yu-hang; Zartman, Robert E.; Zhang, Zhao-feng

2016-01-01

Fine Yin-Shang bronzes containing lead with puzzlingly highly radiogenic isotopic compositions appeared suddenly in the alluvial plain of the Yellow River around 1400 BC. The Tongkuangyu copper deposit in central China is known to have lead isotopic compositions even more radiogenic and scattered than those of the Yin-Shang bronzes. Most of the Yin-Shang bronzes are tin-copper alloys with high lead contents. The low lead and tin concentrations, together with the less radiogenic lead isotopes of bronzes in an ancient smelting site nearby, however, exclude Tongkuangyu as the sole supplier of the Yin-Shang bronzes. Interestingly, tin ingots/prills and bronzes found in Africa also have highly radiogenic lead isotopes, but it remains mysterious as to how such African bronzes may have been transported to China. Nevertheless, these African bronzes are the only bronzes outside China so far reported that have lead isotopes similar to those of the Yin-Shang bronzes. All these radiogenic lead isotopes plot along ~2.0–2.5 Ga isochron lines, implying that deposits around Archean cratons are the most likely candidates for the sources. African cratons along the Nile and even micro-cratons in the Sahara desert may have similar lead signatures. These places were probably accessible by ancient civilizations, and thus are the most favorable suppliers of the bronzes. PMID:26988425

A Noninvasive Isotopic Approach to Estimate the Bone Lead Contribution to Blood in Children: Implications for Assessing the Efficacy of Lead Abatement

PubMed Central

Gwiazda, Roberto; Campbell, Carla; Smith, Donald

2005-01-01

Lead hazard control measures to reduce children’s exposure to household lead sources often result in only limited reductions in blood lead levels. This may be due to incomplete remediation of lead sources and/or to the remobilization of lead stores from bone, which may act as an endogenous lead source that buffers reductions in blood lead levels. Here we present a noninvasive isotopic approach to estimate the magnitude of the bone lead contribution to blood in children following household lead remediation. In this approach, lead isotopic ratios of a child’s blood and 5-day fecal samples are determined before and after a household intervention aimed at reducing the child’s lead intake. The bone lead contribution to blood is estimated from a system of mass balance equations of lead concentrations and isotopic compositions in blood at the different times of sample collection. The utility of this method is illustrated with three cases of children with blood lead levels in the range of 18–29 μg/dL. In all three cases, the release of lead from bone supported a substantial fraction of the measured blood lead level postintervention, up to 96% in one case. In general, the lead isotopic compositions of feces matched or were within the range of the lead isotopic compositions of the household dusts with lead loadings exceeding U.S. Environmental Protection Agency action levels. This isotopic agreement underscores the utility of lead isotopic measurements of feces to identify household sources of lead exposure. Results from this limited number of cases support the hypothesis that the release of bone lead into blood may substantially buffer the decrease in blood lead levels expected from the reduction in lead intake. PMID:15626656

Genetic relations of oceanic basalts as indicated by lead isotopes

USGS Publications Warehouse

Tatsumoto, M.

1966-01-01

The isotopic compositions of lead and the concentrations of lead, uranium, and thorium in samples of oceanic tholeiite and alkali suites are determined, and the genetic relations of the oceanic basalts are discussed. Lead of the oceanic tholeiites has a varying lead-206 : lead-204 ratio between 17.8 and 18.8, while leads of the alkali basalt suites from Easter Island and Guadalupe Island are very radiogenic with lead-206 : lead-204 ratios between 19.3 and 20.4. It is concluded that (i) the isotopic composition of lead in oceanic tholeiite suggests that the upper mantle source region of the tholeiite was differentiated from an original mantle material more than 1 billion years ago and that the upper mantle is not homogeneous at the present time, (ii) less than 20 million years was required for the crystal differentiation within the alkali suite from Easter Island, (iii) no crustal contamination was involved in the course of differentiation of rocks from Easter Island; however, some crustal contamination may have affected Guadalupe Island rocks, and (iv) alkali basalt may be produced from the tholeiite in the oceanic region by crystal differentiation. Alternatively the difference in the isotopic composition of lead in oceanic basalts may be produced by partial melting at different depths of a differentiated upper mantle.

Discrimination of bullet types using analysis of lead isotopes deposited in gunshot entry wounds.

PubMed

Wunnapuk, Klintean; Minami, Takeshi; Durongkadech, Piya; Tohno, Setsuko; Ruangyuttikarn, Werawan; Moriwake, Yumi; Vichairat, Karnda; Sribanditmongkol, Pongruk; Tohno, Yoshiyuki

2009-01-01

In order to discriminate bullet types used in firearms, of which the victims died, the authors investigated lead isotope ratios in gunshot entry wounds from nine lead (unjacketed) bullets, 15 semi-jacketed bullets, and 14 full-jacketed bullets by inductively coupled plasma-mass spectrometry. It was found that the lead isotope ratio of 207/206 in gunshot entry wounds was the highest with lead bullets, and it decreased in order from full-jacketed to semi-jacketed bullets. Lead isotope ratios of 208/206 or 208/207 to 207/206 at the gunshot entry wound were able to discriminate semi-jacketed bullets from lead and full-jacketed ones, but it was difficult to discriminate between lead and full-jacketed bullets. However, a combination of element and lead isotope ratio analyses in gunshot entry wounds enabled discrimination between lead, semi-jacketed, and full-jacketed bullets.

Kinetics of nonoxidative leaching of galena in perchloric, hydrobromic, and hydrochloric acid solutions

NASA Astrophysics Data System (ADS)

Núñez, C.; Espiell, F.; García-Zayas, J.

1988-08-01

Several kinetic studies are presented on the nonoxidative leaching of galena with solutions of hydrocloric, hydrobromic, and perchloric acid. The kinetic parameters were set up in terms of the mean ionic activities of the electrolytes. The apparent order of reaction for the mean ionic activity of perchloric acid is one. For hydrochloric acid the order of reaction over a wide range of concentrations is 3/2 with respect to its mean activity. For hydrobromic acid, whose anion has greater complex-forming power for lead than HC1, the order of reaction is 2. Activation energies are 64.4 kJ/mole for HC1, 71.5 kJ/mole for HC104, and 66.5 kJ mole for HBr. The complete kinetic equations are given for the three reactions.

Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finkelstein, Myra E., E-mail: myraf@ucsc.edu; Kuspa, Zeka E.; Welch, Alacia

Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot frommore » all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ∼20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events. - Highlights: • We conducted a case-based analysis of illegal shootings of California condors. • Blood and feather Pb isotopes were used to reconstruct the illegal shooting events. • Embedded birdshot from the three condors had the same Pb isotope ratios. • Feather and blood Pb isotopes indicated that the condors were shot in a common event. • Ingested shot causes substantially greater lead exposure compared to embedded shot.« less

Element distribution patterns in the ordovician Galena group, Southeastern Minnesota: Indicators of fluid flow and provenance of terrigenous material

USGS Publications Warehouse

Lively, R.S.; Morey, G.B.; Mossler, J.H.

1997-01-01

As part of a regional geochemical investigation of lower Paleozoic strata in the Hollandale embayment of southeastern Minnesota, elemental concentrations in acid-insoluble residues were determined for carbonate rock in the Middle Ordovician Galena Group. Elemental distribution patterns within the insoluble residues, particularly those of Ti, Al, and Zr, show that the Wisconsin dome and the Wisconsin arch, which contributed sediment to the embayment prior to Galena time, continued as weak sources of sediment during this period. In contrast, trace metals commonly associated with Mississippi Valley-type lead-zinc mineralization, including Pb, Zn, Cu, Ag, Ni, Co, As, and Mo, show dispersal patterns that are independent of those associated with primary depositional phenomena. These trace metals are concentrated in southern Minnesota in carbonate rocks near the interface between limestone- and dolostone-dominated strata. Dispersal patterns imply that the metals were carried by a north-flowing regional ground-water system. The results show that the geochemical attributes of insoluble residues can be used to distinguish provenance and transport directions of primary sediments within a depositional basin from effects of subsequent regional ground-water flow systems.

The Balmat-Edwards zinc-lead deposits-synsedimentary ore from Mississippi valley-type fluids.

USGS Publications Warehouse

Whelan, J.F.; Rye, R.O.; Delorraine, W.

1984-01-01

The Balmat-Edwards Zn-Pb district in New York is in Mid-Proterozoic Grenville marbles. Tabular to podiform, generally conformable massive sphalerite-galena orebodies occur at various horizons in the approx 1 km-thick marbles. Metamorphism obscured or obliterated most primary characteristics, whose reconstruction is attempted through detailed S, C, and O isotope studies of the Fowler orebody, and trace element and S isotope studies of sphalerite concentrates and composite ore samples from 22 orebodies. Sulphur isotope data reflect equilibration at near peak metamorphism with some indication of re-equilibration during retrograde metamorphism. The carbon and oxygen isotope composition of gangue carbonates suggests derivation from the host marbles. The oxygen isotope composition of gangue quartz is compatible with a chert origin or metamorphism-equilibration with other minerals. Sulphur and lead isotopes and sulphide mineralogy suggests that the ore fluids were evolved basin brines, chemically like those responsible for Mississippi Valley-type deposits. The large stratigraphic span (> 600 m) of the Balmat orebodies may be due to basin dewatering of million-year intervals. Stratigraphically increasing 34S values of evaporite-anhydrite are postulated to record hydrothermal events and to imply bacterial sulphate reduction on an unusually large scale. Such a stratigraphic increase may be a general exploration guide where sediment-hosted exhalative deposits or Mississippi Valley-type deposits occur.-G.J.N.

Lead isotopic compositions of common arsenical pesticides used in New England

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora; Robinson, Gilpin; Wandless, Gregory; Dillingham, Jeremy

2004-01-01

The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulson, Brian, E-mail: brian.gulson@mq.edu.au; CSIRO Earth Science and Resource Engineering North Ryde, NSW 1670; Korsch, Michael

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments,more » air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. - Highlights: Black-Right-Pointing-Triangle Lead carbonate concentrate. Black-Right-Pointing-Triangle Successful use of Pb isotopes in identifying sources of Pb arising from transport and shipping. Black-Right-Pointing-Triangle Use of Pb isotopes in legal proceedings and their use in cleanup of residences

The lead isotopic age of the Earth can be explained by core formation alone.

PubMed

Wood, Bernard J; Halliday, Alex N

2010-06-10

The meaning of the age of the Earth defined by lead isotopes has long been unclear. Recently it has been proposed that the age of the Earth deduced from lead isotopes reflects volatile loss to space at the time of the Moon-forming giant impact rather than partitioning into metallic liquids during protracted core formation. Here we show that lead partitioning into liquid iron depends strongly on carbon content and that, given a content of approximately 0.2% carbon, experimental and isotopic data both provide evidence of strong partitioning of lead into the core throughout the Earth's accretion. Earlier conclusions that lead is weakly partitioned into iron arose from the use of carbon-saturated (about 5% C) iron alloys. The lead isotopic age of the Earth is therefore consistent with partitioning into the core and with no significant late losses of moderately volatile elements to space during the giant impact.

Lead isotope profiling in dairy calves.

PubMed

Buchweitz, John; McClure-Brinton, Kimberly; Zyskowski, Justin; Stensen, Lauren; Lehner, Andreas

2015-03-01

Lead (Pb) is a common cause of heavy metal poisonings in cattle. Sources of Pb on farms include crankcase oil, machinery grease, batteries, plumbing, and paint chips. Consequently, consumption of Pb from these sources may negatively impact animal health and Pb may be inadvertently introduced into the food supply. Therefore, the scope of poisoning incidents must be clearly assessed and sources of intoxication identified and strategies to mitigate exposure evaluated and implemented to prevent future exposures. Stable isotope analysis by inductively-coupled plasma mass spectrometry (ICP-MS) has proven itself of value in forensic investigations. We report on the extension of Pb stable isotope analysis to bovine tissues and profile comparisons with paint chips and soils collected from an affected dairy farm to elucidate the primary source. Pb occurs naturally as four stable isotopes: (204)Pb, (206)Pb, (207)Pb, and (208)Pb. Herein a case is reported to illustrate the use of (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios to link environmental sources of exposure with tissues from a poisoned animal. Chemical Pb profiling provides a valuable tool for field investigative approaches to Pb poisoning in production agriculture and is applicable to subclinical exposures. Copyright © 2014 Elsevier Inc. All rights reserved.

Hercynian Pb-Zn mineralization types in the Alcudia Valley mining district (Spain) and their reflect in Pb isotopic signatures

NASA Astrophysics Data System (ADS)

García de Madinabeitia, S.; Santos Zalduegui, J. F.; Palero, F.; Gil Ibarguchi, J. I.; Carracedo, M.

2003-04-01

More than 450 ore deposits indexed within the Alcudia Valley of the Central-Iberian Zone (Spain) may be grouped by their tectonic and lithologic characteristics (1,2) as follows: type A of rare stratabound mineralizations, and types B, C, D and E represented by abundant Hercynian veins (post-Namurian). 86 new Pb isotope analyses of galenas from the four vein types reveal that types B and C have similar isotopic ratios with values of μ_2 = 10.07, ω_2 = 40.6 and a mean model age of 564 Ma. Types D and E have μ_2 and ω_2 values of 9.79 and 38.5, respectively, but differ each other with respect to their model ages, 600 Ma (type D) and 335 Ma (type E). The observed variations appear to be related to the geochemical features of the metasedimentary host-rocks of the mineralizations where two distinct types of Pb isotopic ratios have been reported (3): one with μ_2 and ω_2 comparable to those of the D and E types and another with a more radiogenic composition, close to those of the B and C types of galenas. Nägler et al. have suggested partial rehomogeneization of Pb isotopic composition within the metasediments at ca. 330 Ma, that is, prior to the mineralization events, but the extent of this process and its effects on the ore bodies isotopic features is not evident. The origin of the more abundant E type ore bodies has been related to the Hercynian granitic rocks in the area (2, and references therein). Other plutons within this sector of the Central Iberian Zone (e.g., Linares, etc.; cf. accompanying Abstract) associate ore bodies whose Pb isotopic composition is very similar to that of the E type galenas from the Alcudia Valley. The isotopic data obtained thus point to a related or common source material for the various types of granites within the area studied. Yet, the Pb isotopic composition of other mineralizations (B, C, D), likewise located in Hercynian veins, allow to consider different types of Pb-Zn ore bodies and point therefore to different sources of

The use of lead isotope analysis to identify potential sources of lead toxicosis in a juvenile bald eagle (Haliaeetus leucocephalus) with ventricular foreign bodies

USGS Publications Warehouse

Franzen-Klein, Dana; McRuer, David; Slabe, Vincent; Katzner, Todd

2018-01-01

A male juvenile bald eagle (Haliaeetus leucocephalus) was admitted to the Wildlife Center of Virginia with a left humeral fracture a large quantity of anthropogenic debris in the ventriculus, a blood lead level of 0.616 ppm, and clinical signs consistent with chronic lead toxicosis. Because of the poor prognosis for recovery and release, the eagle was euthanatized. Lead isotope analysis was performed to identify potential anthropogenic sources of lead in this bird. The lead isotope ratios in the eagle's femur (0.8773), liver (0.8761), and kidneys (0.8686) were most closely related to lead paint (0.8925), leaded gasoline (0.8450), and zinc smelting (0.8240). The lead isotope ratios were dissimilar to lead ammunition (0.8179) and the anthropogenic debris in the ventriculus. This case report documents foreign body ingestion in a free-ranging bald eagle and demonstrates the clinical utility of lead isotope analysis to potentially identify or exclude anthropogenic sources of lead poisoning in wildlife patients.

Tables for determining lead, uranium, and thorium isotope ages

NASA Technical Reports Server (NTRS)

Schonfeld, E.

1974-01-01

Tables for determining lead, uranium, and thorium isotope ages are presented in the form of computer printouts. Decay constants, analytical expressions for the functions evaluated, and the precision of the calculations are briefly discussed.

Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).

NASA Astrophysics Data System (ADS)

Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente

2015-04-01

The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.

Geology and ore deposits of the Mahd Adh Dhahab District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Luce, Robert W.; Bagdady, Abdulaziz; Roberts, Ralph Jackson

1976-01-01

The principal ore minerals are pyrite, chalcopyrite, sphalerite, galena, and minor tetrahedrite, argentite, and native gold and silver. The gold and silver occurs finely disseminated in the veins and in the altered selvages of the veins. Widespread potassic and propylitic alteration accompanied the ore-forming processes. Potassium feldspar was introduced during an early stage of vein formation. Isotopic analyses of lead in vein potassium feldspar and galena yield a model age of about 900-1050 million years with the possibility of the original lead source having been remobilized about 600 million years ago. Chlorite and carbonate are also prominent vein minerals.

Historical record of lead accumulation and source in the tidal flat of Haizhou Bay, Yellow Sea: Insights from lead isotopes.

PubMed

Zhang, Rui; Guan, Minglei; Shu, Yujie; Shen, Liya; Chen, Xixi; Zhang, Fan; Li, Tiegang

2016-05-15

In order to investigate the historical records of lead contamination and source in coastal region of Haizhou Bay, Yellow Sea, a sediment core was collected from tidal flat, dated by (210)Pb and (137)Cs. Lead and its stable isotopic ratios were determined. The profiles of enrichment factor (EF) and Pb isotope ratios showed increasing trend upward throughout the core, correlating closely with the experience of a rapid economic and industrial development of the catchment. According to Pb isotopic ratios, coal combustion emission mainly contributed to the Pb burden in sediments. Based on end-member model, coal combustion emission dominated anthropogenic Pb sources in recent decades contributing from 48% to 67% in sediment. And the contribution of leaded gasoline was lower than 20%. A stable increase of coal combustion source was found in sediment core, while the contribution of leaded gasoline had declined recently, with the phase-out of leaded gasoline in China. Copyright © 2016 Elsevier Ltd. All rights reserved.

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring.

PubMed

Gulson, Brian; Korsch, Michael; Winchester, Wayne; Devenish, Matthew; Hobbs, Thad; Main, Cleve; Smith, Gerard; Rosman, Kevin; Howearth, Lynette; Burn-Nunes, Laurie; Seow, Jimmy; Oxford, Cameron; Yun, Gracie; Gillam, Lindsay; Crisp, Michelle

2012-01-01

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments, air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

Tracing changes in atmospheric sources of lead contamination using lead isotopic compositions in Australian red wine.

PubMed

Kristensen, Louise Jane; Taylor, Mark Patrick; Evans, Andrew James

2016-07-01

Air quality data detailing changes to atmospheric composition from Australia's leaded petrol consumption is spatially and temporally limited. In order to address this data gap, wine was investigated as a potential proxy for atmospheric lead conditions. Wine spanning sixty years was collected from two wine regions proximal to the South Australian capital city, Adelaide, and analysed for lead concentration and lead and strontium isotopic composition for source apportionment. Maximum wine lead concentrations (328 μg/L) occur prior to the lead-in-air monitoring in South Australia in the later 1970s. Wine lead concentrations mirror available lead-in-air measurements and show a declining trend reflecting parallel reductions in leaded petrol emissions. Lead from petrol dominated the lead in wine ((206)Pb/(207)Pb: 1.086; (208)Pb/(207)Pb: 2.360) until the introduction of unleaded petrol, which resulted in a shift in the wine lead isotopic composition closer to vineyard soil ((206)Pb/(207)Pb: 1.137; (208)Pb/(207)Pb: 2.421). Current mining activities or vinification processes appear to have no impact with recent wine samples containing less than 4 μg/L of lead. This study demonstrates wine can be used to chronicle changes in environmental lead emissions and is an effective proxy for atmospherically sourced depositions of lead in the absence of air quality data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Historic and Industrial Lead within the Northwest Pacific Ocean Evidenced by Lead Isotopes in Seawater.

PubMed

Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

2017-02-07

We report the continued lead (Pb) contamination of the Northwest Pacific Ocean in 2002 and present the first comprehensive Pb isotope data set for that region. In the upper ocean, a Pb concentration maxima (64-113 pmol kg -1 ) extended throughout the entire North Pacific Subtropical Gyre (NPSG). We determined most of the Pb in this feature was from industrial emissions by many nations in the 1980s and 1990s, with the largest contributions from leaded gasoline emissions. In contrast, the deep water (>1000 m) Pb concentrations were lower (6-37 pmol kg -1 ), and constituted a mix of background (natural) Pb and anthropogenic Pb inputs from preceding decades. Deep water below the Western Subarctic Gyre (WSAG) contained more industrial Pb than below the NPSG, which was attributed to a calculated 60-fold greater flux of particulate Pb to abyssal waters near the Asian continent. Assuming Pb isotope compositions in the North Pacific Ocean were homogeneous prior to large-scale 20th century anthropogenic inputs, this evidence suggests a relatively faster change in Pb isotope ratios of North Pacific deep water below the WSAG versus the NPSG.

Lead isotope systematics of some igneous rocks from the Egyptian Shield

NASA Technical Reports Server (NTRS)

Gillespie, J. G.; Dixon, T. H.

1983-01-01

Lead isotope data on whole-rock samples and two feldspar separates for a variety of Pan-African (late Precambrian) igneous rocks for the Egyptian Shield are presented. It is pointed out that the eastern desert of Egypt is a Late Precambrian shield characterized by the widespread occurrence of granitic plutons. The lead isotope ratios may be used to delineate boundaries between Late Precambrian oceanic and continental environments in northeastern Africa. The samples belong to three groups. These groups are related to a younger plutonic sequence of granites and adamellites, a plutonic group consisting of older tonalites to granodiorites, and the Dokhan volcanic suite.

Asian anthropogenic lead contamination in the North Pacific Ocean as evidenced by stable lead isotopic compositions

NASA Astrophysics Data System (ADS)

Zurbrick, Cheryl M.

This dissertation work determined the changing scope of lead (Pb) contamination in the North Pacific Ocean since the phase-out of leaded gasoline in most of the world. Chapters 1 and 2 consisted of validating our method for determining Pb concentrations and isotopic compositions in seawater. Chapter 3 established a baseline of Pb isotopic compositions (PbICs) in the western and central North Pacific in 2002. This was an ideal time to establish such a baseline because China had recently (mid-2000) ceased their use of leaded gasoline and simultaneously began consuming increasingly large amounts of coal, known to have relatively high Pb concentrations. We found subsurface waters were contaminated with Asian industrial Pb, predominantly Chinese coal emissions. In contrast, the abyssal waters were a mix of Asian industrial Pb and background (i.e., natural) Pb. Chapter 4 revisited the western and central North Pacific in 2009 -- 2011 to determine what, if any, changes had occurred in this short time period. We found that Pb in subsurface and abyssal waters of the western North Pacific were similar to Chinese aerosols. Such a large change in the PbICs of abyssal water in 9 years was unanticipated and attributed to the relatively large flux of particle-bound Pb from the euphotic zone to the deep ocean, which was in isotopic equilibrium with the reservoir of dissolved Pb. In contrast, the central North Pacific abyssal water PbICs were similar to values previously reported because of the relatively lower particulate export. Based on comparisons to baseline PbIC data, we determined that abyssal waters in the western and central North Pacific would be isotopically indistinguishable from surface waters in the next three decades. Sources of Pb to coastal California waters were reevaluated in Chapter 5. Prior studies had found that surface waters of the California Current System (CCS) were isotopically consistent with both Asian industrial Pb and US leaded gasoline, still in use

Lead contamination in cocoa and cocoa products: isotopic evidence of global contamination.

PubMed

Rankin, Charley W; Nriagu, Jerome O; Aggarwal, Jugdeep K; Arowolo, Toyin A; Adebayo, Kola; Flegal, A Russell

2005-10-01

In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was lead concentrations of manufactured cocoa and chocolate products were as high as 230 and 70 ng/g, respectively, which are consistent with market-basket surveys that have repeatedly listed lead concentrations in chocolate products among the highest reported for all foods. One source of contamination of the finished products is tentatively attributed to atmospheric emissions of leaded gasoline, which is still being used in Nigeria. Because of the high capacity of cocoa bean shells to adsorb lead, contamination from leaded gasoline emissions may occur during the fermentation and sun-drying of unshelled beans at cocoa farms. This mechanism is supported by similarities in lead isotopic compositions of cocoa bean shells from the different farms (206Pb/207Pb = 1.1548-1.1581; 208Pb/207Pb = 2.4344-2.4394) with those of finished cocoa products (206Pb/207Pb = 1.1475-1.1977; 208Pb/207Pb = 2.4234-2.4673). However, the much higher lead concentrations and larger variability in lead isotopic composition of finished cocoa products, which falls within the global range of industrial lead aerosols, indicate that most contamination occurs during shipping and/or processing of the cocoa beans and the manufacture of cocoa and chocolate products.

Laser photochemical lead isotopes separation for harmless nuclear power engineering

NASA Astrophysics Data System (ADS)

Bokhan, P. A.; Fateev, N. V.; Kim, V. A.; Zakrevsky, D. E.

2016-09-01

The collisional quenching of the metastable 3 P 1,2 and 1 D 2 lead atoms is studied experimentally in the gas flow of the lead atoms, reagent-molecules and a carrier gas Ar. The experimental parameters were similar to the conditions that are required in the operation of the experimental setup for photochemical isotope separation. Excited atoms are generated under electron impact conditions created by a gas glow discharge through the mixture of gases and monitored photoelectrically by attenuation of atomic resonance radiation from hollow cathode 208Pb lamp. The decay of the excited atoms has been studied in the presence various molecules and total cross section data are reported. The flow tube measurements has allowed to separate the physical and chemical quenching channels and measure the rates of the chemical reaction excited lead with N2O, CH2Cl2, SF6 and CuBr molecules. These results are discussed in the prospects of the obtaining isotopically modified lead as a promising coolant in the reactors on the fast-neutron.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region.

PubMed

Sharpe, Ashley E; Kamenov, George D; Gilli, Adrian; Hodell, David A; Emery, Kitty F; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region

PubMed Central

Kamenov, George D.; Gilli, Adrian; Hodell, David A.; Emery, Kitty F.; Brenner, Mark; Krigbaum, John

2016-01-01

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region. PMID:27806065

Lead isotopes and trace metals in dust at Yucca Mountain

USGS Publications Warehouse

Kwak, Loretta; Neymark, Leonid A.; Peterman, Zell E.

2008-01-01

Lead (Pb)-isotope compositions and trace-metal concentrations were determined for samples of dust collected from underground and surface locations at and near the proposed radioactive waste repository at Yucca Mountain, Nevada. Rare earth element concentrations in the dust samples from the underground tunnels are similar to those in wholerock samples of the repository host rocks (Miocene Tiva Canyon Tuff and Topopah Spring Tuff), supporting interpretation that the subsurface dust is mainly composed of rock comminuted during tunnel construction. Other trace metals (arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead, antimony, thallium, and zinc) are variably enriched in the subsurface dust samples relative to the average concentrations in the host rocks. Average concentrations of arsenic and lead in dust samples, high concentrations of which can cause corrosion of waste canisters, have enrichment factors from 1.2 to 1.6 and are insignificant relative to the range of concentrations for these metals observed in the host rock samples. Most dust samples from surface sites also are enriched in many of these trace metals relative to average repository host rocks. At least some of these enrichments may be artifacts of sampling. Plotted on a 208Pb/206Pb-207Pb/206Pb graph, Pb-isotope compositions of dust samples from underground sites form a mixing line extending from host-rock Pb-isotope compositions towards compositions of many of the dust samples from surface sites; however, combined Pb concentration and isotope data indicate the presence of a Pbenriched component in the subsurface dust that is not derived from host rock or surface dust and may derive from anthropogenic materials introduced into the underground environment.

Lead isotopic fingerprinting of aerosols to characterize the sources of atmospheric lead in an industrial city of India

NASA Astrophysics Data System (ADS)

Sen, Indra S.; Bizimis, Michael; Tripathi, Sachchida Nand; Paul, Debajyoti

2016-03-01

Anthropogenic Pb in the environment is primarily sourced from combustion of fossil fuel and high-temperature industries such as smelters. Identifying the sources and pathways of anthropogenic Pb in the environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb-isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, a large city in northern part of India. The study shows that the PM10 aerosols had elevated concentration of Cd, Pb, Zn, As, and Cu in the Kanpur area, however their concentrations are well below the United States Environmental Protection Agency chronic exposure limit. Lead isotopic and trace metal data reveal industrial emission as the plausible source of anthropogenic Pb in the atmosphere in Kanpur. However, Pb isotopic compositions of potential source end-members are required to fully evaluate Pb contamination in India over time. This is the first study that characterizes the isotopic composition of atmospheric Pb in an Indian city after leaded gasoline was phased out by 2000.

Lead Speciation And Bioavailability In Apatite-Amended Sediments

EPA Science Inventory

The in situ sequestration of lead (Pb) in sediment with a phosphate amendment was investigated by Pb speciation and bioavailability. Sediment Pb in preamendment samples was identified as galena (PbS) with trace amounts of absorbed Pb. Sediment exposed to atmospheric conditions ...

Lead Contamination in Cocoa and Cocoa Products: Isotopic Evidence of Global Contamination

PubMed Central

Rankin, Charley W.; Nriagu, Jerome O.; Aggarwal, Jugdeep K.; Arowolo, Toyin A.; Adebayo, Kola; Flegal, A. Russell

2005-01-01

In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was ≤ 0.5 ng/g, which is one of the lowest reported values for a natural food. In contrast, lead concentrations of manufactured cocoa and chocolate products were as high as 230 and 70 ng/g, respectively, which are consistent with market-basket surveys that have repeatedly listed lead concentrations in chocolate products among the highest reported for all foods. One source of contamination of the finished products is tentatively attributed to atmospheric emissions of leaded gasoline, which is still being used in Nigeria. Because of the high capacity of cocoa bean shells to adsorb lead, contamination from leaded gasoline emissions may occur during the fermentation and sun-drying of unshelled beans at cocoa farms. This mechanism is supported by similarities in lead isotopic compositions of cocoa bean shells from the different farms (206Pb/207Pb = 1.1548–1.1581; 208Pb/207Pb = 2.4344–2.4394) with those of finished cocoa products (206Pb/207Pb = 1.1475–1.1977; 208Pb/207Pb = 2.4234–2.4673). However, the much higher lead concentrations and larger variability in lead isotopic composition of finished cocoa products, which falls within the global range of industrial lead aerosols, indicate that most contamination occurs during shipping and/or processing of the cocoa beans and the manufacture of cocoa and chocolate products. PMID:16203244

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, K.F.; Haynam, C.A.; Johnson, M.A.; Worden, E.F.

1999-08-31

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207. 5 figs.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, Karl F.; Haynam, Christopher A.; Johnson, Michael A.; Worden, Earl F.

1999-01-01

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207.

Geology and geochemistry of the Reocín zinc-lead deposit, Basque-Cantabrian Basin, Northern Spain

USGS Publications Warehouse

Velasco, Francisco; Herrero, Jose Miguel; Yusta, Inaki; Alonso, Jose Antonio; Seebold, Ignacio; Leach, David

2003-01-01

fluids responsible for sulfide deposition and the infilling of karst cavities were broadly contemporaneous, indicating a post-Albian age. Vitrinite reflectance data are consistent with previously measured fluid inclusion temperatures and indicate temperatures of ore deposition that were less than 100??C. Carbon and oxygen isotopic data from samples of regional limestone, host-rock dolostone and ore-stage dolomite suggest an early hydrothermal alteration of limestone to dolostone. This initial dolomitization was followed by a second period of dolomite formation produced by the mixing of basinal metal-rich fluids with local modified seawater. Both dolomitization events occurred under similar conditions from fluids exhibiting characteristics of basinal brines. The ??34S values of sulfides are between -1.8 and +8.5 per mil, which is consistent with thermochemical sulfate reduction involving organic matter as the main source of reduced sulfur. Galena lead isotope compositions are among the most radiogenic values reported for Zn-Pb occurrences in Europe, and they are distinct from values reported for galena from other Basque-Cantabrian deposits. This suggests that a significant part of the lead was scavenged from the local underlying Asturian sediments. The stratigraphic and structural setting, timing of epigenetic mineralization, mineralogy, and isotopic geochemistry of sulfide and gangue minerals of the Reoci??n deposit are consistent with the features of most of Mississippi Valley-type ore deposits.

Coral-based history of lead and lead isotopes of the surface Indian Ocean since the mid-20th century

NASA Astrophysics Data System (ADS)

Lee, Jong-Mi; Boyle, Edward A.; Suci Nurhati, Intan; Pfeiffer, Miriam; Meltzner, Aron J.; Suwargadi, Bambang

2014-07-01

Anthropogenic lead (Pb) from industrial activities has greatly altered the distribution of Pb in the present-day oceans, but no continuous temporal Pb evolution record is available for the Indian Ocean despite rapidly emerging industries around the region. Here, we present the coral-inferred annual history of Pb concentration and isotope ratios in the surface Indian Ocean since the mid-20th century (1945-2010). We analyzed Pb in corals from the Chagos Archipelago, western Sumatra and Strait of Singapore - which represent the central Indian Ocean via nearshore sites. Overall, coral Pb/Ca increased in the mid-1970s at all the sites. However, coral Pb isotope ratios evolve distinctively at each site, suggesting Pb contamination arises from different sources in each case. The major source of Pb in the Chagos coral appears to be India's Pb emission from leaded gasoline combustion and coal burning, whereas Pb in western Sumatra seems to be largely affected by Indonesia's gasoline Pb emission with additional Pb inputs from other sources. Pb in the Strait of Singapore has complex sources and its isotopic composition does not reflect Pb from leaded gasoline combustion. Higher 206Pb/207Pb and 208Pb/207Pb ratios found at this site may reflect the contribution of Pb from coals and ores from southern China, Indonesia, and Australia, and local Pb sources in the Strait of Singapore. It is also possible that the Pb isotope ratios of Singapore seawater were elevated through isotope exchange with natural fluvial particles considering its delta setting.

Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shepherd, Thomas J.; British Geological Survey, Keyworth, Nottingham; Dirks, Wendy

We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and {sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5–8 years, living in NE England. By integrating the isotope datamore » with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2–3 years for molars, first 1–2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2 µg Pb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.126–2.079) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.879–0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM{sub 10}, PM{sub 2.5}) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4 µgPb/g) with {sup 208}Pb/{sup 206}Pb (mean ±2σ: 2.145–2.117) {sup 208}Pb/{sup 206}Pb (mean ±2σ: 0.898–0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1–2 months) were readily identified, together with evidence that dentine provides a good proxy for

Contaminated lead environments of man: reviewing the lead isotopic evidence in sediments, peat, and soils for the temporal and spatial patterns of atmospheric lead pollution in Sweden.

PubMed

Bindler, Richard

2011-08-01

Clair Patterson and colleagues demonstrated already four decades ago that the lead cycle was greatly altered on a global scale by humans. Moreover, this change occurred long before the implementation of monitoring programs designed to study lead and other trace metals. Patterson and colleagues also developed stable lead isotope analyses as a tool to differentiate between natural and pollution-derived lead. Since then, stable isotope analyses of sediment, peat, herbaria collections, soils, and forest plants have given us new insights into lead biogeochemical cycling in space and time. Three important conclusions from our studies of lead in the Swedish environment conducted over the past 15 years, which are well supported by extensive results from elsewhere in Europe and in North America, are: (1) lead deposition rates at sites removed from major point sources during the twentieth century were about 1,000 times higher than natural background deposition rates a few thousand years ago (~10 mg Pb m(-2) year(-1) vs. 0.01 mg Pb m(-2) year(-1)), and even today (~1 mg Pb m(-2) year(-1)) are still almost 100 times greater than natural rates. This increase from natural background to maximum fluxes is similar to estimated changes in body burdens of lead from ancient times to the twentieth century. (2) Stable lead isotopes ((206)Pb/(207)Pb ratios shown in this paper) are an effective tool to distinguish anthropogenic lead from the natural lead present in sediments, peat, and soils for both the majority of sites receiving diffuse inputs from long range and regional sources and for sites in close proximity to point sources. In sediments >3,500 years and in the parent soil material of the C-horizon, (206)Pb/(207)Pb ratios are higher, 1.3 to >2.0, whereas pollution sources and surface soils and peat have lower ratios that have been in the range 1.14-1.18. (3) Using stable lead isotopes, we have estimated that in southern Sweden the cumulative anthropogenic burden of

Tracing source pollution in soils using cadmium and lead isotopes.

PubMed

Cloquet, C; Carignan, J; Libourel, G; Sterckeman, T; Perdrix, E

2006-04-15

Tracing the source of heavy metals in the environment is of key importance for our understanding of their pollution and natural cycles in the surface Earth reservoirs. Up to now, most exclusively Pb isotopes were used to effectively trace metal pollution sources in the environment. Here we report systematic variations of Cd isotope ratios measured in polluted topsoils surrounding a Pb-Zn refinery plant in northern France. Fractionated Cd was measured in soil samples surrounding the refinery, and this fractionation can be attributed to the refining processes. Despite the Cd isotopic ratios being precisely measured, the obtained uncertainties are still large compared to the total isotopic variation. Nevertheless, for the first time, Cd isotopically fractionated by industrial processes may be traced in the environment. On the same samples, Pb isotope systematics suggested that materials actually used by the refinery were not the major source of Pb in soils, probably because refined ore origins changed over the 100 years of operation. On the other hand, Cd isotopes and concentrations measured in topsoils allowed identification of three main origins (industrial dust and slag and agriculture), assuming that all Cd ores are not fractionated, as suggested by terrestrial rocks so far analyzed, and calculation of their relative contributions for each sampling point. Understanding that this refinery context was an ideal situation for such a study, our results lead to the possibility of tracing sources of anthropogenic Cd and better constrain mixing processes, fluxes, transport, and phasing out of industrial input in nature.

Dynamic Determination of Some Optical and Electrical Properties of Galena Natural Mineral: Potassium Ethyl Xanthate Solution Interface

NASA Astrophysics Data System (ADS)

Todoran, D.; Todoran, R.; Anitas, E. M.; Szakacs, Zs.

2017-12-01

This paper presents results concerning optical and electrical properties of galena natural mineral and of the interface layer formed between it and the potassium ethyl xanthate solution. The applied experimental method was differential optical reflectance spectroscopy over the UV-Vis/NIR spectral domain. Computations were made using the Kramers-Kronig formalism. Spectral dependencies of the electron loss functions, determined from the reflectance data obtained from the polished mineral surface, display van Hove singularities, leading to the determination of its valence band gap and electron plasma energy. Time dependent measurement of the spectral dispersion of the relative reflectance of the film formed at the interface, using the same computational formalism, leads to the dynamical determination of the spectral variation of its optical and electrical properties. We computed behaviors of the dielectric constant (dielectric permittivity), the dielectric loss function, refractive index and extinction coefficient, effective valence number and of the electron loss functions. The measurements tend to stabilize when the dynamic adsorption-desorption equilibrium is reached at the interface level.

Lead isotope data bank; 2,624 samples and analyses cited

USGS Publications Warehouse

Doe, Bruce R.

1976-01-01

The Lead Isotope Data Bank (LIDB) was initiated to facilitate plotting data. Therefore, the Bank reflects data most often used in plotting rather than comprises a comprehensive tabulation of lead isotope data. Up until now, plotting was done using card decks processed by computer with tapes plotted by a Gerber plotter and more recently a CRT using a batch mode. Lack of a uniform format for sample identification was not a great impediment. With increase in the size of the bank, hand sorting is becoming prohibitive and ·plans are underway to put the bank into a uniform format on DISK with a card backup so that it may be accessed by use of IRIS on the DECK 10 computer at the U.S.G.S. facility in Denver. Plots will be constructed on a CRT. Entry of the bank into the IRIS accessing program is scheduled for completion in FY 1976

Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

NASA Astrophysics Data System (ADS)

Potra, Adriana; Macfarlane, Andrew W.

2014-01-01

New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the

Containing arsenic-enriched groundwater tracing lead isotopic compositions of common arsenical pesticides in a coastal Maine watershed

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.; Robinson, Glipin R.; Colvin, A.S.; Lipfert, G.; Reeve, A.S.

2006-01-01

Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb207Pb = 2.3839-2.4722, and 206Pb207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb 207Pb (1.1870-1.2069), and 208Pb207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g.,208Pb206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of

Record of Anthropocene pollution sources of lead in disturbed peatlands from Southern Poland

NASA Astrophysics Data System (ADS)

Fiałkiewicz-Kozieł, Barbara; De Vleeschouwer, François; Mattielli, Nadine; Fagel, Nathalie; Palowski, Bernard; Pazdur, Anna; Smieja-Król, Beata

2018-04-01

The importance of human impacts on Earth has led to the proposal of a new geologic epoch called the Anthropocene. However markers, recognizable in all records, are required to define this period. Here we combine elemental geochemistry with stable lead (Pb) isotopes and mineralogical analyses to decipher the sources of lead in two exploited ombrotrophic peat bogs (Puścizna Mała and Puścizna Krauszowska) from Southern Poland. The most disturbed parts of the cores, distinguished using bulk density and age-depth models (22-45 cm in PM and 22-46 cm in PK), were excluded from the interpretation. The two studied cores record ca. 2000 years of variations in lead accumulation rates and isotopic compositions. In the lowest part of the cores (2nd to 4th century AD for Puścizna Mała and 2nd century BC to 2nd century AD for Puścizna Krauszowska), the 206Pb/207Pb ratios (1.188) are consistent with natural supplies from the erosion of the nearby Tatra Mountains. From the 9th to the 19th century AD, 206Pb/207Pb ratios (1.176-1.179) are similar to the signatures obtained from Polish galena ores. The highest Pb accumulation rates are found around 1950 AD and reflect the primary influence of bituminous coal combustion together with the secondary influence of leaded gasoline. This result agrees with the occurrence and abundance of spheroidal aluminosilicates, an unambiguous marker of human industrial activity and coal burning as well as with the acceleration of Zn, Cd and Fe accumulation rate. Our results provide evidence that similar geochemical patterns exist in both analysed cores despite differences in the history of peatland exploitation. Therefore, given that extra care is taken to identify the disturbed peat layers, exploited peatlands can be used to record past changes in lead isotopic signature during the Anthropocene.

Changes in the lead isotopic composition of blood, diet and air in Australia over a decade: Globalization and implications for future isotopic studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulson, Brian; Mizon, Karen; Korsch, Michael

2006-01-15

Source apportionment in biological or environmental samples using the lead isotope method, where there are diverse sources of lead, relies on a significant difference between the isotopic composition in the target media and the sources. Because of the unique isotopic composition of Australian lead, source apportionment has been relatively successful in the past. Over the period of a decade, the {sup 206}Pb/{sup 204}Pb ratio for Australian (mainly female) adults has shown an increase from a geometric mean of 16.8-17.3. Associated with this increase, there has been a decrease in mean blood lead concentration from 4.7 to 2.3 {mu}g/dL, or aboutmore » 5% per year, similar to that observed in other countries. Lead in air, which up until 2000 was derived largely from the continued use of leaded gasoline, showed an overall increase in the {sup 206}Pb/{sup 204}Pb ratio during 1993-2000 from 16.5 to 17.2. Since 1998 the levels of lead in air were less than 0.2 {mu}g/m{sup 3} and would contribute negligibly to blood lead. Over the 10-year period, the {sup 206}Pb/{sup 204}Pb ratio in diet, based mainly on quarterly 6-day duplicate diets, increased from 16.9 to 18.3. The lead concentration in diet showed a small decrease from 8.7 to 6.4 {mu}g Pb/kg although the daily intake increased markedly from 7.4 to 13.9 {mu}g Pb/day during the latter part of the decade probably reflecting differences in demographics. The changes in blood lead from sources such as lead in bone or soil or dust is not dominant because of the low {sup 206}Pb/{sup 204}Pb ratios in these media. Unless there are other sources not identified and analysed for these adults, it would appear that in spite of our earlier conclusions to the contrary, diet does make an overall contribution to blood lead, and this is certainly the case for specific individuals. Certain population groups from south Asia, south-east Asia, the Middle East and Europe (e.g. UK) are unsuitable for some studies as their isotopic ratios in

Surface chemical studies on selective separation of pyrite and galena in the presence of bacterial cells and metabolic products of Paenibacillus polymyxa.

PubMed

Patra, Partha; Natarajan, K A

2006-06-15

Selective separation of pyrite and galena from mixture of the two minerals was achieved through interaction with cells and metabolic products from a culture of Paenibacillus polymyxa. Adsorption of cells and metabolic products onto minerals and electrokinetic studies of minerals after interaction with cells and metabolic products were carried out to examine the resulting surface modification on the mineral surfaces. Flocculation and flotation techniques were successfully applied in the selective separation of minerals after bacterial interaction. The effect of varying conditions for production of extracellular polysaccharides and protein provided an insight into the possible mechanism involved in microbially induced flocculation and flotation of pyrite and galena.

The Sampling and Analysis Plan, Galena Airport and Kalakaket Creek Radio Relay Station, Alaska. Addendum

DTIC Science & Technology

1994-09-08

information deactivated during 1993. Currently, approximately 30 required in a QAPP per the U.S. Environmental caretakers are present at the facility...the total analytical cost. A subset of those Galena Airport-The current environmental samples collected and screened will be sent to an investigative...sampling report United States Environmental Protection Agency (US preparation. EPA), USAF, state, and local requirements. Ms. Sandy Smith is

Geology, hydrology, and results of tracer testing in the Galena-Platteville aquifer at a waste-disposal site near Byron, Illinois

USGS Publications Warehouse

Kay, Robert T.; Yeskis, Douglas J.; Prinos, Scott T.; Morrow, William S.; Vendl, Mark

1999-01-01

A study was conducted by the U.S. Geological Survey and the U.S. Environmental Protection Agency of the geohydrology of the dolomite bedrock at a waste-disposal site near Byron, Illinois. The study was designed to identify and characterize the flow pathways through the bedrock aquifer beneath the site. The geologic units of concern at the site are the Glenwood Formation of the Ancell Group, and the Platteville and Galena Groups. These deposits compose the Galena-Platteville aquifer and the underlying Harmony Hill Shale semiconfining unit. The Galena-Platteville aquifer is an unconfined aquifer. Geophysical logging, water levels, and aquifer-test data indicate the presence of interconnected, hydraulically active fractures in the middle of the Galena-Platteville aquifer (the upper flow pathway), and a second set of hydraulically active fractures (the lower flow pathway). The lower flow pathway may be present through much of the site. Few hydraulically active fractures are present in the upper part of the aquifer near the center of the site, but appear to be more numerous in the upper part of the aquifer in the western and northeastern parts of the site. Water-level data obtained during the tracer test indicate that pumping effects were present near the pumped wells. Pumping effects may have been present at several wells located along directions of identified fracture orientation from the pumped well. The upper part of the aquifer did not appear to be hydraulically well connected to the flow pathways supplying water to the pumped well. Large background changes in water levels obscured the effects of pumping and prevented calculation of aquifer properties. The velocity of the bromide tracer through the lower flow pathway under the hydraulic gradient resulting from the pumping was about 152 feet per day. Solution of the Darcy velocity equation results in a calculated effective porosity for this interval of 3.5 percent, indicating hydraulic interconnection between the

Oceanic Pb-isotopic sources of proterozoic and paleozoic volcanogenic massive sulfide deposits on Prince of Wales Island and vicinity, southeastern Alaska

USGS Publications Warehouse

Ayuso, Robert A.; Karl, Susan M.; Slack, John F.; Haeussler, Peter J.; Bittenbender, Peter E.; Wandless, Gregory A.; Colvin, Anna

2005-01-01

Volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity in southeastern Alaska are associated with Late Proterozoic through Cambrian volcanosedimentary rocks of the Wales Group and with Ordovician through Early Silurian felsic volcanic rocks of the Moira Sound unit (new informal name). The massive sulfide deposits in the Wales Group include the Big Harbor, Copper City, Corbin, Keete Inlet, Khayyam, Ruby Tuesday, and Stumble-On deposits, and those in the Moira Sound unit include the Barrier Islands, Moira Copper, Niblack, and Nichols Bay deposits. Pb-isotopic signatures were determined on sulfide minerals (galena, pyrite, chalcopyrite, pyrrhotite, and sphalerite) to constrain metal sources of the massive sulfides and for comparison with data for other deposits in the region. Except for the Ruby Tuesday deposit, galena is relatively rare in most of these deposits. Pb-isotopic signatures distinguish the mainly Cu+Zn±Ag±Au massive sulfide deposits in the Wales Group from the Zn+Cu±Ag±Au massive sulfide deposits in the Moira Sound unit. Among the older group of deposits, the Khayyam deposit has the widest variation in Pb-isotopic ratios (206Pb/204Pb=17.169–18.021, 207Pb/204Pb=15.341–15.499, 208Pb/204Pb=36.546–37.817); data for the other massive sulfide deposits in the Wales Group overlap the isotopic variations in the Khayyam deposit. Pb-isotopic ratios for both groups of deposits are lower than those on the average crustal Pbevolution curve (µ=9.74), attesting to a large mantle influence in the Pb source. All the deposits show no evidence for Pb evolution primarily in the upper or lower continental crust. Samples from the younger group of deposits have scattered Pb-isotopic compositions and plot as a broad band on uranogenic and thorogenic Pb diagrams. Data for these deposits overlap the trend for massive sulfide deposits in the Wales Group but extend to significantly more radiogenic Pb-isotopic values. Pb-isotopic ratios of

Lead-isotopic data from sulfide minerals from the Cascade Range, Oregon and Washington

USGS Publications Warehouse

Church, S.E.; LeHuray, A.P.; Grant, A.R.; Delevaux, M.H.; Gray, J.E.

1986-01-01

Lead-isotopic studies of mineral deposits associated with Tertiary plutons found in the Cascade Range of Oregon and Washington demonstrate a rather uniform isotopic composition in various sulfide minerals ( 206Pb 204Pb = 18.84 to 19.05; 207Pb 204Pb = 15.57 to 15.62; 208Pb 204Pb = 38.49 to 38.74), show less variation than data from the volcanic rocks of the Cascade Range and fall within the mixing array defined by the MORB regression line and continental sediments. An evaluation of the role of crustal assimilation by hydrothermal convection during emplacement was made on five sulfide deposits associated with a single composite batholith, the Cloudy Pass pluton. The Pb-isotopic data and mass balance calculations suggest that only minor amounts of the lead were derived from the overlying Precambrian (?) Swakane Biotite Gneiss during emplacement. The bulk of the metal that occurs in sulfide deposits in the Cascade mineral belt appears to have been derived from subducted continental detritus. The variation of the Pb-isotopic signature of Sulfides from specific districts or deposits suggests that there is a correlation with age and structure of the crust. 206Pb 204Pb is greater than 18.92 in northern Washington and southern Oregon where deposits have intruded Mesozoic or older crust. However, the ore deposits between the northern Oregon border and central Oregon, south of Eugene, have intruded younger crust composed largely of mafic and andesitic volcanic rocks and 206Pb 204Pb lies between 18.84 and 18.92. This region, previously called the Columbia embayment, appears to be underlain by Tertiary volcanic rocks. Lead-isotopic data may be used to define the boundaries between discontinuous blocks of Mesozoic crust and Tertiary volcanic cover. ?? 1986.

Altitude, depth, and thickness of the Galena-Platteville Bedrock Unit in the subcrop area of Illinois and Wisconsin

USGS Publications Warehouse

Brown, Timothy A.; Dunning, Charles P.; Sharpe, Jennifer B.

2000-01-01

The report series will enable investigators involved in site-specific studies within the subcrop area to understand the regional geologic framework of the unit and to find additional reference sources. This report consists of four sheets that show the altitude (sheet 1), depth from land surface (sheet 2), total thickness (sheet 3), and location of altitude data (sheet 4) of the lithologic units that constitute the Galena-Platteville bedrock unit within the subcrop area. The sheets also show major known geologic features within the Galena-Platteville study area in Illinois and Wisconsin. A geographic information system (GIS) was used to generate data layers (coverages) from point data and from published and unpublished contour maps at various scales and detail. Standard GIS procedures were used to change the coverages into the maps shown on the sheets presented in this report. A list of references for the data used to prepare the maps is provided. 

Geochemical Peculiarities of Galena and Sphalerite from Polymetallic Deposits of the Dal'negorskii Ore Region (Primorsky Krai, Russia)

NASA Astrophysics Data System (ADS)

Rogulina, L. I.; Moiseenko, V. G.; Ponomarchuk, V. A.

2018-04-01

New data on the composition of the major minerals from the skarn and vein polymetallic deposits of the Dal'negorskii ore region are reported. Analysis of galena and sphalerite was carried out by the X-ray fluorescent energy-dispersive method of synchrotron radiation for the first time. It is shown that the minor elements in major minerals of different deposits are typomorphic. Among these elements are Fe, Cu, Ni, Cd, Ag, Sn, and Sb, as well as In in sphalerite and Te in galena. The high concentrations of Ag, Cu, Te, Cd, and In in the extracted minerals indicate the complex character of mineralization. The compositional patterns of ore minerals characterize the sequence of mineral formation from the skarn to vein ores, and the sequence of deposits from the mesothermal to epithermal conditions. This provides geochemical evidence for the stage model of the formation of mineralization in the Dal'negorskii ore region.

Characteristics of lead isotope ratios and elemental concentrations in PM 10 fraction of airborne particulate matter in Shanghai after the phase-out of leaded gasoline

NASA Astrophysics Data System (ADS)

Zheng, Jian; Tan, Mingguang; Shibata, Yasuyuki; Tanaka, Atsushi; Li, Yan; Zhang, Guilin; Zhang, Yuanmao; Shan, Zuci

The stable lead (Pb) isotope ratios and the concentrations of 23 elements, including heavy metals and toxic elements, were measured in the PM 10 airborne particle samples collected at seven monitoring sites in Shanghai, China, to evaluate the current elemental compositions and local airborne Pb isotope ratio characteristics. Some source-related samples, such as cement, coal and oil combustion dust, metallurgic dust, vehicle exhaust particles derived from leaded gasoline and unleaded gasoline, and polluted soils were analyzed for their Pb content and isotope ratio and compared to those observed in PM 10 samples. Airborne Pb concentration ranged from 167 to 854 ng/m 3 in the seven monitored sites with an average of 515 ng/m 3 in Shanghai, indicating that a high concentration of Pb remains in the air after the phasing out of leaded gasoline. Lead isotopic compositions in airborne particles ( 207Pb/ 206Pb, 0.8608±0.0018; 208Pb/ 206Pb, 2.105±0.005) are clearly distinct from the vehicle exhaust particles ( 207Pb/ 206Pb, 0.8854±0.0075; 208Pb/ 206Pb, 2.145±0.006), suggesting that the automotive lead is not currently the major component of Pb in the air. By using a binary mixing equation, a source apportionment based on 207Pb/ 206Pb ratios, indicates that the contribution from automotive emission to the airborne Pb is around 20%. The Pb isotope ratios obtained in the source-related samples confirmed that the major emission sources are metallurgic dust, coal combustion, and cement.

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

PubMed

Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

2014-02-01

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

Hydrologic Effects of the 1988 Galena Fire, Black Hills Area, South Dakota

USGS Publications Warehouse

Driscoll, Daniel G.; Carter, Janet M.; Ohlen, Donald O.

2004-01-01

The Galena Fire burned about 16,788 acres of primarily ponderosa pine forest during July 5-8, 1988, in the Black Hills area of South Dakota. The fire burned primarily within the Grace Coolidge Creek drainage basin and almost entirely within the boundaries of Custer State Park. A U.S. Geological Survey gaging station with streamflow records dating back to 1977 was located along Grace Coolidge Creek within the burned area. About one-half of the gaging station's 26.8-square-mile drainage area was burned. The drainage basin for Bear Gulch, which is tributary to Grace Coolidge Creek, was burned particularly severely, with complete deforestation occurring in nearly the entirety of the area upstream from a gaging station that was installed in 1989. A study to evaluate effects of the Galena Fire on streamflow, geomorphology, and water quality was initiated in 1988. The geomorphologic and water-quality components of the study were completed by 1990 and are summarized in this report. A data-collection network consisting of streamflow- and precipitation-gaging stations was operated through water year 1998 for evaluation of effects on streamflow characteristics, including both annual-yield and peak-flow characteristics, which are the main focus of this report. Moderately burned areas did not experience a substantial increase in the rate of surface erosion; however, severely burned areas underwent surficial erosion nearly twice that of the unburned areas. The sediment production rate of Bear Gulch estimated 8 to 14 months after the fire was 870 ft3/acre (44 tons/acre). Substantial degradation of stream channels within the severely burned headwater areas of Bear Gulch was documented. Farther downstream, channel aggradation resulted from deposition of sediments transported from the headwater areas. The most notable water-quality effect was on concentrations of suspended sediment, which were orders of magnitude higher for Bear Gulch than for the unburned control area. Effects on

A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

NASA Astrophysics Data System (ADS)

Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

2016-08-01

evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one

Lead isotope ratios for bullets, forensic evaluation in a Bayesian paradigm.

PubMed

Sjåstad, Knut-Endre; Lucy, David; Andersen, Tom

2016-01-01

Forensic science is a discipline concerned with collection, examination and evaluation of physical evidence related to criminal cases. The results from the activities of the forensic scientist may ultimately be presented to the court in such a way that the triers of fact understand the implications of the data. Forensic science has been, and still is, driven by development of new technology, and in the last two decades evaluation of evidence based on logical reasoning and Bayesian statistic has reached some level of general acceptance within the forensic community. Tracing of lead fragments of unknown origin to a given source of ammunition is a task that might be of interest for the Court. Use of data from lead isotope ratios analysis interpreted within a Bayesian framework has shown to be suitable method to guide the Court to draw their conclusion for such task. In this work we have used isotopic composition of lead from small arms projectiles (cal. .22) and developed an approach based on Bayesian statistics and likelihood ratio calculation. The likelihood ratio is a single quantity that provides a measure of the value of evidence that can be used in the deliberation of the court. Copyright © 2015 Elsevier B.V. All rights reserved.

Lead Isotopes and Temporal Records of Atmospheric Aerosol and Pollutants in Lichens

NASA Astrophysics Data System (ADS)

Getty, S. R.; Nash, T.; Asmerom, Y.

2001-05-01

Lichens are useful receptors of atmospheric particulate matter (PM) and pollutants due to their retention of body parts (unlike plants), slow growth rates, fairly uniform morphologies, lack of a vascular system, and sessile character over decades to centuries. Lichen biomonitoring has been used widely to map patterns of aerosol deposition, yet few studies have tested whether lichens can preserve a temporal record of airborne PM and pollutants. We show with U-Pb data that epilithic lichens (rock as host) can retain in their porous structure an integrated, decadal-scale history of changing aerosol inputs to desert ecosystems. Three lichens resided along an 80-km transect from a copper smelter (Douglas, AZ) closed in early 1987, to the ENE into adjacent New Mexico. For the radially growing lichen (Xanthoparmelia sp.), U-Pb data were obtained along cm-scale transects in the growth direction on a single thallus. Profiles from lichen rim to interior show increasing [Pb] and [U], or net accumulation with thallus age. Total lead contents are highest near the smelter. In contrast, each lead isotope profile (206Pb/207Pb) is flat during smelter operation, showing low ratios near the smelter (1.152) and high ratios (1.175) 80 km away. This suggests comparable mixtures of crust and smelter lead per locality over decades. Since smelter closure, lichens 80 km from the smelter show a sharp upturn in lead ratio in the recently grown lichen rim, indicating that smelter lead is either dispersed by aeolian recycling, or suppressed in desert soils. The amplitude and position of the isotope signal suggests a soil recovery "half-life" of about 13 yrs, a radial growth rate of 0.57+/-0.1 mm/yr, and a total lichen age of 105+/-18 yrs. Lichens near the smelter have no upturn in isotope ratio, indicating continued aeolian recylcing of lead from soils about 11 yrs after closure. Results at a far-removed desert site (c. New Mexico) also argue that isotope profiles reflect aerosol deposition

Geology, S-Pb isotopes, and 40Ar/39Ar geochronology of the Zhaxikang Sb-Pb-Zn-Ag deposit in Southern Tibet: implications for multiple mineralization events at Zhaxikang

NASA Astrophysics Data System (ADS)

Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang

2018-03-01

Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that

Tracing geogenic and anthropogenic sources in urban dusts: Insights from lead isotopes

NASA Astrophysics Data System (ADS)

Del Rio-Salas, R.; Ruiz, J.; De la O-Villanueva, M.; Valencia-Moreno, M.; Moreno-Rodríguez, V.; Gómez-Alvarez, A.; Grijalva, T.; Mendivil, H.; Paz-Moreno, F.; Meza-Figueroa, D.

2012-12-01

Tracing the source of metals in the environment is critical to understanding their pollution level and fate. Geologic materials are an important source of airborne particulate matter, but the contribution of contaminated soil to concentrations of Pb in airborne dust is not yet widely documented. To examine the potential significance of this mechanism, surface soil samples were collected, as well as wind-transported dust trapped at 1 and 2 m height at seven different locations including residential, industrial, high-traffic and rural sites. Samples of dust deposited on roofs from 24 schools were also obtained and analyzed for Pb isotope ratios. Spatial distribution of Pb of airborne and sedimented dust suggests a process dominated by re-suspension/sedimentation, which was controlled by erosion, traffic and topography of the urban area. Anthropogenic lead input in the city grades outward the urban zone toward geogenic values. Our results shows that Pb-isotopic signatures of leaded gasoline are imprinted in dust sedimented on roofs. Considering that leaded-gasoline has not been in use in Mexico since two decades ago, this signature shows not only a Pb-legacy in soil, but also a re-suspension process affecting air column below 3 m in height. The combination of the 207Pb/206Pb data of the surrounding rocks and urban dust, reveal three well-defined zones with remarkable anthropogenic influence, which correspond to the oldest urban sectors. This work highlights the importance of spatial characterization of metals in particles suspended below a height of 3 m of the airborne column, a fact that should be considered to identify exposure paths to humans and the potential risks. Lead isotope signatures allowed the identification of geogenic and anthropogenic emission sources for dust, a matter that deserves consideration in the efforts to control airborne metal emissions.

Lead-isotopic evidence for distinct source of granite and for distinct basement in the northern Appalachians, Maine.

USGS Publications Warehouse

Ayuso, R.A.

1986-01-01

Lead-isotopic compositions of feldspars in high-level Devonian granitic plutons across the northern Appalachians were measured. The presence of three fundamentally different sources of granites was indicated by three distinct lead-isotope groups. Plutons in the coastal lithotectonic block are the most radiogenic (206Pb/204Pb) 18.25-19.25; 207Pb/204Pb 15.59-15.67; 208Pb/204Pb 38.00-38.60); plutons in northern Maine are the least radiogenic (206Pb/204Pb 18.00-18.50; 207Pb/204Pb 15.51-15.55; 208Pb/204Pb 37.80-38.38). Intermediate lead-isotope values characterize the plutons in central Maine. All plutons show relatively radiogenic lead values for their ages and suggest the imprint of continental crustal sources, particularly in the coastal block. These plutons were formed in different crustal fragments in a continental environment, that were juxtaposed after emplacement of the granites.-L.C.H.

Lead isotope relations in oceanic Ridge basalts from the Juan de Fuca-Gorda Ridge area N.E. Pacific Ocean

USGS Publications Warehouse

Church, S.E.; Tatsumoto, M.

1975-01-01

Lead isotopic analyses of a suite of basaltic rocks from the Juan de Fuca-Gorda Ridge and nearby seamounts confirm an isotopically heterogeneous mantle known since 1966. The process of mixing during partial melting of a heterogeneous mantle necessarily produces linear data arrays that can be interpreted as secondary isochrons. Moreover, the position of the entire lead isotope array, with respect to the geochron, requires that U/Pb and Th/Pb values are progressively increased over the age of the earth. Partial melting theory also dictates analogous behavior for the other incompatible trace elements. This process explains not only the LIL element character of MOR basalts, but also duplicates the spread of radiogenic lead data collected from alkali-rich oceanic basalts. This dynamic, open-system model of lead isotopic and chemical evolution of the mantle is believed to be the direct result of tectonic flow and convective overturn within the mantle and is compatible with geophysical models of a dynamic earth. ?? 1975 Springer-Verlag.

A modified lead-matrix separation procedure shown for lead isotope analysis in Trojan silver artefacts as an example.

PubMed

Vogl, Jochen; Paz, Boaz; Koenig, Maren; Pritzkow, Wolfgang

2013-03-01

A modified Pb-matrix separation procedure using NH4HCO3 solution as eluent has been developed and validated for determination of Pb isotope amount ratios by thermal ionization mass spectrometry. The procedure is based on chromatographic separation using the Pb·Spec resin and an in-house-prepared NH4HCO3 solution serving as eluent. The advantages of this eluent are low Pb blanks (<40 pg mL(-1)) and the property that NH4HCO3 can be easily removed by use of a heating step (>60 °C). Pb recovery is >95 % for water samples. For archaeological silver samples, however, the Pb recovery is reduced to approximately 50 %, but causes no bias in the determination of Pb isotope amount ratios. The validated procedure was used to determine lead isotope amount ratios in Trojan silver artefacts with expanded uncertainties (k = 2) <0.09 %.

Lead isotope ratios for bullets, a descriptive approach for investigative purposes and a new method for sampling of bullet lead.

PubMed

Sjåstad, Knut-Endre; Simonsen, Siri Lene; Andersen, Tom H

2014-11-01

To establish a link between a bullet fired from a suspected firearm, investigation of striation marks are one of the corner stones in the forensic laboratory. Nevertheless, on some occasions, the bullet may be deformed to such extent that traditional investigation of striation marks will be impossible. Fragments of lead can be investigated by lead isotope ratio determination in order to distinguish between bullets with different origin. This approach initially seems reasonable, since the abundance of lead isotopes varies significantly in nature. To make a method valid for forensic purposes, it is important to have a fundamental understanding of the variation within a box of lead bullets and the expected variation between boxes. Studies of variability within and between boxes of ammunition are imperative to perform any type of forensic interpretation, both in an investigative and evaluative context. This work presents an extensive study of variability within and between boxes of ammunition by use of multicollector inductive coupled mass spectrometry. As a first approximation to classify bullets to any given source, a simple and robust graphical method is presented. In addition, an easy-to-use sampling procedure of lead is presented. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

An update of the Pb isotope inventory in post leaded-petrol Singapore environments.

PubMed

Carrasco, Gonzalo; Chen, Mengli; Boyle, Edward A; Tanzil, Jani; Zhou, Kuanbo; Goodkin, Nathalie F

2018-02-01

Pb is a trace metal that tracks anthropogenic pollution in natural environments. Despite recent leaded petrol phase out around Southeast Asia, the region's growth has resulted in continued exposure of Pb from a variety of sources. In this study, sources of Pb into Singapore, a highly urbanised city-state situated in the central axis of Southeast Asia, are investigated using isotopic ratios and concentrations. We compiled data from our previous analyses of aerosols, incineration fly ash and sediments, with new data from analyses of soil from gas stations, water from runoff and round-island coastal seawater to obtain a spatio-temporal overview of sources of Pb into the Singapore environment. Using 206 Pb/ 207 Pb ratio, we identified three main Pb source origins: natural Pb (1.215 ± 0.001), historic/remnant leaded petrol (1.123 ± 0.013), and present-day industrial and incinerated waste (1.148 ± 0.005). Deep reservoir sediments bore larger traces of Pb from leaded petrol, but present-day runoff waters and coastal seawater were a mix of industrial and natural sources with somewhat variable concentrations. We found temporal variability in Pb isotopic ratio in aerosols indicating alternating transboundary Pb sources to Singapore that correspond to seasonal changes in monsoon winds. By contrast, seasonal monsoon circulation did not significantly influence isotopic ratios of coastal seawater Pb. Instead, seawater Pb was driven more by location differences, suggesting stronger local-scale drivers of Pb such as point sources, water flushing, and isotope exchange. The combination of multiple historic and current sources of Pb shown in this study highlights the need for continued monitoring of Pb in Southeast Asia, especially in light of emerging industries and potential large sources of Pb such as coal combustion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Constraining recent lead pollution sources in the North Pacific using ice core stable lead isotopes

NASA Astrophysics Data System (ADS)

Kreutz, K. J.; Osterberg, E. C.; Gross, B.; Handley, M.; Wake, C. P.; Yalcin, K.

2009-12-01

Trends and sources of lead aerosol pollution in the North Pacific boundary layer from 1970-2001 are investigated using a high-resolution ice core record recovered from Eclipse Icefield (3017 masl; St. Elias Mountains, Canada). Average Pb concentrations in the ice core are enriched 31.8 times above crustal values based on ratios with five crustal reference elements (La, Ce, Pr, Al and Ti), indicating that >90% of the Pb deposited is anthropogenic. Isotopic analyses (208Pb/207Pb and 206Pb/207Pb) confirm that the Pb deposited at Eclipse Icefield is predominantly anthropogenic. Annually averaged Pb concentrations range from 25.6 ng/l to 96.7 ng/l (67.6 ng/l mean) and show no long term trend for the 1970-2001 period, contrary to other ice core records from the North Atlantic and the North Pacific. The stable Pb isotope ratio (208Pb/207Pb and 206Pb/207Pb) field indicates that recent Eclipse Icefield Pb pollution represents a variable mixture of North American, Central Eurasian and Asian (Chinese and Japanese) emissions transported across the Pacific basin, with Chinese coal combustion likely being the primary source. Increasing 208Pb/207Pb and 206Pb/207Pb ratios from the 1970’s through 2001 reflect the progressive East Asian industrialization concurrent with a decrease in Eurasian Pb emissions. We compare Pb isotope results from the Eclipse Icefield to data recently acquired from Denali National Park, where snowpit samples were collected from the Kahiltna Pass region (3048 masl). Pb isotope data from both sites are used to evaluate the relative importance of Asian emissions at similar altitudes yet different latitudes.

Use of Lead Isotopes to Identify Sources of Metal and Metalloid Contaminants in Atmospheric Aerosol from Mining Operations

PubMed Central

Félix, Omar I.; Csavina, Janae; Field, Jason; Rine, Kyle P.; Sáez, A. Eduardo; Betterton, Eric A.

2014-01-01

Mining operations are a potential source of metal and metalloid contamination by atmospheric particulate generated from smelting activities, as well as from erosion of mine tailings. In this work, we show how lead isotopes can be used for source apportionment of metal and metalloid contaminants from the site of an active copper mine. Analysis of atmospheric aerosol shows two distinct isotopic signatures: one prevalent in fine particles (< 1 μm aerodynamic diameter) while the other corresponds to coarse particles as well as particles in all size ranges from a nearby urban environment. The lead isotopic ratios found in the fine particles are equal to those of the mine that provides the ore to the smelter. Topsoil samples at the mining site show concentrations of Pb and As decreasing with distance from the smelter. Isotopic ratios for the sample closest to the smelter (650 m) and from topsoil at all sample locations, extending to more than 1 km from the smelter, were similar to those found in fine particles in atmospheric dust. The results validate the use of lead isotope signatures for source apportionment of metal and metalloid contaminants transported by atmospheric particulate. PMID:25496740

Metals and metalloids in atmospheric dust: Use of lead isotopic analysis for source apportionment

NASA Astrophysics Data System (ADS)

Felix Villar, Omar I.

Mining activities generate aerosol in a wide range of sizes. Smelting activities produce mainly fine particles (<1 microm). On the other hand, milling, crushing and refining processes, as well tailings management, are significant sources of coarse particles (> 1 microm). The adverse effects of aerosols on human health depend mainly on two key characteristics: size and chemical composition. One of the main objectives of this research is to analyze the size distribution of contaminants in aerosol produced by mining operations. For this purpose, a Micro-Orifice Uniform Deposit Impactor (MOUDI) was utilized. Results from the MOUDI samples show higher concentrations of the toxic elements like lead and arsenic in the fine fraction (<1 microm). Fine particles are more likely to be deposited in the deeper zones of the respiratory system; therefore, they are more dangerous than coarse particles that can be filtered out in the upper respiratory system. Unfortunately, knowing the total concentration of contaminants does not give us enough information to identify the source of contamination. For this reason, lead isotopes have been introduced as fingerprints for source apportionment. Each source of lead has specific isotopic ratios; by knowing these ratios sources can be identified. During this research, lead isotopic ratios were analyzed at different sites and for different aerosol sizes. From these analyses it can be concluded that lead isotopes are a powerful tool to identify sources of lead. Mitigation strategies could be developed if the source of contamination is well defined. Environmental conditions as wind speed, wind direction, relative humidity and precipitation have an important role in the concentration of atmospheric dust. Dry environments with low relative humidity are ideal for the transport of aerosols. Results obtained from this research show the relationship between dust concentrations and meteorological parameters. Dust concentrations are highly correlated

Sulfur and oxygen isotopic study of Paleozoic sediment-hosted Zn-Pb(-Ag-Au-Ba-F) deposits and associated hydrothermal alteration zones in the Nome Complex, Seward Peninsula, Alaska

USGS Publications Warehouse

Shanks, W.C. Pat; Slack, John F.; Till, Alison B.; Thurston, Roland; Gemery-Hill, Pamela

2014-01-01

The stratabound Nelson deposit, and the deformed veins at the Galena and Quarry deposits, may be older than the Aurora Creek-Christophosen and Wheeler North deposits. The Nelson deposit has a lower and narrower range of δ34S values (1.9 to 10.4‰), averaging about 8‰. The Galena and Quarry veins display δ34S values that are similar to those of the stratabound Nelson deposit. Barite samples from the Aurora Creek-Christophosen, Wheeler North, and Quarry deposits have 34S-enriched δ34S values between 25 and 30‰ that are consistent with derivation of the sulfur from coeval (Paleozoic) seawater sulfate. Given their δ34S values, it is likely that the Aurora Creek-Christophosen and Wheeler North deposits formed in closed sub-basins with euxinic conditions that led to extreme Rayleigh distillation to produce the very large range and very high δ34S values. The Nelson deposit probably formed within an anoxic but not euxinic sub-basin. At Nelson, sulfide was likely derived by a subsurface thermochemical sulfate reduction (TSR) reaction, similar to reactions that are inferred to have produced the sulfides in the Galena and Quarry deposits, which are interpreted as feeder veins for the stratabound deposits. Calculations of oxygen isotope temperatures are based on the assumption that evolved seawater with δ18O of 3‰ was the mineralizing and altering fluid related to the formation of the sulfide deposits. Temperatures of aluminous alteration and sulfide mineralization were between 109 and 209 °C, determined on the basis of oxygen isotope fractionations between the mineralizing fluid and proportionate amounts of quartz and muscovite in the rocks. These temperature estimates agree well with known temperatures of SEDEX mineralization worldwide. Sulfur isotope values also are generally consistent with the known ranges in SEDEX deposits worldwide (δ34S ≈ -5 to 25‰).

Isotopic generator for bismuth-212 and lead-212 from radium

DOEpatents

Atcher, Robert W.; Friedman, Arnold M.; Hines, John

1987-01-01

A method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal'negorsk Ore Region (Primorye)

NASA Astrophysics Data System (ADS)

Rogulina, L. I.; Moiseenko, V. G.; Odarichenko, E. G.; Voropayeva, E. N.

2018-03-01

The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag-Pb-Zn deposits of the region. It was pointed out that the δ34S modal values range from-1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ34S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.

Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits

PubMed Central

Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

2016-01-01

Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538

Lead concentration and isotope chronology in two coastal environments in Western and South East Asia

NASA Astrophysics Data System (ADS)

Carrasco, G. G.; Chen, M.; Boyle, E. A.; Zhao, N.; Nurhati, I. S.; Gevao, B.; al Ghadban, A.; Switzer, A.; Lee, J. M.

2014-12-01

Lead is a trace metal that is closely related to anthropogenic activity, mainly via leaded gasoline and coal combustion. The study of lead concentrations and isotopes in seawater, sediments, corals and aerosols allows for a systematic look at its sources and their time evolution in a natural environment. We will discuss results from two projects in Western and South East Asia, regions that have seen dramatic socio-economical changes over the past half-century that may have left environmental signals. These results highlight the usefulness of the method, indicate the degree of complexity of these systems, and point to the need for a continuous monitoring of anthropogenic trace metals in the small-medium coastal scale to be able to asses the larger scale effects of human activity. On the one hand, coastal Kuwait is heavily influenced by the Shat al-Arab river and shows a clear anthropogenic signature from Kuwait city. A mix of two sources can be tracked through the coral and sediment chronological records, with Pb206/Pb207 ratios (1.202 and 1.151) that approach the suspected source values (1.21 and 1.12) and eliminate the possibility of other sources. Through a wide sediment geographic distribution, the strength of the anthropogenic signature is modulated. On the other hand, Singapore offers a more complex system, where an apparent mix of two sources (extreme isotope ratios 1.215 and ~1.14) occurs also, but where either an unresolved potentially important third source (isotope ratio ~1.18), or an isotope exchange process should be invoked. The sediment and coral records allows us to track the changes through time; however, there seems to be incongruence with the aerosol isotope record. Further potential sources are being explored currently and will be discussed.

Isotope-ratio measurements of lead in NIST standard reference materials by multiple-collector inductively coupled plasma mass spectrometry.

PubMed

Platzner, I; Ehrlich, S; Halicz, L

2001-07-01

The capability of a second-generation Nu Instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been evaluated for precise and accurate isotope-ratio determinations of lead. Essentially the mass spectrometer is a double-focusing instrument of Nier-Johnson analyzer geometry equipped with a newly designed variable-dispersion ion optical device, enabling the measured ion beams to be focused into a fixed array of Faraday collectors and an ion-counting assembly. NIST SRM Pb 981, 982, and 983 isotopic standards were used. Addition of thallium to the lead standards and subsequent simultaneous measurement of the thallium and lead isotopes enabled correction for mass discrimination, by use of the exponential correction law and 205Tl/203Tl = 2.3875. Six measurements of SRM Pb-982 furnished the results 206Pb/204Pb = 36.7326(68), 207Pb/204Pb = 17.1543(30), 208Pb/204Pb = 36.7249(69), 207Pb/206Pb = 0.46700(1), and 208Pb/206Pb = 0.99979(2); the NIST-certified values were 36.738(37), 17.159(25), 36.744(50), 0.46707(20), and 1.00016(36), respectively. Direct isotope lead analysis in silicates can be performed without any chemical separation. NIST SRM 610 glass was dissolved and introduced into the MC-ICP-MS by means of a micro concentric nebulizer. The ratios observed were in excellent agreement with previously reported data obtained by TIMS and laser ablation MC-ICP-MS, despite the high Ca/Pb concentration ratio (200/1) and the presence of many other elements at levels comparable with that of lead. Approximately 0.2 microg lead are sufficient for isotope analysis with ratio uncertainties between 240 and 530 ppm.

Lead isotopes reveal bilateral asymmetry and vertical continuity in the Hawaiian mantle plume.

PubMed

Abouchami, W; Hofmann, A W; Galer, S J G; Frey, F A; Eisele, J; Feigenson, M

2005-04-14

The two parallel chains of Hawaiian volcanoes ('Loa' and 'Kea') are known to have statistically different but overlapping radiogenic isotope characteristics. This has been explained by a model of a concentrically zoned mantle plume, where the Kea chain preferentially samples a more peripheral portion of the plume. Using high-precision lead isotope data for both centrally and peripherally located volcanoes, we show here that the two trends have very little compositional overlap and instead reveal bilateral, non-concentric plume zones, probably derived from the plume source in the mantle. On a smaller scale, along the Kea chain, there are isotopic differences between the youngest lavas from the Mauna Kea and Kilauea volcanoes, but the 550-thousand-year-old Mauna Kea lavas are isotopically identical to Kilauea lavas, consistent with Mauna Kea's position relative to the plume, which was then similar to that of present-day Kilauea. We therefore conclude that narrow (less than 50 kilometres wide) compositional streaks, as well as the larger-scale bilateral zonation, are vertically continuous over tens to hundreds of kilometres within the plume.

A lead isotope perspective on urban development in ancient Naples.

PubMed

Delile, Hugo; Keenan-Jones, Duncan; Blichert-Toft, Janne; Goiran, Jean-Philippe; Arnaud-Godet, Florent; Romano, Paola; Albarède, Francis

2016-05-31

The influence of a sophisticated water distribution system on urban development in Roman times is tested against the impact of Vesuvius volcanic activity, in particular the great eruption of AD 79, on all of the ancient cities of the Bay of Naples (Neapolis). Written accounts on urbanization outside of Rome are scarce and the archaeological record sketchy, especially during the tumultuous fifth and sixth centuries AD when Neapolis became the dominant city in the region. Here we show that isotopic ratios of lead measured on a well-dated sedimentary sequence from Neapolis' harbor covering the first six centuries CE have recorded how the AD 79 eruption was followed by a complete overhaul of Neapolis' water supply network. The Pb isotopic signatures of the sediments further reveal that the previously steady growth of Neapolis' water distribution system ceased during the collapse of the fifth century AD, although vital repairs to this critical infrastructure were still carried out in the aftermath of invasions and volcanic eruptions.

A lead isotope perspective on urban development in ancient Naples

PubMed Central

Delile, Hugo; Keenan-Jones, Duncan; Goiran, Jean-Philippe; Arnaud-Godet, Florent; Romano, Paola; Albarède, Francis

2016-01-01

The influence of a sophisticated water distribution system on urban development in Roman times is tested against the impact of Vesuvius volcanic activity, in particular the great eruption of AD 79, on all of the ancient cities of the Bay of Naples (Neapolis). Written accounts on urbanization outside of Rome are scarce and the archaeological record sketchy, especially during the tumultuous fifth and sixth centuries AD when Neapolis became the dominant city in the region. Here we show that isotopic ratios of lead measured on a well-dated sedimentary sequence from Neapolis’ harbor covering the first six centuries CE have recorded how the AD 79 eruption was followed by a complete overhaul of Neapolis’ water supply network. The Pb isotopic signatures of the sediments further reveal that the previously steady growth of Neapolis’ water distribution system ceased during the collapse of the fifth century AD, although vital repairs to this critical infrastructure were still carried out in the aftermath of invasions and volcanic eruptions. PMID:27185923

A new method for stable lead isotope extraction from seawater.

PubMed

Zurbrick, Cheryl M; Gallon, Céline; Flegal, A Russell

2013-10-24

A new technique for stable lead (Pb) isotope extraction from seawater is established using Toyopearl AF-Chelate 650M(®) resin (Tosoh Bioscience LLC). This new method is advantageous because it is semi-automated and relatively fast; in addition it introduces a relatively low blank by minimizing the volume of chemicals used in the extraction. Subsequent analyses by HR ICP-MS have a good relative external precision (2σ) of 3.5‰ for (206)Pb/(207)Pb, while analyses by MC-ICP-MS have a better relative external precision of 0.6‰. However, Pb sample concentrations limit MC-ICP-MS analyses to (206)Pb, (207)Pb, and (208)Pb. The method was validated by processing the common Pb isotope reference material NIST SRM-981 and several GEOTRACES intercalibration samples, followed by analyses by HR ICP-MS, all of which showed good agreement with previously reported values. Copyright © 2013 Elsevier B.V. All rights reserved.

Potential of Opuntia ficus-indica for air pollution biomonitoring: a lead isotopic study.

PubMed

El Hayek, Eliane; El Samrani, Antoine; Lartiges, Bruno; Kazpard, Veronique; Benoit, Mathieu; Munoz, Marguerite

2015-11-01

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.

Reconstruction of historical lead contamination and sources in Lake Hailing, Eastern China: a Pb isotope study.

PubMed

Zhang, Rui; Guan, Minglei; Shu, Yujie; Shen, Liya; Chen, Xixi; Zhang, Fan; Li, Tiegang; Jiang, Tingchen

2016-05-01

The history records of lead and its stable isotopic ratios were determined in a sediment core to receive anthropogenic impacts on the Lake Hailing in eastern China. The sediment core was dated based on (210)Pb, (137)Cs, and (239+240)Pu. The historical changes of Pb/Al and Pb isotope ratios showed increasing trend upward throughout the core, suggesting changes in energy usage and correlating closely with the experience of a rapid economic and industrial development of the catchment, Linyi City, in eastern China. Based on the mixing end member model of Pb isotope ratios, coal combustion emission dominated anthropogenic Pb sources in the half part of the century contributing 13 to 43 % of total Pb in sediment. Moreover, contributions of chemical and organic fertilizer were 1-13 and 5-14 %, respectively. In contrast, the contribution of leaded gasoline was low than 8 %. The results indicated that historical records of Pb contamination predominantly sourced from coal combustion and chemical and organic fertilizer in the catchment. In addition, an increase of coal combustion source and fertilizers was found throughout the sediment core, whereas the contribution of leaded gasoline had declined after 2000s, which is attributed to the phaseout of leaded gasoline in China.

Evidence for Proterozoic and late Cretaceous-early Tertiary ore-forming events in the Coeur d'Alene district, Idaho and Montana

USGS Publications Warehouse

Leach, D.L.; Hofstra, A.H.; Church, S.E.; Snee, L.W.; Vaughn, R.B.; Zartman, R.E.

1998-01-01

New 40Ar/39Ar age spectra on sericite and lead isotope data on tetrahedrite, siderite, galena, bournonite, and stibnite, together with previously published isotopic, geochemical, and geologic studies provide evidence for two major vein-forming events in the Coeur d'Alene district and surrounding area of the Belt basin. The data suggest that the zinc- and lead-rich veins (e.g., Bunker Hill and Star-Morning mines) formed in the Proterozoic (1.0 Ga), whereas the silver-rich veins (e.g., Silver belt mines), antimony veins (e.g., US Antimony mine), and gold-bearing quartz veins (Murry subdistrict) formed in Late Cretaceous to early Tertiary time.

Lead isotope ratios in tree bark pockets: an indicator of past air pollution in the Czech Republic.

PubMed

Conkova, M; Kubiznakova, J

2008-10-15

Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 microg g(-1)) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 microg g(-1)) was found at the Kosetice EMEP "background pollution" site. Changes in (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the (206)Pb/(207)Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the (208)Pb/(206)Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ((206)Pb/(207)Pb of 1.11) lead to lower (206)Pb/(207)Pb in bark pockets over time. High-radiogenic lignite-derived Pb ((206)Pb/(207)Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic.

A lead isotope distribution study in swine tissue using ICP-MS

USGS Publications Warehouse

May, T.W.; Wiedmeyer, Ray H.; Brown, L.D.; Casteel, S.W.

1999-01-01

In the United States lead is an ubiquitous environmental pollutant that is a serious human health hazard, especially for women of childbearing age, developing fetuses, and young children. Information concerning the uptake and distribution of lead to maternal and fetal tissues during pregnancy is poorly documented. A study was designed using domestic swine and lead isotope enrichment methodology to focus on maternal absorption and distribution of lead into bone and soft tissues, including the fetal compartment, under varying conditions of oral lead exposure and during altered physiological states (pregnant vs unbred). Total lead levels and Pb207/Pb206 ratios in bone (femur and vertebra), blood, and soft tissues (liver, kidney, brain) were determined by ICP-MS. Lead in fetal tissues derived from maternal bone could be differentiated from that derived from exogenous dosing. Unbred swine absorbed much less lead than pregnant females receiving the same dose. The accuracy and precision of ICP-MS at the instrumental level and for the entire method (sample collection, digestion, and analysis) were evaluated for both Pb207/Pb206 ratios and total lead. Several changes were suggested in method design to improve both instrumental and total method precision.

Lead isotope systematics of some Apollo 17 soils and some separated components from 76501

NASA Technical Reports Server (NTRS)

Church, S. E.; Tilton, G. R.

1974-01-01

Isotopic lead data from bulk samples of Apollo 17 soils were analyzed, and they define a chord in a concordia diagram, showing the presence of a component or components containing excess radiogenic lead with Pb-207/Pb-206 equal to about 1.32. The chord is distinctly different from the cataclysm chord, for which Pb-207/Pb-206 is approximately 1.45. Nitric acid analysis of plagioclase indicates lead ages of around 4.35 AE, in agreement with previous findings. Agglutinates from soil 76501,34 show loss of approximately 15% of lead.

INTERLABORATORY COMPARISON OF MASS SPECTROMETRIC METHODS FOR LEAD ISOTOPES AND TRACE ELEMENTS IN NIST SRM 1400 BONE ASH

EPA Science Inventory

The results of an interlaboratory comparison are reported for he lead isotope composition and for trace element concentrations in NIST SRM 1400 Bone Ash obtained using quadrupole and magnetic-sector inductively coupled plasma mass spectrometry (ICP-MS) and (for the Pb isotopes on...

External lead contamination of women's nails by surma in Pakistan: Is the biomarker reliable?

PubMed

Ikegami, Akihiko; Takagi, Mai; Fatmi, Zafar; Kobayashi, Yayoi; Ohtsu, Mayumi; Cui, Xiaoyi; Mise, Nathan; Mizuno, Atsuko; Sahito, Ambreen; Khoso, Aneeta; Kayama, Fujio

2016-11-01

Adverse health effects of heavy metals are a public health concern, especially lead may cause negative health impacts to human fetal and infantile development. The lead concentrations in Pakistani pregnant women's nails, used as a biomarker, were measured to estimate the lead exposure. Thirteen nail samples out of 84 nails analyzed contained lead higher than the concentration (13.6 μg/g) of the fatal lead poisoning case, raising the possibility of an external contamination. Eye cosmetics such as surma are recognized as one of the important sources of lead exposure in Pakistan. We collected in Pakistan 30 eye cosmetics made in Pakistan, Saudi Arabia and western countries. As the metal composition analysis by energy dispersive X-ray fluorescence spectrometry revealed that some surma samples contained lead more than 96%, the surma might contaminate the nail specimen. Scanning electron microscopy observations showed that lead-containing surma consists of fine particle of galena (ore of lead sulfide) in respirable dust range (less than 10 μm). In addition, relative in vitro bioavailability of lead in the surma was determined as 5.2%. Thus, lead-containing surma consists of inhalable and bioavailable particles, and it contributes an increased risk of lead exposure. Moreover, the relationship between the surma and the lead-contaminated nails by lead isotope ratios analysis indicated the potential of lead contamination in nails by surma. These results suggest that lead in the nails was derived both from body burden of lead and external contamination by lead-containing surma. Therefore, nail is not suited as a biomarker for lead exposure in the countries where surma used, because we may overestimate lead exposure by surface lead contamination in the nail by surma. Copyright © 2016 Elsevier Ltd. All rights reserved.

Two mineralization events in the Baiyinnuoer Zn-Pb deposit in Inner Mongolia, China: Evidence from field observations, S-Pb isotopic compositions and U-Pb zircon ages

NASA Astrophysics Data System (ADS)

Jiang, Si-Hong; Chen, Chun-Liang; Bagas, Leon; Liu, Yuan; Han, Ning; Kang, Huan; Wang, Ze-Hai

2017-08-01

The Xing-Mong Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB) and has experienced multiple tectonic events. The Baiyinnuoer Pb-Zn deposit may be a rare case that documents two periods of mineralization in the tectonically complex XMOB. There are two types of Pb-Zn mineralization in the deposit: (1) skarn-type ore, hosted by the skarn in the contact zone between marble and granodiorite and within the marble and (2) vein-type ore, hosted by crystal tuff and feldspar porphyry. This study revealed that the host rocks, mineral assemblages, mineralization occurrences, S-Pb isotopes, and ages between the two types of ore are notably different. Zircon U-Pb dating indicates that the granodiorite was emplaced in the Early Triassic (244 ± 1 to 242 ± 1 Ma), the crystal tuff was deposited in the Early Cretaceous (140 ± 1 to 136 ± 1 Ma), and the feldspar porphyry was intruded in the Early Cretaceous (138 ± 2 to 136 ± 2 Ma). The first skarn mineralization occurred at ∼240 Ma and the second vein-type Pb-Zn mineralization took place between 136 and 129 Ma. Thus the Triassic orebodies were overprinted by Early Cretaceous mineralization. The sphalerite and galena from the skarn mineralization have higher δ34S values (-4.7 to +0.3‰) than the sphalerite, galena and aresenopyrite from the vein-type mineralization (-7.5 to -4.2‰), indicating different sulfur sources or ore-forming processes for the two types of mineralization. The Pb isotopic compositions of the two types of ore are very similar, suggesting similar lead sources. Geochemistry and Nd-Pb-Hf isotopic systematics of the igneous rocks in the region show that the Triassic granodiorite was generated from hybridization of mafic and felsic magmas due to strong crust-mantle interaction under the collisional setting that resulted following the closure of the Paleo-Asian Ocean and the collision of North China and Siberian cratons at the end of the Permian; while the

Isotopic generator for bismuth-212 and lead-212 based on radium

DOEpatents

Hines, J.J.; Atcher, R.W.; Friedman, A.M.

1985-01-30

Disclosed are method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

Investigation of off-site airborne transport of lead from a superfund removal action site using lead isotope ratios and concentrations

USGS Publications Warehouse

Pribil, Michael J.; Maddaloni, Mark A.; Staiger, Kimberly; Wilson, Eric; Magriples, Nick; Ali, Mustafa; Santella, Dennis

2014-01-01

Lead (Pb) concentration and Pb isotopic composition of surface and subsurface soil samples were used to investigate the potential for off-site air transport of Pb from a former white Pb processing facility to neighboring residential homes in a six block area on Staten Island, NY. Surface and subsurface soil samples collected on the Jewett White Pb site were found to range from 1.122 to 1.138 for 206Pb/207Pb and 2.393 to 2.411 for 208Pb/207Pb. The off-site surface soil samples collected from residential backyards, train trestle, near site grass patches and background areas varied from 1.144 to 1.196 for 206Pb/207Pb and 2.427 to 2.464 for 208Pb/207Pb. Two soil samples collected along Richmond Terrace, where Jewett site soils accumulated after major rain events, varied from 1.136 to 1.147 for 206Pb/207Pb and 2.407 to 2.419 for 208Pb/207Pb. Lead concentration for on-site surface soil samples ranged from 450 to 8000 ug/g, on-site subsurface soil samples ranged from 90,000 to 240,000 ug/g and off-site samples varied from 380 to 3500 ug/g. Lead concentration and isotopic composition for the Staten Island off-site samples were similar to previously published data for other northeastern US cities and reflect re-suspension and re-mobilization of local accumulated Pb. The considerable differences in both the Pb isotopic composition and Pb concentration of on-site and off-site samples resulted in the ability to geochemically trace the transport of particulate Pb. Data in this study indicate minimal off-site surface transport of Pb from the Jewett site into the neighboring residential area.

VHF-UHF Noise Surveys at Gulkana, Elmendorf AFB, Galena AFB, Kotzebue and Cape Lisburne, Alaska and NRL, Pomonkey, Maryland

DTIC Science & Technology

1993-02-01

61 6.6 Galena AFB Meteor Scatter Site ...... ............. .. 66 6.7 Kotzebue Meteor Scatter and Army National Guard ...Measurement Setup at the Army National Guard 75 Facility inh Kotzebue 6.7-3 Kotzebue 5 August 1992 (a) Cumulative Spectra 77 40-50 MHYz; (b) Time Series...signals originating from any place on Earth can be expected throughout the day and night . At frequencies above approximately 15 MHz propagation is still

Lead concentrations and isotope ratios in street dust determined by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

PubMed

Nageotte, S M; Day, J P

1998-01-01

A major source of environmental lead, particularly in urban areas, has been from the combustion of leaded petrol. Street dust has previously been used to assess urban lead contamination, and the dust itself can also be a potential source of lead ingestion, particularly to children. The progressive reduction of lead in petrol, in recent years, would be expected to have been reflected in a reduction of lead in urban dust. We have tested this hypothesis by repeating an earlier survey of Manchester street dust and carrying out a comparable survey in Paris. Samples were collected from streets and parks, lead was extracted by digestion with concentrated nitric acid and determined by electrothermal atomic absorption spectrometry. Lead isotope ratios were measured by inductively coupled plasma mass spectrometry. Results for Manchester show that lead concentrations have fallen by about 40% (street dust averages, 941 micrograms g-1 (ppm) in 1975 down to 569 ppm in 1997). In Paris, the lead levels in street dust are much higher and significant differences were observed between types of street (not seen in Manchester). Additionally, lead levels in parks were much lower than in Manchester. Samples collected under the Eiffel Tower had very high concentrations and lead isotope ratios showed that this was unlikely to be fallout from motor vehicles but could be due to the paint used on the tower. Isotope ratios measurements also revealed that lead additives used in France and the UK come from different sources.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

PubMed

Gulson, Brian; Kamenov, George D; Manton, William; Rabinowitz, Michael

2018-04-11

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208 Pb/ 206 Pb and 207 Pb/ 206 Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields

PubMed Central

Gulson, Brian; Manton, William; Rabinowitz, Michael

2018-01-01

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields. PMID:29641487

A two century record of lead isotopes in high altitude Alpine snow and ice

NASA Astrophysics Data System (ADS)

Rosman, K. J. R.; Ly, C.; Van de Velde, K.; Boutron, C. F.

2000-03-01

A 140 m snow/ice core drilled at Mont Blanc, France, has been analysed for Pb isotopes, Pb and Ba concentrations. The 206Pb/ 207Pb ratio, which was measured by thermal ionisation mass spectrometry, decreased steadily from ˜1.18 about two centuries ago to ˜1.17 in 1960, then fell rapidly to ˜1.15 by 1968. Evidence of the Italian (Turin) isotopic lead experiment (IILE) was found in samples dated ˜1977 where the ratio dipped to 1.117. By the early 1990s it had returned to mid 1960s values. Large seasonal variations were found in Pb and Ba concentrations. Summer samples were associated with smooth changes in the 206Pb/ 207Pb ratio while larger fluctuations were encountered in winter which is consistent with a low altitude inversion near Mont Blanc in the winter and free transfer of pollutants from lower to higher altitudes at other times. A plot of 208Pb/ 207Pb versus 206Pb/ 207Pb ratios reveals three isotopic groupings, associated with the periods pre-1923, 1923-1968 and 1969-1991. In the first group, the isotopic composition is consistent with local mining, smelting and coal burning, while in the second, motor vehicle exhaust emissions dominate. In the third group, motor vehicle emissions also dominate but the Pb is even less radiogenic. During this period the IILE occurred and there was a reduction in the use of leaded gasoline in Europe. A comparison of the Mont Blanc and Summit (central Greenland) records shows they contain similar 206Pb/ 207Pb ratios between 1960 and 1968, although small differences in isotopic composition can be detected by also considering the 208Pb/ 207Pb ratio. However, after 1969 the two records diverge markedly, with the Greenland ratios being dominated by the highly radiogenic Mississippi valley-type Pb from the USA and with the Mont Blanc ratios moving to lower values particularly about the time of the IILE.

Constraining recent lead pollution sources in the North Pacific using ice core stable lead isotopes

NASA Astrophysics Data System (ADS)

Gross, B. H.; Kreutz, K. J.; Osterberg, E. C.; McConnell, J. R.; Handley, M.; Wake, C. P.; Yalcin, K.

2012-08-01

Trends and sources of lead (Pb) aerosol pollution in the North Pacific rim of North America from 1850 to 2001 are investigated using a high-resolution (subannual to annual) ice core record recovered from Eclipse Icefield (3017 masl; St. Elias Mountains, Canada). Beginning in the early 1940s, increasing Pb concentration at Eclipse Icefield occurs coevally with anthropogenic Pb deposition in central Greenland, suggesting that North American Pb pollution may have been in part or wholly responsible in both regions. Isotopic ratios (208Pb/207Pb and 206Pb/207Pb) from 1970 to 2001 confirm that a portion of the Pb deposited at Eclipse Icefield is anthropogenic, and that it represents a variable mixture of East Asian (Chinese and Japanese) emissions transported eastward across the Pacific Ocean and a North American component resulting from transient meridional atmospheric flow. Based on comparison with source material Pb isotope ratios, Chinese and North American coal combustion have likely been the primary sources of Eclipse Icefield Pb over the 1970-2001 time period. The Eclipse Icefield Pb isotope composition also implies that the North Pacific mid-troposphere is not directly impacted by transpolar atmospheric flow from Europe. Annually averaged Pb concentrations in the Eclipse Icefield ice core record show no long-term trend during 1970-2001; however, increasing208Pb/207Pb and decreasing 206Pb/207Pb ratios reflect the progressive East Asian industrialization and increase in Asian pollutant outflow. The post-1970 decrease in North American Pb emissions is likely necessary to explain the Eclipse Icefield Pb concentration time series. When compared with low (lichen) and high (Mt. Logan ice core) elevation Pb data, the Eclipse ice core record suggests a gradual increase in pollutant deposition and stronger trans-Pacific Asian contribution with rising elevation in the mountains of the North Pacific rim.

The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

NASA Technical Reports Server (NTRS)

Chen, J. H.; Wasserburg, G. J.

1981-01-01

The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

Lead isotopes tracing the life cycle of a catchment: From source rock via weathering to human impact

NASA Astrophysics Data System (ADS)

Negrel, P. J.; Petelet-Giraud, E.; Guerrot, C.; Millot, R.

2015-12-01

Chemical weathering of rocks involves consumption of CO2, a greenhouse gas with a strong influence on climate. Among rocks exposed to weathering, basalt plays a major role in the carbon cycle as it is more easily weathered than other crystalline silicate rocks. This means that basalt weathering acts as a major atmospheric CO2 sink. The present study investigated the lead isotopes in rock, soil and sediment for constraining the life cycle of a catchment, covering source rocks, erosion processes and products, and anthropogenic activities. For this, we investigated the Allanche river drainage basin in the Massif Central, the largest volcanic areas in France, that offers opportunities for selected geochemical studies since it drains a single type of virtually unpolluted volcanic rock, with agricultural activity increasing downstream. Soil and sediment are derived exclusively from basalt weathering, and their chemistry, coupled to isotope tracing, should shed light on the behavior of chemical species during weathering from parental bedrock. Bedrock samples of the basin, compared to regional bedrock of the volcanic province, resulted from a complex history and multiple mantle reservoir sources and mixing. Regarding soils and sediments, comparison of Pb and Zr normalized to mobile K shows a linear evolution of weathering processes, whereby lead enrichment from atmospheric deposition is the other major contributor. Lead-isotope ratios showed that most of the lead budget in sediment and soil results from bedrock weathering with an influence of past mining and mineral processing of ores in the Massif Central, and deposition of lead-rich particles from gasoline combustion, but no lead input from agricultural activity. A classic box model was used to investigate the dynamics of sediment transfer at the catchment scale, the lead behavior in the continuum bedrock-soil-sediment and the historical evolution of anthropogenic aerosol emissions.

Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

NASA Astrophysics Data System (ADS)

Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej

2015-04-01

The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur

New isotopic evidence of lead contamination in wheat grain from atmospheric fallout.

PubMed

Yang, Jun; Chen, Tongbin; Lei, Mei; Zhou, Xiaoyong; Huang, Qifei; Ma, Chuang; Gu, Runyao; Guo, Guanghui

2015-10-01

Crops could accumulate trace metals by soil-root transfer and foliar uptake from atmospheric fallout, and an accurate assessment of pollution sources is a prerequisite for preventing heavy metal pollution in agricultural products. In this study, we examined Pb isotope rates to trace the sources of Pb in wheat grain grown in suburbs. Results showed that, even in zones with scarcely any air pollution spots, atmospheric fallout was still a considerable source of Pb accumulation in wheat. The concentration of Pb in wheat grain has poor correlation with that in farm soil. The Pb concentration in wheat grains with dust in bran coat was significantly higher than that in wheat grains, which indicates that Pb may accumulate by foliar uptake. The Pb isotope rate has obvious differences between the soil and atmospheric fallout, and scatter ratio is significantly closer between the wheat grain and atmospheric fallout. Atmospheric fallout is a more significant source of Pb concentration in wheat grains than in soil. As far as we know, this is the first study on the main sources of lead in grain crop (wheat) samples with isotope. This study aims to improve our understanding of the translocation of foliar-absorbed metals to nonexposed parts of plants.

Chemical data and lead isotopic compositions of geochemical baseline samples from streambed sediments and smelter slag, lead isotopic compositions in fluvial tailings, and dendrochronology results from the Boulder River watershed, Jefferson County, Montana

USGS Publications Warehouse

Unruh, Daniel M.; Fey, David L.; Church, Stan E.

2000-01-01

IntroductionAs a part of the U.S. Geological Survey Abandoned Mine Lands Initiative, metal-mining related wastes in the Boulder River study area in northern Jefferson County, Montana, have been evaluated for their environmental effects. The study area includes a 24-km segment of the Boulder River in and around Basin, Montana and three principal tributaries to the Boulder River: Basin Creek, Cataract Creek, and High Ore Creek. Mine and prospect waste dumps and mill wastes are located throughout the drainage basins of these tributaries and in the Boulder River. Mine-waste material has been transported into and down streams, where it has mixed with and become incorporated into the streambed sediments. In some localities, mine waste material was placed directly in stream channels and was transported downstream forming fluvial tailings deposits along the stream banks. Water quality and aquatic habitat have been affected by trace-element-contaminated sediment that moves from mine wastes into and down streams during snowmelt and storm runoff events within the Boulder River watershed.Present-day trace element concentrations in the streambed sediments and fluvial tailings have been extensively studied. However, in order to accurately evaluate the impact of mining on the stream environments, it is also necessary to evaluate the pre-mining trace-element concentrations in the streambed sediments. Three types of samples have been collected for estimation of pre-mining concentrations: 1) streambed sediment samples from the Boulder River and its tributaries located upstream from historical mining activity, 2) stream terrace deposits located both upstream and downstream of the major tributaries along the Boulder River, and 3) cores through sediment in overbank deposits, in abandoned stream channels, or beneath fluvial tailings deposits. In this report, we present geochemical data for six stream-terrace samples and twelve sediment-core samples and lead isotopic data for six terrace

The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing

NASA Astrophysics Data System (ADS)

Carey, A.; Darrah, T.; Harrold, Z.; Prutsman-Pfeiffer, J.; Poreda, R.

2008-12-01

Lead isotope and rare earth element composition of modern human bones are analyzed to explore their utility for geographical provenancing. DNA analysis is the standard for identification of individuals. DNA analysis requires a DNA match for comparison. Thus, DNA analysis is of limited use in cases involving unknown remains. Trace elements are incorporated into bones and teeth during biomineralization, recording the characteristics of an individual's geochemical environment. Teeth form during adolescence, recording the geochemical environment of an individual's youth. Bones remodel throughout an individual's lifetime. Bones consist of two types of bone tissue (cortical and trabecular) that remodel at different rates, recording the geochemical environment at the time of biomineralization. Cortical bone tissue, forming the outer surface of bones, is dense, hard tissue that remodels in 25-30 yrs. Conversely, trabecular bone tissue, the inner cavity of bones, is low density, porous and remodels in 2-5 years. Thus, analyzing teeth and both bone tissues allows for the development of a geographical time line capable of tracking immigration patterns through time instead of only an individual's youth. Geochemical isotopic techniques (Sr, O, C, N) have been used for geographical provenancing in physical anthropology. The isotopic values of Sr, C, O, N are predominantly a function of soil compositions in areas where food is grown or water is consumed. Application of these provenancing techniques has become difficult as an individual's diet may reflect the isotopic composition of foods obtained at the local grocer as opposed to local soil compositions. Thus, we explore the use of REEs and Pb isotopes for geographical provenancing. Pb and REEs are likely more reliable indicators of modern geographical location as their composition are high in bio-available sources such as local soils, atmospheric aerosols, and dust as opposed to Sr, C, O, N that are controlled by food and

Western US Seismic Observations Viewed Through Lead Isotope Maps

NASA Astrophysics Data System (ADS)

Bouchet, R. A.; Blichert-Toft, J.; Levander, A.; Reid, M. R.; Albarede, F.

2013-12-01

To shed light on the nature and history of the different geological units identified by the seismic models that have come from USArray in the western US, we compiled literature Pb isotope compositions of ores (n=1200), K-feldspars from granites (n=400), and felsic plutonic rocks (n=1300), data that for most part were not in the NAVDAT database. We complemented this compilation by analyzing the Pb isotope compositions of K-feldspars (76) and whole-rocks (6) of felsic xenoliths and felsic plutonic rocks from the Colorado Plateau (CP). The raw Pb isotope abundances for the complete data set were converted into three independent, geologically informative parameters in the form of the model age T (time of last U/Pb fractionation) and the two chemical ratios 238U/204Pb (μ) and 232Th/238U (κ). These parameters were then imaged on isotopic maps of the western US using 0.5°×0.5° grid-cell averaging for μ and κ and a 0.5°×0.5° grid-cell maximum after removing the 2.5% highest values (outliers) for T. Comparing these chemical maps to seismic maps of tomographic anomalies [1] and Moho and LAB depths determined from receiver functions [2] leads to the following observations: (i) Pb model ages: they match geological ages mostly where the continental mantle is cold and the Moho is deep. Elsewhere, Pb model ages are younger than geological ages. We interpret this feature as the chronological expression of a delayed cooling of deep crustal layers below the closure temperature (˜550-700°C) of Pb in K-feldspar, the major host of this element in the crust [3] or of age resetting by orogenic activity. (ii) While U/Pb (μ) does not vary systematically with other geochemical or seismic data, high Th/U (κ) values are usually observed where Vp/Vs is also high, as in the Snake River basin and central Colorado. High kappa values also form a 'ridge' trending south from northwestern Utah through the Basin and Range into the Mojave-Yavapai block. High-κ areas may reflect the

Occurrence of silver minerals in a silver-rich pocket in the massive sulfide zinc-lead ores in the Edwards mine, New York

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serviss, C.R.; Grout, C.M.; Hagni, R.D.

1985-01-01

Ore microscopic examination of uncommon silver-rich ores from the Edwards mine has detected three silver minerals, native silver, freibergite, and argentite, that were previously unreported in the literature from the Balmat-Edwards district. The zinc-lead ore deposits of the Balmat-Edwards District in northern New York are composed of very coarse-grained massive sulfides, principally sphalerite, galena, and pyrite. The typical ores contain small amounts of silver in solid solution galena. Galena concentrates produced from those ores have contained an average of 15 ounces of silver per ton of 60% lead concentrates. In contrast to the typical ore a silver-rich pocket, that measuredmore » three feet by three feet on the vertical mine face and was the subject of this study, contained nearly 1% silver in a zinc ore. Ore microscopic study shows that this ore is especially characterized by abundant, relatively fine-grained chalcopyrite with anhedral pyrite inclusions. Fine-grained sphalerite, native silver, argentite, freibergite and arsenopyrite occur in association with the chalcopyrite and as fracture-fillings in gangue minerals. Geochemically anomalous amounts of tin, barium, chromium, and nickel also are present in the silver-rich pocket. The silver-rich pocket may mark the locus of an early feeder vent or alternatively it may record a hydrothermal event that was superimposed upon the event responsible for the metamorphic ore textures.« less

Trace Metals and Lead Isotopes in modern Sediments Near Rio de Janeiro, Brazil

NASA Astrophysics Data System (ADS)

Boyle, E. A.; Lazzari, L.; Wagener, A. L.; Carreira, R.; Godoy, J. M.; Noble, A.; Carrasco, G. G.; Moos, S. B.

2014-12-01

This work focuses on the export of trace metals and combustion residues from land to ocean and on the Southeast continental margin of Brazil and its historical variability using stable lead isotopes. Two sediment cores were collected, one in highly impacted Guanabara Bay and the other on the Southeast continental shelf. Continental shelf samples were analyzed for trace element concentrations [Mn (117±50 ppm), Ni (6.5±2.3 ppm), Zn (5.0±1.5), (233±46 ppm), ], Pb (5.4±2.4 ppm), as well as Cu, Ag, Cd, Sr, Ba, Tl, U and Pb isotope ratios & Pb-210. Most of the elements show higher concentrations on the upper part of the core compared to the bottom. Downcore changes of the concentrations of these elements were similar. The sediments of adjacent rivers and bays around the upper section of the southeast continental shelf of Brazil are considered highly enriched with Pb, Zn, Cu and Cr such as Guanabara Bay, Sepetiba Bay and Paraíba do Sul River compared with the natural concentrations and other regions in the world. A [Pb] maximum is seen between samples from 24 to 43 cm (~8 ppm). Utilization of tetraethyl lead (TEL) gasoline in Brazil was phased out beginning in 1983 and was largely completed by 1988. Continental shelf Pb-206/Pb-207 varies between 1.174 near the core top to 1.190 at 100 cm, with a sharp difference between samples at 6 and 8 cm. Higher core top Pb, Zn, and Ni corroborate the recent anthropogenic influence on the southeast continental shelf of Brazil. For Guanabara Bay sediment samples [Pb] varies between 90 ppm near the top to 1 ppm at the bottom. Pb-206/Pb-207 varies between 1.161 near the core top to 1.165 near the bottom. Using triple isotope plots we can discern different sources of lead to the region and how these vary with time.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb

Lead isotopic studies of lunar soils - Their bearing on the time scale of agglutinate formation

NASA Technical Reports Server (NTRS)

Church, S. E.; Tilton, G. R.; Chen, J. H.

1976-01-01

Fines (smaller than 75 microns) and bulk soil were studied to analyze loss of volatile lead; losses of the order of 10% to 30% radiogenic lead during the production of agglutinates are assessed. Lead isotope data from fine-agglutinate pairs are analyzed for information on the time scale of micrometeorite bombardment, from the chords generated by the data in concordia diagrams. Resulting mean lead loss ages were compared to spallogenic gas exposure ages for all samples. Labile parentless radiogenic Pb residing preferentially on or in the fines is viewed as possibly responsible for aberrant lead loss ages. Bulk soils plot above the concordia curve (in a field of excess radiogenic Pb) for all samples with anomalous ages.

Preliminary mineralogic, fluid inclusion, and stable isotope study of the Mahd adh Dhahab gold mine, Kingdom of Saudi Arabia

USGS Publications Warehouse

Rye, Robert O.; Hall, W.E.; Cunningham, C.G.; Czamanske, G.K.; Afifi, A.M.; Stacey, J.S.

1983-01-01

reservoir at depth. The d18O values of all stages of vein quartz in the South orebody range between 8.5 and 11.1 per mil. This range is similar to that for quartz from the North orebody and indicates that the hydrothermal system consisted of dominantly exchanged meteoric water, which was uniform in temperature and d18O content throughout the area during the entire period of mineralization. Lead isotope analyses of two galena samples indicate that the lead in the South orebody is less radiogenic than that from the North orebody and confirm that the lead was derived from oceanic crust approximately 700 Ma ago.

Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

USGS Publications Warehouse

Pfaff, Katharina; Koenig, Alan; Wenzel, Thomas; Ridley, Ian; Hildebrandt, Ludwig H.; Leach, David L.; Markl, Gregor

2011-01-01

Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

Lead isotope ratio measurements as indicators for the source of lead poisoning in Mute swans (Cygnus olor) wintering in Puck Bay (northern Poland).

PubMed

Binkowski, Łukasz J; Meissner, Włodzimierz; Trzeciak, Marta; Izevbekhai, Kelvin; Barker, James

2016-12-01

Lead (Pb) poisoning is most commonly linked amongst anthropogenically-caused deaths in waterfowl and this is often associated with hunting and fishing activities. However, the exact identification of the source may be difficult with commonly-used techniques. We have studied isotope ratios using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS) to investigate the source of Pb in the blood of Mute swans (n = 49) wintering in northern Poland. We compared the values of isotopic ratios from blood and ammunition pellets available on the Polish market. The mean Pb concentrations found was 0.241 μg/g (w/w) and nearly half of the blood specimens had elevated Pb levels (higher than the cited 0.23 μg/g w/w threshold of poisoning). Only the mean 208/206 Pb isotope ratio was similar in blood and pellet samples. Mean ratios of isotopes 206/204, 206/207 and 208/207 in swans' blood and in pellets differed significantly. Moreover, coefficients of variation were higher in blood samples than in pellets. These discrepancies and significant differences in abundance of 204 Pb and 207 Pb isotopes in both materials indicated that pellets available today on the Polish market were not the source of Pb in the blood of Mute swans wintering in northern Poland. Copyright © 2016 Elsevier Ltd. All rights reserved.

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

NASA Astrophysics Data System (ADS)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

High-precision Pb isotopic measurements of teeth and environmental samples from Sofia (Bulgaria): insights for regional lead sources and possible pathways to the human body

NASA Astrophysics Data System (ADS)

Kamenov, George D.

2008-08-01

High-precision Pb isotopic measurements on teeth and possible sources in a given area can provide important insights for the lead (Pb) sources and pathways in the human body. Pb isotopic analyses on soils from the area of Sofia, Bulgaria show that Pb is contributed by three end-members represented by two natural sources and leaded gasoline. Sequential leaching experiments reveal that the alumosilicate fraction of the soils is mainly controlled by natural Pb derived from two mountain massifs bordering the city. Around 1/3 to a half of the Pb in the soil leachates, however, can be explained by contamination from leaded gasoline. Contemporary teeth from Sofia residents show very similar Pb isotopic compositions to the soil leachates, also indicating that around 1/3 to a half of the Pb can be explained by derivation from leaded gasoline. The remarkable isotopic similarities between the teeth and the most labile fractions of the local soils suggest that the lead can be derived from the latter. Pb incorporation in the human body via soil-plant-human or soil-plant-animal-human chains is unlikely due to the fact that no significant farming occurs in the city area. The isotopic compositions of the local soil labile fractions can be used as approximation of the bioaccessible lead for humans. Considering all possible scenarios it appears that soil and/or soil-born dust inhalation and/or ingestion is the most probable pathway for incorporation of local soil lead in the local population. The high-precision Pb isotope data presented in this work indicate that apparently the local soil is what plays major role in the human Pb exposure.

Isotopic evidence of spatial magnitude of the Pb deposition near a lead smelter

NASA Astrophysics Data System (ADS)

Flament, P.; Franssens, M.; Debout, K.; Weis, D.

2003-05-01

In order to détermine the dry deposition of lead around a Pb-Zn refinery, two cross-sectional sampling experiments, using deposition plates, have been performed on a daiiy basis, ucder representative meteorological situations (north-easterly and south-westerly winds). The amount of lead deposited as well as its isotopic composition (expressed by the ^{206}Pb/^{207}Pb ratio) are systematically measured. For a daily production of approximately 670 metric tons of (Pb+Zn) the dry fallout, greater than 1000 μg Pb.h^{-1}.m^{-2} on the edge of the plant, falls to about 100 μg Pb.h^{-1}.m^{-2}, four kilometres away from the refinery. This value is still ten times higher than th urban background (<10 μg Pb.h^{-1}.m^{-2}). The spatial extension of the dry deposition plume is evidenced by the evolution of the isotopic signature of the refinery (1.10<^{206}Pb/^{207}), clearly distinct from the urban backgrounde signature (1.15<^{206}Pb/^{207}Pb<1.16). As a first estimate, the extension of the deposition plume seems not to be linked to the wind speed. At the opposite, diffuse emissions from slag heaps are related to this parameter.

Sulfur-, oxygen-, and carbon-isotope studies of Ag-Pb-Zn vein-breccia occurrences, sulfide-bearing concretions, and barite deposits in the north-central Brooks Range, with comparisons to shale-hosted stratiform massive sulfide deposits: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Kelley, Karen D.; Leach, David L.; Johnson, Craig A.

2000-01-01

Stratiform shale-hosted massive sulfide deposits, sulfidebearing concretions and vein breccias, and barite deposits are widespread in sedimentary rocks of Late Devonian to Permian age in the northern Brooks Range. All of the sulfide-bearing concretions and vein breccias are hosted in mixed continental-marine clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. The clastic rocks and associated sulfide occurrences underlie chert and shale of Mississippian-Pennsylvanian(?) age that contain large stratiform massive sulfide deposits like that at Red Dog. The relative stratigraphic position of the vein breccias, as well as previously published mineralogical, geochemical, and lead-isotope data, suggest that the vein breccias formed coevally with overlying shale-hosted massive sulfide deposits and that they may represent pathways of oreforming hydrothermal fluids. Barite deposits are hosted either in Mississippian chert and limestone (at essentially the same stratigraphic position as the shale-hosted massive sulfide deposits) or Permian chert and shale. Although most barite deposits have no associated base-metal mineralization, barite occurs with massive sulfide deposits at the Red Dog deposit.Galena and sphalerite from most vein breccias have δ34S values from –7.3 to –0.7‰ (per mil) and –5.1 to 3.6‰, respectively; sphalerite from sulfide-bearing concretions have δ34S values of 0.7 and 4.7‰. This overall range in δ34S values largely overlaps with the range previously determined for galena and sphalerite from shale-hosted massive sulfide deposits at Red Dog and Drenchwater. The Kady vein-breccia occurrence is unusual in having higher δ34S values for sphalerite (12.1 to 12.9‰) and pyrite (11.3‰), consistent with previously published values for the shale-hosted Lik deposit. The correspondence in sulfur isotopic compositions between the stratiform and vein-breccia deposits suggests that they share a common source of reduced sulfur, or

The lead isotopic composition of dust in the vicinity of a uranium mine in northern Australia and its use for radiation dose assessment.

PubMed

Bollhöfer, Andreas; Honeybun, Russell; Rosman, Kevin; Martin, Paul

2006-08-01

Airborne lead isotope ratios were measured via Thermal Ionisation Mass Spectrometry in samples from the vicinity of Ranger uranium mine in northern Australia. Dust deposited on leaves of Acacia spp. was washed off and analysed to gain a geographical snapshot of lead isotope ratios in the region. Aerosols were also collected on Teflon filters that were changed monthly over one seasonal cycle using a low volume diaphragm pump. Lead isotope ratios in dust deposited on leaves overestimate the relative amount of mine origin airborne lead, most likely due to a difference of the size distribution of particles collected on leaves and true aerosol size distribution. Seasonal measurements show that the annual average mine contribution to airborne lead concentrations in Jabiru East, approximately 2.5 km northwest of the mine, amounted to 13%, with distinct differences between the wet and dry season. The relative contribution of mine origin lead deposited on leaves in the dry season drops to less than 1% at a distance of 12.5 km from the mine along the major wind direction. An approach is outlined, in which lead isotope ratios are used to estimate the effective radiation dose received from the inhalation of mine origin radioactivity trapped in or on dust. Using the data from our study, this dose has been calculated to be approximately 2 microSv year(-1) for people living and working in the area.

The Management of Lead Concentrate Acquisition in "Trepca"

NASA Astrophysics Data System (ADS)

Haxhiaj, Ahmet; Fan, Maoming; Haxhiaj, Bajram

Based on the placement of lead and its consumption in industry branches, the paper deals with the composition of lead in the ores of Kopaonik, grinding and flotation recovery of galena. In the flotation process, the flotation machine, the flotation reagents, chemical composition of the flotation concentrates and tailings were discussed in this paper. Verification of the chemical composition of Pb concentrates with Pb, Zn, and Ag, etc. was conducted in this study. It is special that the ratio of Pb to Zn in Kopaonik massive composition is 1.4:1.0. During the flotation, lead tends to float with concentrate more than allowed. In this investigation, effects have been made to minimize the loss of Pb to concentrates. This paper as such gave the first effects in optimizing of these parameters with positive effects in the flotation process in Trepca.

Using trace element content and lead isotopic composition to assess sources of PM in Tijuana, Mexico

NASA Astrophysics Data System (ADS)

Salcedo, D.; Castro, T.; Bernal, J. P.; Almanza-Veloz, V.; Zavala, M.; González-Castillo, E.; Saavedra, M. I.; Perez-Arvízu, O.; Díaz-Trujillo, G. C.; Molina, L. T.

2016-05-01

PM2.5 samples were collected at two urban sites (Parque Morelos (PQM) and CECyTE (CEC)) in Tijuana during the Cal-Mex campaign from May 24 to June 5, 2010. Concentration of trace elements (Mg, Al, Ti, V, Mn, Fe, Co, Ni, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Ba, La, Ce, and Pb), and Pb isotopic composition were determined in order to study the sources of PM impacting each site. Other chemical analysis (gravimetric, elemental and organic carbon (EC/OC), and polycyclic aromatic hydrocarbons (PAHs)), were also performed. Finally, back-trajectories were calculated to facilitate the interpretation of the chemical data. Trace elements results show that CEC is a receptor site affected by mixed regional sources: sea salt, mineral, urban, and industrial. On the other hand, PQM seems to be impacted mainly by local sources. In particular, Pb at CEC is of anthropogenic, as well as crustal origin. This conclusion is supported by the lead isotopic composition, whose values are consistent with a combination of lead extracted from US mines, and lead from bedrocks in the Mexican Sierras. Some of the time variability observed can be explained using the back-trajectories.

Authenticity of Benin metalworks evaluated by inductively coupled plasma mass spectrometry and lead isotope analyses

NASA Astrophysics Data System (ADS)

Fabbri, E.; Soffritti, C.; Merlin, M.; Vaccaro, C.; Garagnani, G. L.

2017-05-01

Two metal plaques and a cock statuette belonging to a private collection and stylistically consistent with the Royal Art of Benin (Nigeria) were investigated in order to verify their authenticity. The characterization of alloys and patinas were carried out by inductively coupled plasma mass spectrometry, optical microscopy, scanning electron microscopy and energy dispersion spectroscopy, and X-Ray diffraction spectrometry. Furthermore, thermal ionization mass spectrometry was used to assess the abundances of lead isotopes and to attempt a dating by the measurement of 210Pb/204Pb ratio. The results showed that all three artefacts were mainly composed of low lead-brass alloys, with relatively high concentrations of zinc, antimony, cadmium and aluminum in the solid copper solution. Microstructures were mostly dendritic, typical of as-cast brasses, and characterized by recrystallized non-homogeneous twinned grains in areas corresponding to surface decorations, probably due to multiple hammering steps followed by partial annealing treatments. The matrix was composed of a cored α-Cu solid solution together with non-metallic inclusions, lead globules and Sn-rich precipitates in interdendritic spaces. On the surface of all metalworks, both copper and zinc oxides, a non-continuous layer of sulphur-containing contaminants and chloride-containing compounds, were identified. The lead isotope results were consistent with brasses produced shortly before or after 1900 CE. Overall, the data obtained by different techniques supported the hypothesis that the three artefacts were not authentic.

The distribution of lead concentrations and isotope compositions in the eastern Tropical Atlantic Ocean

NASA Astrophysics Data System (ADS)

Bridgestock, Luke; Rehkämper, Mark; van de Flierdt, Tina; Paul, Maxence; Milne, Angela; Lohan, Maeve C.; Achterberg, Eric P.

2018-03-01

Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600-900 m, 35 pmol kg-1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818-1.1824, 208Pb/207Pb = 2.4472-2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50-60 years. In contrast, North Atlantic Deep Water (2000-4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762-1.184, 208Pb/207Pb = 2.4482-2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80-100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distributions is particularly apparent in seawater in the

Lead Isotopic Source Signatures for Rains and River Waters in Taiwan

NASA Astrophysics Data System (ADS)

You, C.; Cheng, M.; Lee, M.; Lin, F.

2002-12-01

Lead isotopic compositions and Pb contents in rains and river waters are sensitive proxies for air-pollutant sources and their transport processes. We have collected more than 100 wet precipitations between 1998 and 2001 at Peng-Chia Yu, an offshore island in northern Taiwan, and two other cities, Taichung and Tainan, located at central and southern Taiwan. Additional 14 river waters collected along the Er-Ren-Shi River, Tainan were investigated for systematic comparison. All collected samples were analyzed for major ions (i.e., Cl, Na, Mg, Ca, SO4, NO3 and NH4) by ion chromatography, trace elements and Pb isotopes by ICP-MS (Element II) installed at NCKU. The Peng-Chia Yu rains show large seasonal variation in major ions where Na and Cl are much higher in the winter season. Significant industrial contributions of SO4, NH4 and nsCa are detected at Taichung and Tainan. Trace element results display a more complicated picture, suggesting mixing among seasalt, Asia continental dust, and atmospheric pollutant. These chemical data can be understood in terms of seasonal wind direction changes due to the Asian monsoon system. In winter, the northerly cold wind blow materials with high concentration of anthropogenic input (i.e., Pb and SO4) and dust source (i.e., Al and Ca) from the Asia continent. In contrast, the intertropical convergence zone (ITCZ) migrates northward and caused southwest monsoon prevail in the summer. The 208Pb/207Pb ratio shows consistent seasonal trends as that of Pb contents, possibly a result of mixing between Asia atmospheric sources and seasalt. For the Er-ren Shi River waters, Pb and Pb isotopic compositions vary systematically downstream. Pb concentrations decrease rapidly from 5200 ppt at upstream stations to a value of less than 50 ppt near the estuary whereas 208Pb/207Pb varied between 2.087 and 2.124. The 208Pb/206Pb vs. 1/Pb plot demonstrates a mixing trend between anthropogenic sources and seawater. These results demonstrate that Pb and

Lead isotopes in soils and groundwaters as tracers of the impact of human activities on the surface environment: The Domizio-Flegreo Littoral (Italy) case study

USGS Publications Warehouse

Grezzi, G.; Ayuso, R.A.; de Vivo, B.; Lima, A.; Albanese, S.

2011-01-01

The isotopic signature of geogenic and anthropogenic materials, in combination with concentration data for pollutants, can help trace the origin and the extent of contamination in the environment. This approach is particularly effective if naturally occurring and anthropogenically introduced metals have different isotopic ratios. Lead isotope analysis on soils from 7 profiles (1. m depth) and on groundwaters from 8 wells have been used to determine the impact of human activities on the surface environment of Domizio-Flegreo Littoral. Result obtained show that in sub-rural areas the isotopic composition of the samples collected along the soil profiles of Domizio-Flegreo Littoral is likely mostly controlled by the nature of the parent geologic material (natural) while in more urbanized areas (Giugliano) Pb isotopic composition in superficial soils is mostly influenced by anthropic sources such as motor vehicles. Lead isotopic ratios in groundwaters also show that the use of pesticides and, probably, the influence of aerosols and the presence of illegal waste disposal can influence water quality. ?? 2010 Elsevier B.V.

Geochronological and lead-isotope evidences for rapid crust formation in middle-proterozoic time: The Labrador example

NASA Technical Reports Server (NTRS)

Schaerer, Urs

1988-01-01

Extensive U-Pb geochronological studies in the Grenville and Makkovik provinces have shown that eastern Labrador is underlain by two distinct crustal blocks. In order to substantiate the juvenile character of the middle-Proterozoic crustal block, the isotopic compositon of lead in leached k-feldspars from the same rocks were analyzed. The results of the analysis are briefly discussed.

Precipitation of lead-zinc ores in the Mississippi Valley-type deposit at Treves, Cevennes region of southern France

USGS Publications Warehouse

Leach, D.; Macquar, J.-C.; Lagneau, V.; Leventhal, J.; Emsbo, P.; Premo, W.

2006-01-01

The Trèves zinc–lead deposit is one of several Mississippi Valley-type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ34S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to −21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur-rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced

Evidencing lead deposition at the urban scale using "short-lived" isotopic signatures of the source term (Pb-Zn refinery)

NASA Astrophysics Data System (ADS)

Franssens, Matthias; Flament, Pascal; Deboudt, Karine; Weis, Dominique; Perdrix, Espéranza

2004-09-01

To demonstrate the ability of the lead isotope signature technique to evidence the spatial extent of an industrial Pb deposition plume at a local scale, dry deposition of lead in the urban environment of a Pb-Zn refinery was investigated, as a study case, using transient ("short-lived") isotopic signatures of the industrial source. Sampling campaigns were achieved in representative weather conditions, on an 8-h basis. Dry deposition rates measured downwind from refinery emissions (≈102-103 μg Pb m-2 h-1), cross-sectionally in a 3-5 km radius area around the plant, represent 10-100 times the urban background dry fallout, measured upwind, as well as fallout measured near other potential sources of anthropogenic Pb. The Pb-Zn refinery isotopic signature (approx. 1.100<206Pb/207Pb<1.135) is made identifiable, using the same set of Pb and Zn ores for 2 days before sampling and during field experiments, by agreement with the executive staff of the plant. This source signature is less radiogenic than signatures of urban background Pb aerosols (1.155<206Pb/207Pb<1.165) and minor sources of Pb aerosols (1.147<206Pb/207Pb<1.165). By a simple binary mixing model calculation, we established the extension of the industrial Pb deposition plume. Fifty to eighty percents of total lead settled by the dry deposition mode, 3-4 km away from the refinery, still have an industrial origin. That represents from 40 to 80 μg Pb m-2 h-1, in an area where the blood lead level exceeds 100 μg Pb l-1 for 30% of men and 12% of women living there. We demonstrate here that stable Pb isotope analysis is able to evidence the Pb dry deposition plume in stabilised aerodynamic conditions, using a short-lived source term, suggesting that this methodology is able to furnish valuable data to validate industrial Pb aerosols dispersion models, at the urban scale.

Constraints of C-O-S isotope compositions and the origin of the Ünlüpınar volcanic-hosted epithermal Pb-Zn ± Au deposit, Gümüşhane, NE Turkey

NASA Astrophysics Data System (ADS)

Akaryali, Enver; Akbulut, Kübra

2016-03-01

The Eastern Pontide Orogenic Belt (EPOB) constitutes one of the best examples of the metallogenic provinces in on the Alpine-Himalayan belt. This study focuses on the genesis of the Ünlüpınar Pb-Zn ± Au deposit in the southern part of the Eastern Pontide Orogenic Belt. The main lithological units in the study area are the Early Carboniferous Kurtoğlu Metamorphic Complex the Late Carboniferous Köse Granitoid and the Early-Middle Jurassic Şenköy Formation. The studied deposit is hosted by the Şenköy Formation, which consists predominantly of basaltic-andesitic rocks and associated pyroclastic rocks that are calc-alkaline in composition. Silicic, sulfidic, argillic, chloritic, hematitic, carbonate and limonite are the most obvious alteration types observed in the deposit site. Ore microscopy studies exhibit that the mineral paragenesis in deposits includes pyrite, chalcopyrite, sphalerite, galena, gold, quartz and calcite. Electron microprobe analyses conducted on sphalerite indicate that the Zn/Cd ratio varies between 84 and 204, and these ratios point at a hydrothermal deposit related to granitic magmas. Fluid inclusion studies in calcite and quartz show that the homogenization temperature of the studied deposit ranges between 90-160 °C and 120-330 °C respectively. The values of sulfur isotope analysis of pyrite, sphalerite and galena minerals vary between 1.6‰ and 5.7‰, and the results of oxygen and carbon isotope analysis range between 8.4‰ and 18‰ and -5‰ and -3.6‰, respectively. The average formation temperature of the ore was calculated as 264 °C with a sulfur isotope geothermometer. All of the data indicate that the Ünlüpınar deposit is an epithermal vein-type mineralization that was formed depending on the granitic magmatism.

Lead isotopic evidence for mixed sources of Proterozoic granites and pegmatites, Black Hills, South Dakota, USA

NASA Astrophysics Data System (ADS)

Krogstad, Eirik J.; Walker, Richard J.; Nabelek, Peter I.; Russ-Nabelek, Carol

1993-10-01

The lead isotopic compositions of K-feldspars separated from the ca. 1700 Ma Harney Peak Granite complex and spatially associated granitic pegmatites indicate that these rocks were derived from at least two sources. It has been reported previously that the core of the Harney Peak Granite complex is dominated by relatively lower/ gd18O (avg. 11.5 %.) granites, whereas higher / gd18O (avg. 13.2%.) granites occur around the periphery of the complex. The higher δ 18O granites and one simple pegmatite have low values of 207Pb /204Pb for their 206Pb /204Pb Thus, they likely were derived from a source with a short crustal residence time. This source may have been the pelitic schists into which the Harney Peak Granite complex and pegmatites were intruded. Feldspars from granites with lower / gd18O values have significantly higher 207Pb /204Pb for their 206Pb /204Pb . The data define a linear array with a slope equivalent to an age of ca. 2.6 Ga with t 2 defined to be 1.7 Ga. Such a slope could represent a mixing array or a secondary isochron for the source. These low δ18O granites could have been derived from a source with a high U/ Pb and with a crustal residence beginning before the Proterozoic. The source (s) of these granites may have been a sediment derived from late Archean continental crust. The highly evolved Tin Mountain pegmatite has lead isotopic systematics intermediate between those of the two granite groups, suggesting either a mixed source or contamination. Two late Archean granites, the Little Elk Granite and the Bear Mountain Granite, had precursors with high U/Pb and low Th/U histories. The Th/U history of the Bear Mountain Granite is too low for this rock to have been an important component of the source of the Proterozoic granites. However, crustal rocks with lead isotopic compositions similar to those of the Little Elk Granite were an important source of lead for some of the Proterozoic granitic rocks.

Removal of arsenic in flotation of galena and sphalerite

NASA Astrophysics Data System (ADS)

Yu, Dae-hwan; Kim, Min-kyu; Han, Oh-hyung; Park, Chul-hyun

2017-04-01

In Korea, Janggun mine that produces the concentrate of galena (PbS) /sphalerite (ZnS) containing arsenic of 1.3% charges a penalty of US 3/ton to LS-Nikko smelter. Hence in this work, flotation tests for removal of arsenopyrite (FeAsS) from sulfide minerals were carried out using lab scale flotation cell, which maintain grade and recovery of PbS and ZnS in comparison to flotation plant. Particularly, this study was focused on investigating the combination of several chemical reagents such as depressant, collector, activator and etc. that affect flotation performance. In the straight differential flotation for PbS, a PbS grade of 67.80% and a recovery of 80.2% could be obtained with FeAsS removal of 84.1% (0.2% As) under the conditions of 20% feed solids concentration, pH 8.5, 50g/t frother (AF65), 50g/t collector (AP242) and 600g/t As depressant (NaHSO3) and 600g/t Zn depressant (ZnSO4). In the ZnS flotation, the maximum separation achievable for ZnS has been shown to be a grade of 50.27% and a recovery of 88.7%. At this time, FeAsS removal of 87.8% (0.16% As) could be successfully accomplished under pH 11, and 1.2kg/t Zn activator (CuSO4), 100g/t frother (AF65), 100g/t collector (AP211) and 400g/t As depressant (NaHSO3). Acknowledgments This work was supported by the Energy and Resources Engineering Program Grant funded by the Ministry of Trade, Industry and Energy, Korea

Determination of lead, cadmium, indium, thallium and silver in ancient ices from Antarctica by isotope dilution-thermal ionization mass spectrometry

USGS Publications Warehouse

Matsumoto, A.; Hinkley, T.K.

1997-01-01

The concentrations of five chalcophile elements (Pb, Cd, In, Tl and Ag) and the lead isotope rarios in ancient ices from the Taylor Dome near coastal Antarctica, have been determined by the isotope dilutionthermal ionization mass spectrometry (ID-TIMS), with ultra-clean laboratory techniques. The samples were selected from segments of cores, one of which included a visible ash layer. Electric conductivity measurement (ECM) or dielectric properties (DEP) gave distinctive sharp peaks for some of the samples c hosen. Exterior portions of the sample segments were trimmed away by methods described here. Samples w ere evaporated to dryness and later separated into fractions for the five elements using an HBr-HNO3 a nion exchange column method. The concentrations are in the range 2.62-36.7 pg Pb/g of ice, 0.413-2.83 pg Cd/g, 0.081-0.34 pg In/g, 0.096-2.8 pg Tl/g and 0.15-0.84 pg Ag/g. respectively. The dispersions in duplicate analyses are about ??1% for lead and cadmium, ??2% for indium. ??4% for thallium and ??6% for silver, respectively. The concentrations of lead obtained are commonly higher than those in the present-day Antarctic surface snows, but the isotope ratios are distinctively higher than those of the present-day snows and close to those of the other ancient ice collected from a different Antarctic area.

Two-step extraction method for lead isotope fractionation to reveal anthropogenic lead pollution.

PubMed

Katahira, Kenshi; Moriwaki, Hiroshi; Kamura, Kazuo; Yamazaki, Hideo

2018-05-28

This study developed the 2-step extraction method which eluted the Pb adsorbing on the surface of sediments in the first solution by aqua regia and extracted the Pb absorbed inside particles into the second solution by mixed acid of nitric acid, hydrofluoric acid and hydrogen peroxide solution. We applied the method to sediments in the enclosed water area and found out that the isotope ratios of Pb in the second solution represented those of natural origin. This advantage of the method makes it possible to distinguish the Pb between natural origin and anthropogenic source on the basis of the isotope ratios. The results showed that the method was useful to discuss the Pb sources and that anthropogenic Pb in the sediment samples analysed was mainly derived from China because of transboundary air pollution.

Source apportionment of lead in the blood of women of reproductive age living near tailings in Taxco, Guerrero, Mexico: An isotopic study.

PubMed

Vázquez Bahéna, Analine Berenice; Talavera Mendoza, Oscar; Moreno Godínez, Ma Elena; Salgado Souto, Sergio Adrián; Ruiz, Joaquín; Huerta Beristain, Gerardo

2017-04-01

The concentration and isotopic composition of lead in the blood of forty seven women of reproductive age (15-45y) exposed to multiple sources in two rural communities of the mining region of Taxco, Guerrero in southern Mexico were determined in order to identify specific contributing sources and their apportionment and to trace probable ingestion pathways. Our data indicate that >36% of the studied women have blood lead concentrations above 10μgdL -1 and up to 87% above 5μgdL -1 . Tailings contain between 2128 and 5988mgkg -1 of lead and represent the most conspicuous source in the area. Lead contents in indoor dust are largely variable (21.7-987mgkg -1 ) but only 15% of samples are above the Mexican Regulatory Guideline for urban soils (400mgkg -1 ). By contrast, 85% of glazed containers (range: 0.026-68.6mgkg -1 ) used for cooking and food storage are above the maximum 2mgL -1 of soluble lead established in the Mexican Guideline. The isotopic composition indicates that lead in the blood of 95% of the studied women can be modeled in terms of a mixing system between local ores (and derivatives), glazed pottery and Morelos bedrock, end-members, with the two former being largely the most important contributors. Only one sample shows influence of indoor paints. Indoor dust is dominated by ores and derivatives but some samples show evidence of contribution from a less radiogenic source very likely represented by interior paints. This study supports the application of lead isotopic ratios to identify potential sources and their apportionment in humans exposed to multiple sources of lead from both, natural and anthropogenic origin. Copyright © 2017 Elsevier B.V. All rights reserved.

Lead Isotope Characteristics of the Mindyak Gold Deposit, Southern Urals: Evidence for the Source of Metals

NASA Astrophysics Data System (ADS)

Chugaev, A. V.; Znamensky, S. E.

2018-01-01

The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide-carbonate-quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite 206Pb/204Pb = 18.250-18.336, 207Pb/204Pb = 15.645-15.653, 208Pb/204Pb = 38.179-38.461; while for late pyrite 206Pb/204Pb = 18.102-18.378, 207Pb/204Pb = 15.635-15.646, 208Pb/204Pb = 38.149-38.320. The model parameters μ2 (238U/204Pb = 9.91 ± 2), ω2 (232Th/204Pb = 38.5 ± 4), and 232Th/238U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.

Surface dust wipes are the best predictors of blood leads in young children with elevated blood lead levels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulson, Brian, E-mail: brian.gulson@mq.edu.au; CSIRO Earth Science and Resource Engineering, North Ryde NSW 2113; Anderson, Phil

Background: As part of the only national survey of lead in Australian children, which was undertaken in 1996, lead isotopic and lead concentration measurements were obtained from children from 24 dwellings whose blood lead levels were ≥15 µg/dL in an attempt to determine the source(s) of their elevated blood lead. Comparisons were made with data for six children with lower blood lead levels (<10 µg/dL). Methods: Thermal ionisation and isotope dilution mass spectrometry were used to determine high precision lead isotopic ratios ({sup 208}Pb/{sup 206}Pb, {sup 207}Pb/{sup 206}Pb and {sup 206}Pb/{sup 204}Pb) and lead concentrations in blood, dust from floormore » wipes, soil, drinking water and paint (where available). Evaluation of associations between blood and the environmental samples was based on the analysis of individual cases, and Pearson correlations and multiple regression analyses based on the whole dataset. Results and discussion: The correlations showed an association for isotopic ratios in blood and wipes (r=0.52, 95% CI 0.19–0.74), blood and soil (r=0.33, 95% CI −0.05–0.62), and blood and paint (r=0.56, 95% CI 0.09–0.83). The regression analyses indicated that the only statistically significant relationship for blood isotopic ratios was with dust wipes (B=0.65, 95% CI 0.35–0.95); there were no significant associations for lead concentrations in blood and environmental samples. There is a strong isotopic correlation of soils and house dust (r=0.53, 95% CI 0.20–0.75) indicative of a common source(s) for lead in soil and house dust. In contrast, as with the regression analyses, no such association is present for bulk lead concentrations (r=−0.003, 95% CI −0.37–0.36), the most common approach employed in source investigations. In evaluation of the isotopic results on a case by case basis, the strongest associations were for dust wipes and blood. -- Highlights: • Children with elevated blood lead ≥15 µg/dL compared with a group

Isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) for the certification of lead and cadmium in environmental standard reference materials.

PubMed

Murphy, K E; Beary, E S; Rearick, M S; Vocke, R D

2000-10-01

Lead (Pb) and cadmium (Cd) have been determined in six new environmental standard reference materials (SRMs) using isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The SRMs are the following: SRM 1944, New York-New Jersey Waterway Sediment, SRMs 2583 and 2584, Trace Elements in Indoor Dust, Nominal 90 mg/kg and 10,000 mg/kg Lead, respectively, SRMs 2586 and 2587, Trace Elements in Soil Containing Lead from Paint, Nominal 500 mg/kg and 3,000 mg/kg Lead, respectively, and SRM 2782, Industrial Sludge. The capabilities of ID ICP-MS for the certification of Pb and Cd in these materials are assessed. Sample preparation and ratio measurement uncertainties have been evaluated. Reproducibility and accuracy of the established procedures are demonstrated by determination of gravimetrically prepared primary standard solutions and by comparison with isotope dilution thermal ionization mass spectrometry (ID TIMS). Material heterogeneity was readily demonstrated to be the dominant source of uncertainty in the certified values.

Levels and source apportionment of children's lead exposure: could urinary lead be used to identify the levels and sources of children's lead pollution?

PubMed

Cao, Suzhen; Duan, Xiaoli; Zhao, Xiuge; Wang, Beibei; Ma, Jin; Fan, Delong; Sun, Chengye; He, Bin; Wei, Fusheng; Jiang, Guibin

2015-04-01

As a highly toxic heavy metal, the pollution and exposure risks of lead are of widespread concern for human health. However, the collection of blood samples for use as an indicator of lead pollution is not always feasible in most cohort or longitudinal studies, especially those involving children health. To evaluate the potential use of urinary lead as an indicator of exposure levels and source apportionment, accompanying with environmental media samples, lead concentrations and isotopic measurements (expressed as (207)Pb/(206)Pb, (208)Pb/(206)Pb and (204)Pb/(206)Pb) were investigated and compared between blood and urine from children living in the vicinities of a typical coking plant and lead-acid battery factory. The results showed urinary lead might not be a preferable proxy for estimating blood lead levels. Fortunately, urinary lead isotopic measurements could be used as an alternative for identifying the sources of children's lead exposure, which coincided well with the blood lead isotope ratio analysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

United States Air Force 611th Civil Engineer Squadron, Elmendorf, AFB, Alaska. Final engineering evaluation/cost analysis, million gallon hill source area of the West Unit, Galena Airport, Alaska

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-02-05

This decision document presents the selected removal action for the Million Gallon Hill source area of the Installation Restoration Program (IRP) site ST009, otherwise known as the West Unit at Galena Airport, Alaska. The information from the RI Report is summarized, along with an analysis of potential removal action alternatives in the Engineering Evaluation/Cost Analysis (EE/CA).

Genetic interpretation of lead-isotopic data from the Columbia River basalt group, Oregon, Washington, and Idaho.

USGS Publications Warehouse

Church, S.E.

1985-01-01

Lead-isotopic data for the high-alumina olivine plateau basalts and most of the Colombia River basalt group plot within the Cascade Range mixing array. The data for several of the formations form small, tight clusters and the Nd and Sr isotopic data show discrete variation between these basalt groups. The observed isotopic and trace-element data from most of the Columbia River basalt group can be accounted for by a model which calls for partial melting of the convecting oceanic-type mantle and contamination by fluids derived from continental sediments which were subducted along the trench. These sediments were transported in the low-velocity zone at least 400 km behind the active arc into a back-arc environment represented by the Columbia Plateau province. With time, the zone of melting moved up, resulting in the formation of the Saddle Mt basalt by partial melting of a 2600 m.y.-old sub-continental lithosphere characterized by high Th/U, Th/Pb, Rb/Sr and Nd/Sm ratios and LREE enrichment. Partial melting of old sub-continental lithosphere beneath the continental crust may be an important process in the formation of continental tholeiite flood basalt sequences world-wide. -L.di H.

Geogenic lead isotope signatures from meat products in Great Britain: Potential for use in food authentication and supply chain traceability.

PubMed

Evans, Jane A; Pashley, Vanessa; Richards, Gemma J; Brereton, Nicola; Knowles, Toby G

2015-12-15

This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration. Copyright © 2015. Published by Elsevier B.V.

Field isotopic study of lead fate and compartmentalization in earthworm-soil-metal particle systems for highly polluted soil near Pb recycling factory.

PubMed

Goix, Sylvaine; Mombo, Stéphane; Schreck, Eva; Pierart, Antoine; Lévêque, Thibaut; Deola, Frédéric; Dumat, Camille

2015-11-01

Earthworms are important organisms in soil macrofauna and play a key role in soil functionality, and consequently in terrestrial ecotoxicological risk assessments. Because they are frequently observed in soils strongly polluted by metals, the influence of earthworm bioturbation on Pb fate could therefore be studied through the use of Pb isotopes. Total Pb concentrations and isotopic composition ((206)Pb, (207)Pb and (208)Pb) were then measured in earthworms, casts and bulk soils sampled at different distance from a lead recycling factory. Results showed decreasing Pb concentrations with the distance from the factory whatever the considered matrix (bulk soils, earthworm bodies or cast samples) with higher concentrations in bulk soils than in cast samples. The bivariate plot (208)Pb/(206)Pb ratios versus (206)Pb/(207)Pb ratios showed that all samples can be considered as a linear mixing between metallic process particulate matter (PM) and geochemical Pb background. Calculated anthropogenic fraction of Pb varied between approximately 84% and 100%. Based on Pb isotopic signatures, the comparison between casts, earthworms and bulk soils allowed to conclude that earthworms preferentially ingest the anthropogenic lead fraction associated with coarse soil organic matter. Actually, soil organic matter was better correlated with Pb isotopic ratios than with Pb content in soils. The proposed hypothesis is therefore a decrease of soil organic matter turnover due to Pb pollution with consequences on Pb distribution in soils and earthworm exposure. Finally, Pb isotopes analysis constitutes an efficient tool to study the influence of earthworm bioturbation on Pb cycle in polluted soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

United States Air Force 611th Civil Engineer Squadron, Elmendorf AFB, Alaska. Final engineering evaluation/cost analysis potential tce impact to the drinking water supply, Galena Airport, Alaska

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-02-05

This decision document presents the selected removal action to address potential trichloroethene (TCE) impact to drinking water supply wells, located in the Installation Restoration Program (IRP) site ST009, otherwise known as the West Unit, at Galena Airport, Alaska. The information fron the RI Report is summarized, along with an analysis of potential removal action alternatives, in the Engineering Evaluation/Cost Analysis (EE/CA).

United States Air Force 611th Civil Engineer Squadron, Elmendorf AFB, Alaska. Final engineering evaluation/cost analysis: Petroleum, oil, and lubricants area, Galena Airport, Alaska

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-02-05

This decision document presents the selected removal action for the Installation Restoration Program (IRP) site ST005, otherwise known as the POL Tank Farm, at Galena Airport, Alaska. This decision is based on the administrative record for this site, specifically the draft Remedial Investigation Report (March 1995) and the Treatability Study Report (January 1995) (PB95-225314). The information from these documents is summarized, along with an analysis of potential removal action alternatives in the Engineering Evaluation/Cost Analysis (EE/CA).

Ultrafine particles derived from mineral processing: A case study of the Pb-Zn sulfide ore with emphasis on lead-bearing colloids.

PubMed

Mikhlin, Yuri; Vorobyev, Sergey; Romanchenko, Alexander; Karasev, Sergey; Karacharov, Anton; Zharkov, Sergey

2016-03-01

Although mining and mineral processing industry is a vast source of heavy metal pollutants, the formation and behavior of micrometer- and nanometer-sized particles and their aqueous colloids entered the environment from the technological media has received insufficient attention to date. Here, the yield and characteristics of ultrafine mineral entities produced by routine grinding of the Pb-Zn sulfide ore (Gorevskoe ore deposit, Russia) were studied using laser diffraction analysis (LDA), dynamic light scattering (DLS) and zeta potential measurement, microscopy, X-ray photoelectron spectroscopy, with most attention given to toxic lead species. It was revealed, in particular, that the fraction of particles less that 1 μm in the ground ore typical reaches 0.4 vol. %. The aquatic particles in supernatants were micrometer size aggregates with increased content of zinc, sulfur, calcium as compared with the bulk ore concentrations. The hydrodynamic diameter of the colloidal species decreased with time, with their zeta potentials remaining about -12 mV. The colloids produced from galena were composed of 20-50 nm PbS nanoparticles associated with lead sulfate and thiosulfate, while the surface oxidation products at precipitated galena were largely lead oxyhydroxides. The size and zeta potential of the lead-bearing colloids decreased with time down to about 100 nm and from -15 mV to -30 mV, respectively. And, conversely, lead sulfide nanoparticles were mobilized before the aggregates during redispersion of the precipitates in fresh portions of water. The potential environmental impact of the metal-bearing colloids, which is due to the large-scale production and relative stability, is discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

NASA Astrophysics Data System (ADS)

Baron, S.; Carignan, J.; Ploquin, A.

2003-04-01

Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Nuclear volume effects in equilibrium stable isotope fractionations of mercury, thallium and lead

PubMed Central

Yang, Sha; Liu, Yun

2015-01-01

The nuclear volume effects (NVEs) of Hg, Tl and Pb isotope systems are investigated with careful evaluation on quantum relativistic effects via the Dirac’s formalism of full-electron wave function. Equilibrium 202Hg/198Hg, 205Tl/203Tl, 207Pb/206Pb and 208Pb/206Pb isotope fractionations are found can be up to 3.61‰, 2.54‰, 1.48‰ and 3.72‰ at room temperature, respectively, larger than fractionations predicted by classical mass-dependent isotope fractionations theory. Moreover, the NVE can cause mass-independent fractionations (MIF) for odd-mass isotopes and even-mass isotopes. The plot of vs. for Hg-bearing species falls into a straight line with the slope of 1.66, which is close to previous experimental results. For the first time, Pb4+-bearing species are found can enrich heavier Pb isotopes than Pb2+-bearing species to a surprising extent, e.g., the enrichment can be up to 4.34‰ in terms of 208Pb/206Pb at room temperature, due to their NVEs are in opposite directions. In contrast, fractionations among Pb2+-bearing species are trivial. Therefore, the large Pb fractionation changes provide a potential new tracer for redox conditions in young and closed geologic systems. The magnitudes of NVE-driven even-mass MIFs of Pb isotopes (i.e., ) and odd-mass MIFs (i.e., ) are almost the same but with opposite signs. PMID:26224248

Coupling lead isotopes and element concentrations in epiphytic lichens to track sources of air emissions in the Alberta Oil Sands Region

EPA Science Inventory

A study was conducted that coupled use of element concentrations and lead (Pb) isotope ratios in the lichen Hypogymnia physodes collected during 2002 and 2008, to assess the impacts of air emissions from the Alberta Oil Sands Region (AOSR, Canada) mining and processing operations...

Determining tissue-lead levels in large game mammals harvested with lead bullets: human health concerns.

PubMed

Tsuji, L J S; Wainman, B C; Jayasinghe, R K; VanSpronsen, E P; Liberda, E N

2009-04-01

Recently, the use of lead isotope ratios has definitively identified lead ammunition as a source of lead exposure for First Nations people, but the isotope ratios for lead pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden; however, few studies have determined if lead bullet fragments are present in big game carcasses. We found elevated tissue-lead concentrations (up to 5,726.0 microg/g ww) in liver (5/9) and muscle (6/7) samples of big game harvested with lead bullets and radiographic evidence of lead fragments. Thus, we would advise that the tissue surrounding the wound channel be removed and discarded, as this tissue may be contaminated by lead bullet fragments.

High-precision lead isotopes and stripy plumes: Revisiting the Society chain in French Polynesia

NASA Astrophysics Data System (ADS)

Cordier, Carole; Chauvel, Catherine; Hémond, Christophe

2016-09-01

An increasing number of geochemical studies looked for spatial organization of the isotopic variations along Pacific volcanic island chains (e.g., Hawaii, Marquesas, Samoa and Society Islands) in order to discuss the possible zoning of the plume conduits. Here, we reexamine the occurrence of isotopic stripes in the Society archipelago in French Polynesia, using new Sr-Nd-Hf-Pb isotope ratios of sixty-six lavas from six islands (Mehetia, Moorea, Maupiti, Huahine, Raiatea, Bora-Bora). We demonstrate that the Pb isotope variability observed using literature data is an analytical artifact related to the poor control of mass fractionation during Pb measurements by conventional TIMS technique. New MC-ICP-MS Pb data demonstrate that the isotopic stripes as previously defined disappear. They rather show that individual islands cover a significant part of the entire isotopic range of the chain. We suggest, therefore, that the dominant characteristic of the Society plume is small-scale heterogeneities, evenly distributed within the plume conduit. At a global scale, we show that some ocean island chains with similar geochemical and isotopic characteristics, such as Samoa and Society Islands, define different arrays when variations of Nd with high-precision Pb isotopes are considered. We proposed that this puzzling observation might record differences in recycling age of the basalt + sediment mixture subducted into the mantle and sampled by mantle plume.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2008-01-01

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry (n=53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206Pb/204Pb from 18.186 to 18.391, 207Pb/204Pb from 15.617 to 15.657, 208Pb/204Pb from 38.052 to 38.210, 206Pb/207Pb from c. 1.1625 to 1.1760 and 208Pb/207Pb from c. 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206Pb/204Pb from 18.495 to 19.747 (one sample at 21.495), 207Pb/204Pb from 15.595 to 15.722 (one sample at 15.839), 208Pb/204Pb from 38.186 to 39.162,206Pb/207Pb from c.1.1860 to 1.2575 (one sample at 1.3855) and 208Pb/207Pb from c. 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more

Lead theft--a study of the "uniqueness" of lead from church roofs.

PubMed

Bond, John W; Hainsworth, Sarah V; Lau, Tien L

2013-07-01

In the United Kingdom, theft of lead is common, particularly from churches and other public buildings with lead roofs. To assess the potential to distinguish lead from different sources, 41 samples of lead from 24 church roofs in Northamptonshire, U.K, have been analyzed for relative abundance of trace elements and isotopes of lead using X-ray fluorescence (XRF) and inductively coupled plasma mass spectrometry, respectively. XRF revealed the overall presence of 12 trace elements with the four most abundant, calcium, phosphorus, silicon, and sulfur, showing a large weight percentage standard error of the mean of all samples suggesting variation in the weight percentage of these elements between different church roofs. Multiple samples from the same roofs, but different lead sheets, showed much lower weight percentage standard errors of the mean suggesting similar trace element concentrations. Lead isotope ratios were similar for all samples. Factors likely to affect the occurrence of these trace elements are discussed. © 2013 American Academy of Forensic Sciences.

Lead exposure in raptors from Japan and source identification using Pb stable isotope ratios.

PubMed

Ishii, Chihiro; Nakayama, Shouta M M; Ikenaka, Yoshinori; Nakata, Hokuto; Saito, Keisuke; Watanabe, Yukiko; Mizukawa, Hazuki; Tanabe, Shinsuke; Nomiyama, Kei; Hayashi, Terutake; Ishizuka, Mayumi

2017-11-01

Lead (Pb) poisoning is widespread among raptors and water birds. In Japan, fragments of Pb ammunition are still found in endangered eagles although more than 10 years have passed since legislation regarding use of Pb ammunition was introduced. This study was performed to investigate Pb exposure in raptors from various locations in Japan. We measured hepatic and renal Pb concentrations and hepatic Pb isotope ratios of Steller's sea eagles (Haliaeetus pelagicus), white-tailed sea eagles (Haliaeetus albicilla), golden eagles (Aquila chrysaetos), and 13 other species (total 177 individuals) that were found dead, as well as blood samples from three eagles found in a weakened state during 1993-2015 from Hokkaido (northern part), Honshu (the main island), and Shikoku (a southern island) of Japan. In the present study in Hokkaido, one quarter of the sea eagles showed a high Pb concentration, suggesting exposure to abnormally high Pb levels and Pb poisoning. Pb isotope ratios indicated that endangered Steller's sea eagle and white-tailed sea eagle were poisoned by Pb ammunition that was used illegally in Hokkaido. In other areas of Japan, both surveillance and regulations were less extensive than in Hokkaido, but Pb poisoning in raptors was also noted. Therefore, Pb poisoning is still a serious problem in raptors in various areas of Japan due to accidental ingestion of materials containing Pb, especially Pb ammunition. Copyright © 2017. Published by Elsevier Ltd.

U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA

NASA Astrophysics Data System (ADS)

Rasbury, T.; Luczaj, J.

2017-12-01

Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the

A 500 year sediment lake record of anthropogenic and natural inputs to Windermere (English Lake District) using double-spike lead isotopes, radiochronology, and sediment microanalysis.

PubMed

Miller, Helen; Croudace, Ian W; Bull, Jonathan M; Cotterill, Carol J; Dix, Justin K; Taylor, Rex N

2014-07-01

A high-resolution record of pollution is preserved in recent sediments from Windermere, the largest lake in the English Lake District. Data derived from X-ray core scanning (validated against wavelength dispersive X-ray fluorescence), radiochronological techniques ((210)Pb and (137)Cs) and ultrahigh precision, double-spike mass spectrometry for lead isotopes are combined to decipher the anthropogenic inputs to the lake. The sediment record suggests that while most element concentrations have been stable, there has been a significant increase in lead, zinc, and copper concentrations since the 1930s. Lead isotope down-core variations identify three major contributory sources of anthropogenic (industrial) lead, comprising gasoline lead, coal combustion lead (most likely source is coal-fired steam ships), and lead derived from Carboniferous Pb-Zn mineralization (mining activities). Periods of metal workings do not correlate with peaks in heavy metals due to the trapping efficiency of up-system lakes in the catchment. Heavy metal increases could be due to flood-induced metal inwash after the cessation of mining and the weathering of bedrock in the catchment. The combination of sediment analysis techniques used provides new insights into the pollutant depositional history of Windermere and could be similarly applied to other lake systems to determine the timing and scale of anthropogenic inputs.

Pb isotopes of Gorgona Island (Colombia): isotopic variations correlated with magma type

NASA Astrophysics Data System (ADS)

Dupré, B.; Echeverría, L. M.

1984-02-01

Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8 × 2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206Pb/ 204Pb˜ 19.75 ) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle source regions, and by mixing or contamination between them.

Genesis of the Bangbule Pb-Zn-Cu polymetallic deposit in Tibet, western China: Evidence from zircon U-Pb geochronology and S-Pb isotopes

NASA Astrophysics Data System (ADS)

Kan, Tian; Zheng, Youye; Gao, Shunbao

2016-04-01

The Banbule Pb-Zn-Cu skarn deposit is located in the Longger-Gongbujiangda volcanic magma arc in the Gangdese-Nyainqentanglha Plate. It is the only lead-zinc polymetallic deposit discovered in the westernmost Nyainqentanglha metallogenic belt. The measured and indicated resources include 0.9 Mt of Pb+Zn (4.77% Pb and 4.74% Zn, respectively), 6499 t of Cu, and 178 t of Ag (18.75g/t Ag). The orebodies mainly occur as lenses, veins and irregular shapes in the contact zone between the quartz-porphyry and limestone of the Upper Permian Xiala Formation, or in the boundaries between limestone and sandstone. Pb-Zn-Cu mineralization in the Banbule deposit is closely associated with skarns. The ore minerals are dominated by galena, sphalerite, chalcopyrite, bornite, and magnetite, with subordinate pyrite, malachite, and azurite. The gangue minerals are mainly garnet, actinolite, diopside, quartz, and calcite. The ore-related quartz-porphyry displays LA-ICP-MS zircon U-Pb age of 77.31±0.74 Ma. The δ34S values of sulfides define a narrow range of -0.8 to 4.7‰ indicating a magmatic source for the ore-forming materials. Lead isotopic systematics yield 206Pb/204Pb of 18.698 to 18.752, 207Pb/204Pb of 15.696 to 15.760, and 208Pb/204Pb of 39.097 to 39.320. The data points are constrained around the growth curves of upper crust and orogenic belt according to the tectonic discrimination diagrams. The calculated Δβ - Δγ values plot within the magmatic field according to the discrimination diagram of Zhu et al. (1995). The S-Pb isotopic data suggest that Bangbule is a typical skarn deposit, and the Pb-Zn-Cu mineralization is genetically related to the quartz-porphyry in the mining district. The discovery of the Bangbule deposit indicates that there is metallogenic potential in the westernmost Nyainqentanglha belt, which is of great importance for the exploration work in this area.

Tracing dust transport from Middle-East over Delhi in March 2012 using metal and lead isotope composition

NASA Astrophysics Data System (ADS)

Kumar, S.; Aggarwal, S. G.; Malherbe, J.; Barre, J. P. G.; Berail, S.; Gupta, P. K.; Donard, O. F. X.

2016-05-01

A severe dust-storm which was originated in Middle-East crossed over Delhi during March 20-22, 2012. We have collected these dust-storm (DS) aerosol samples, and analyzed them for selected metals (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Se, Sn, Sr, V and Zn) together with after dust-storm (ADS) and winter (WS) samples. High aerosol mass loadings were observed in DS samples (1097-1965 μg/m3). On the contrary, metals derived prominently from the anthropogenic sources were found lower in concentration compared to that of ADS and WS aerosols. We observed significantly high concentrations of Ni and V (which are abundantly found in crude oils of Middle-East origin) in the DS samples than that of ADS and WS samples. Also enrichment factor (EF) of these metals with respect to Fe shows no significant enrichment (<10). Fe (and Sr) concentrations were also 3-5 fold higher in DS samples compared to ADS and WS. These results suggest that Ni and V can be used as tracers for dust aerosols transported from Middle-East region. Lead isotope signatures can tell about the variation in the sources of urban aerosols. Therefore Pb isotope analyses of these samples were performed using MC-ICP-MS. The isotope ratios, 208Pb/206Pb is determined to be (mean ± sd) 2.1315 ± 0.0018, 2.1370 ± 0.0022 and 2.1389 ± 0.0016, whereas 206Pb/207Pb is 1.1311 ± 0.0022, 1.1244 ± 0.0017 and 1.1233 ± 0.0016 in DS, ADS and WS aerosols, respectively. There is a clear distinction in Pb isotope composition between DS and urban (ADS and WS) aerosols. Further, these results suggest that in urban aerosols, Pb is less radiogenic in nature compared to that of in transported dust aerosols collected in New Delhi.

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaffney, A M; Borg, L E; Connelly, J N

2006-12-22

Uranium-lead ratios (commonly represented as {sup 238}U/{sup 204}Pb = {mu}) calculated for the sources of martian basalts preserve a record of petrogenetic processes that operated during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of {mu} values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range ({sup 206}Pb/{sup 204}Pb = 11.16-11.61). In contrast, themore » Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in {sup 206}Pb/{sup 204}Pb-{sup 207}Pb/{sup 204}Pb-{sup 208}Pb/{sup 204}Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial contamination. Despite the contamination, we are able to use the U-Pb data to determine the initial {sup 206}Pb/{sup 204}Pb of QUE 94201 (11.086 {+-} 0.008) and calculate the {mu} value of the QUE 94201 mantle source to be 1.823 {+-} 0.008. This is the lowest {mu} value calculated for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that {mu} values in martian source reservoirs vary by at least 100%. The range of source {mu} values further indicates that the {mu} value of bulk silicate Mars is approximately three. The amount of variation in the {mu} values of the mantle sources ({mu} {approx} 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

PubMed

Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan

2017-12-19

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Transboundary atmospheric lead pollution.

PubMed

Erel, Yigal; Axelrod, Tamar; Veron, Alain; Mahrer, Yitzak; Katsafados, Petros; Dayan, Uri

2002-08-01

A high-temporal resolution collection technique was applied to refine aerosol sampling in Jerusalem, Israel. Using stable lead isotopes, lead concentrations, synoptic data, and atmospheric modeling, we demonstrate that lead detected in the atmosphere of Jerusalem is not only anthropogenic lead of local origin but also lead emitted in other countries. Fifty-seven percent of the collected samples contained a nontrivial fraction of foreign atmospheric lead and had 206Pb/207Pb values which deviated from the local petrol-lead value (206Pb/207Pb = 1.113) by more than two standard deviations (0.016). Foreign 206Pb/207Pb values were recorded in Jerusalem on several occasions. The synoptic conditions on these dates and reported values of the isotopic composition of lead emitted in various countries around Israel suggest that the foreign lead was transported to Jerusalem from Egypt, Turkey, and East Europe. The average concentration of foreign atmospheric lead in Jerusalem was 23 +/- 17 ng/m3, similar to the average concentration of local atmospheric lead, 21 +/- 18 ng/ m3. Hence, the load of foreign atmospheric lead is similar to the load of local atmospheric lead in Jerusalem.

Tracing the origin of pollution in French Alpine snow and aerosols using lead isotopic ratios.

PubMed

Veysseyre, A M; Bollhöfer, A F; Rosman, K J; Ferrari, C P; Boutron, C F

2001-11-15

Fresh snow samples collected at 15 remote locations and aerosols collected at one location in the French Alps between November 1998 and April 1999 have been analyzed for Pb concentration and isotopic composition by thermal ionization mass spectrometry. The snow samples contained 19-1300 pg/g of Pb with isotopic ratios 206Pb/207Pb (208Pb/207Pb) of 1.1279-1.1607 (2.3983-2.4302). Airborne Pb concentrations at one sampling site ranged from 0.42 to 6.0 ng/m3 with isotopic ratios of 1.1321-1.1427 (2.4029-2.4160). Air mass trajectory analysis combined with isotopic compositions of potential source regions did not show discernible evidence of the long-range atmospheric transport of pollutants. Isotopic ratios in the Alpine snow samples and thus the free troposphere were generally higher than airborne Pb isotopic ratios in urban France, which coupled with the relatively high Pb concentrations suggested a regional anthropogenic Pb source, probably Italy but possibly Eastern Europe.

In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ~3.5Ga Pilbara cherts

USGS Publications Warehouse

Kozdon, R.; Kita, N.T.; Huberty, J.M.; Fournelle, J.H.; Johnson, C.A.; Valley, J.W.

2010-01-01

Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions , from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical

Mineralogical, stable isotope, and fluid inclusion studies of spatially related porphyry Cu and epithermal Au-Te mineralization, Fakos Peninsula, Limnos Island, Greece

NASA Astrophysics Data System (ADS)

Fornadel, Andrew P.; Voudouris, Panagiotis Ch.; Spry, Paul G.; Melfos, Vasilios

2012-05-01

of magmatic fluids with meteoric water in the epithermal environment is responsible for the dilution of the ore fluids that formed Stage 3 veins. Eutectic melting temperatures of -35.4 to -24.3 °C for Type I inclusions hosted in both porphyry- and epithermal-style veins suggest the presence of CaCl2, MgCl2, and/or FeCl2 in the magmatic-hydrothermal fluids. Sulfur isotope values of pyrite, galena, sphalerite, and molybdenite range from δ34S = -6.82 to -0.82 per mil and overlap for porphyry and epithermal sulfides, which suggests a common sulfur source for the two styles of mineralization. The source of sulfur in the system was likely the Fakos quartz monzonite for which the isotopically light sulfur isotope values are the result of changes in oxidation state during sulfide deposition (i.e., boiling) and/or disproportionation of sulfur-rich magmatic volatiles upon cooling. It is less likely that sulfur in the sulfides was derived from the reduction of seawater sulfate or leaching of sulfides from sedimentary rocks given the absence of primary sulfides in sedimentary rocks in the vicinity of the deposit. Late-stage barite (δ34S = 10.5 per mil) is inferred to have formed during mixing of seawater with magmatic ore fluids. Petrological, mineralogical, fluid inclusion, and sulfur isotope data indicate that the metallic mineralization at Fakos Peninsula represents an early porphyry system that is transitional to a later high- to intermediate-sulfidation epithermal gold system. This style of mineralization is similar to porphyry-epithermal metallic mineralization found elsewhere in northeastern Greece (e.g., Pagoni Rachi, St. Demetrios, St. Barbara, Perama Hill, Mavrokoryfi, and Pefka).

Geochemical character and origin of oils in Ordovician reservoir rock, Illinois and Indiana, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guthrie, J.M.; Pratt, L.M.

1995-11-01

Twenty-three oils produced from reservoirs within the Ordovician Galena Group (Trenton equivalent) and one oil from the Mississippian Ste. Genevieve Limestone in the Illinois and Indiana portions of the Illinois basin are characterized. Two end-member oil groups (1) and (2) and one intermediate group (1A) are identified using conventional carbon isotopic analysis of whole and fractionated oils, gas chromatography (GC) of saturated hydrocarbon fractions, isotope-ratio-monitoring gas chromatography/mass spectrometry (irm-GC/MS) of n-alkanes ranging from C{sub 15} to C{sub 25}, and gas chromatography/mass spectrometry (GC/MS) of the aromatic hydrocarbon fractions. Group 1 is characterized by high odd-carbon predominance in mid-chain n-alkanes (C{submore » 15}-C{sub 19}), low abundance Of C{sub 20+}, n-alkanes, and an absence of pristane and phytane. Group IA is characterized by slightly lower odd-carbon predominance of mid-chain n-alkanes, greater abundance of C{sub 20+} n-alkanes compared to group 1, and no pristane and phytane. Conventional correlations of oil to source rock based on carbon isotopic-type curves and hopane (m/z 191) and sterane (m/z 217) distributions are of limited use in distinguishing Ordovician-reservoired oil groups and determining their origin. Oil to source rock correlations using the distribution and carbon isotopic composition of n-alkanes and the m/z 133 chromatograms of n-alkylarenes show that groups 1 and 1A originated from strata of the Upper Ordovician Galena Group. Group 2 either originated solely from the Upper Ordovician Maquoketa Group or from a mixture of oils generated from the Maquoketa Group and the Galena Group. The Mississippian-reservoired oil most likely originated from the Devonian New Albany Group. The use of GC, irm-GC/MS, and GC/MS illustrates the value of integrated molecular and isotopic approaches for correlating oil groups with source rocks.« less

The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

NASA Astrophysics Data System (ADS)

Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

2014-04-01

Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

Precambrian ophiolites of Arabia; a summary of geologic settings, U-Pb geochronology, lead isotope characteristics, and implications for microplate accretion, Kingdom of Saudi Arabia

USGS Publications Warehouse

Pallister, John S.; Stacey, J.S.; Fischer, L.B.; Premo, W.R.

1988-01-01

Feldspar lead-isotope data are of three types: 1) lead from the ophiolitic rocks and arc tonalites of the northwestern Arabian Shield and ophiolitic rocks of the Nabitah suture zone is similar to lead in present midocean ridge basalt, 2) anomalous radiogenic data from the Thurwah ophiolite are from rocks that contain zircons from pre-late Proterozoic continental crust, and 3) feldspar from the Urd ophiolite shows retarded uranogenic lead growth and is related either to an anomalous oceanic mantle source, or in an unknown manner to ancient continental mantle or lower crust of the eastern Arabian Shield.

Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

USGS Publications Warehouse

Church, S.E.

2010-01-01

The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis

PubMed Central

Valentine, Benjamin; Kamenov, George D.; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people’s movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape. PMID:25923705

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis.

PubMed

Valentine, Benjamin; Kamenov, George D; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people's movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape.

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

USGS Publications Warehouse

Dunlap, C.E.; Alpers, Charles N.; Bouse, R.; Taylor, Howard E.; Unruh, D.M.; Flegal, A.R.

2008-01-01

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km2) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment. ?? 2008 Elsevier Ltd.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats.

PubMed

Nakata, Hokuto; Nakayama, Shouta M M; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-10

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown ( Rattus norvegicus , n = 43) and black ( R. rattus , n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats

PubMed Central

Nakata, Hokuto; Nakayama, Shouta M. M.; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B.; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-01

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown (Rattus norvegicus, n = 43) and black (R. rattus, n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed. PMID:28075384

Lead isotopes in North Pacific deep water - Implications for past changes in input sources and circulation patterns

USGS Publications Warehouse

van de Flierdt, T.; Frank, M.; Halliday, A.N.; Hein, J.R.; Hattendorf, B.; Gunther, D.; Kubik, P.W.

2003-01-01

The sources of non-anthropogenic Pb in seawater have been the subject of debate. Here we present Pb isotope time-series that indicate that the non-anthropogenic Pb budget of the northernmost Pacific Ocean has been governed by ocean circulation and riverine inputs, which in turn have ultimately been controlled by tectonic processes. Despite the fact that the investigated locations are situated within the Asian dust plume, and proximal to extensive arc volcanism, eolian contributions have had little impact. We have obtained the first high-resolution and high-precision Pb isotope time-series of North Pacific deep water from two ferromanganese crusts from the Gulf of Alaska in the NE Pacific Ocean, and from the Detroit Seamount in the NW Pacific Ocean. Both crusts were dated applying 10 Be/9Be ratios and yield continuous time-series for the past 13.5 and 9.6 Myr, respectively. Lead isotopes show a monotonic evolution in 206Pb/204Pb from low values in the Miocene (??? 18.57) to high values at present day (??? 18.84) in both crusts, even though they are separated by more than 3000 km along the Aleutian Arc. The variation exceeds the amplitude found in Equatorial Pacific deep water records by about three-fold. There also is a striking similarity in 207Pb/204Pb and 208Pb/ 204Pb ratios of the two crusts, indicating the existence of a local circulation cell in the sub-polar North Pacific, where efficient lateral mixing has taken place but only limited exchange (in terms of Pb) with deep water from the Equatorial Pacific has occurred. Both crusts display well-defined trends with age in Pb-Pb isotope mixing plots, which require the involvement of at least four distinct Pb sources for North Pacific deep water. The Pb isotope time-series reveal that eolian supplies (volcanic ash and continent-derived loess) have only been of minor importance for the dissolved Pb budget of marginal sites in the deep North Pacific over the past 6 Myr. The two predominant sources have been young

Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt

NASA Astrophysics Data System (ADS)

Zoheir, Basem; Emam, Ashraf; Pitcairn, Iain K.; Boskabadi, Arman; Lehaye, Yann; Cooper, Matthew J.

2018-04-01

Trace element composition of sulfides and O, C, Sr and S isotopic data are assessed to constrain the evolution and potential fluid and metal sources of the Um Garayat gold deposit. Ore microscopy and BSE investigations of quartz veins show blocky arsenopyrite and pyrite replaced in part by pyrrhotite, chalcopyrite, sphalerite, galena, and gersdorffite. Free-milling gold occurs commonly in close association with the late sulfides, and along fractures in pyrite. On the other hand, recrystallized pyrite is disseminated in host metavolcaniclastic/metasedimentary rocks that commonly contain carbonaceous material. In situ LA-ICP-MS analysis of sulfides shows the recrystallized pyrite enriched in most trace elements, while blocky pyrite contains only some traces of arsenic. Detected concentrations of gold (up to 17 ppm) were only reported in arsenopyrite disseminated in quartz veins. The δ34S values of blocky pyrite and pyrrhotite in quartz veins define a narrow range (1.6 to 3.7‰), suggesting a homogenous sulfur source which is consistent with the dominantly mafic host rocks. The recrystallized pyrite has a distinctive sulfur isotope composition (δ34S - 9.3 to - 10.6‰), which is rather comparable to diagenetic sulfides. Hydrothermal carbonate in quartz veins and wallrock have nearly constant values of δ18O (10.5 to 11.9‰) and δ13C (- 4.2 to - 5.5‰). Based on constraints from mineral assemblages and chlorite thermometry, data of six samples indicate that carbonate precipitation occurred at 280 °C from a homogenous hydrothermal fluid with δ18OH2O 4.4 ± 0.7‰ and δ13C = 3.7 ± 0.8‰. Strontium isotope values of two samples (87Sr/86Sr = 0.7024 and 0.7025) are similar to the initial 87Sr/86Sr ratios of island arc metabasalts ( 710 Ma) in the South Eastern Desert. The generally homogenous sulfur, C, O, Sr isotope data are suggestive of metamorphogenic fluids, likely produced from dominantly mafic volcanic rocks at the greenschist-amphibolite facies transition.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

Black, Jay R.; Young, Edward D.; Kavner, Abby

2010-02-01

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

Geochemical sources of metal contamination in a coal mining area in Chhattisgarh, India using lead isotopic ratios.

PubMed

Das, Avijit; Patel, Subhra Sarita; Kumar, Rajeev; Krishna, K V S S; Dutta, Saikat; Saha, Manik Chandra; Sengupta, Siladitya; Guha, Dipayan

2018-04-01

A geochemical study of the trace metals and lead isotopic ratios of soil and sediments in Korba, Chhattisgarh, India is presented here for the first time. Korba, the nation's 'power hub' is also the fifth among its eighty-eight most critically polluted industrial hotspots. A very high mean concentration (in mg kg-1) of V (308), Cr (567), Mn (3442), Co (92), Cu (218), Zn (426), Pb (311), Th (123) and U (32) characterized the sediments of the studied area with mean I geo values of the trace metals ranging from -2.29 to 3.27. In the two-ratio scatter Pb isotope plot of the different environmental matrices, except for human blood, coal, soil, sediments, non-washed leaves, flyash and diesel overlapped linearly in the mixing line between diesel as the highest anthropogenic end member and a core sediment fraction representing its geogenic counterpart. The mean 207 Pb/ 206 Pb Pb ratio decreased in the order of diesel (0.9012) > flyash (0.8757) > coal (0.8498) soils and sediments (0.8374) > lowest core sediment fraction (0.8017). Principal Component Analysis (PCA) of the trace metal data extracted V, Cr, Cu, Zn, Pb, U and Th in the first component PC1. The northeastern part of the study area revealed major hotspots of V, Cu, Co, Zn and Pb near the flyash dykes of the power stations. Human blood used as a biomarker for Pb pollution in this study had a mean blood lead level of 28 μg/dl with a distinctive high 207 Pb/ 206 Pb ratio of 0.8828. Published by Elsevier Ltd.

Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

PubMed

Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

2010-07-30

The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright 2010 John Wiley & Sons, Ltd.

Determination of lead, uranium, thorium, and thallium in silicate glass standard materials by isotope dilution mass spectrometry

USGS Publications Warehouse

Barnes, I.L.; Garner, E.L.; Gramlich, J.W.; Moore, L.J.; Murphy, T.J.; Machlan, L.A.; Shields, W.R.; Tatsumoto, M.; Knight, R.J.

1973-01-01

A set of four standard glasses has been prepared which have been doped with 61 different elements at the 500-, 50-, 1-, and 0.02-ppm level. The concentrations of lead, uranium, thorium, and thallium have been determined by isotope dilution mass spectrometry at a number of points in each of the glasses. The results obtained from independent determinations in two laboratories demonstrate the homogeneity of the samples and that precision of the order of 0.5% (95% L.E.) may be obtained by the method even at the 20-ppb level for these elements. The chemical and mass spectrometric procedures necessary are presented.

Identification of sources of lead in children in a primary zinc-lead smelter environment.

PubMed Central

Gulson, Brian L; Mizon, Karen J; Davis, Jeff D; Palmer, Jacqueline M; Vimpani, Graham

2004-01-01

We compared high-precision lead isotopic ratios in deciduous teeth and environmental samples to evaluate sources of lead in 10 children from six houses in a primary zinc-lead smelter community at North Lake Macquarie, New South Wales, Australia. Teeth were sectioned to allow identification of lead exposure in utero and in early childhood. Blood lead levels in the children ranged from 10 to 42 micro g/dL and remained elevated for a number of years. For most children, only a small contribution to tooth lead can be attributed to gasoline and paint sources. In one child with a blood lead concentration of 19.7 microg/dL, paint could account for about 45% of lead in her blood. Comparison of isotopic ratios of tooth lead levels with those from vacuum cleaner dust, dust-fall accumulation, surface wipes, ceiling (attic) dust, and an estimation of the smelter emissions indicates that from approximately 55 to 100% of lead could be derived from the smelter. For a blood sample from another child, > 90% of lead could be derived from the smelter. We found varying amounts of in utero-derived lead in the teeth. Despite the contaminated environment and high blood lead concentrations in the children, the levels of lead in the teeth are surprisingly low compared with those measured in children from other lead mining and smelting communities. PMID:14698931

Lead isotopic composition of trinitite melt glass: evidence for the presence of Canadian industrial lead in the first atomic weapon test.

PubMed

Bellucci, Jeremy J; Simonetti, Antonio; Wallace, Christine; Koeman, Elizabeth C; Burns, Peter C

2013-08-06

The Pb isotopic compositions for 51 spots of melt glass in 11 samples of trinitite have been determined by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trinitite glass yields a large range of Pb isotopic compositions (i.e., (206)Pb/(204)Pb = 17.08-19.04), which reflect mixing between industrial Pb from materials used in the Trinity test and natural geologic components. Areas within trinitite melt glass containing high concentrations of both Cu and Pb, which are derived from the bomb and blast site-related components, were used for delineating the Pb isotopic composition corresponding to the anthropogenic Pb component. Comparison between the isotopic composition estimated here for the industrial Pb used in the Trinity test and those from known Pb deposits worldwide indicates close agreement with ore from the Buchans mine (Newfoundland, Canada). The Buchans mine was active during the time of the Trinity test and was operated by the American Smelting and Refining Company, which could have provided the Pb used in the test. The industrial Pb used in the Trinity test materials is not documented in the literature (or declassified) but could have been present in bricks, solder, pigs, or some other anthropogenic component related to the experiment.

Isotopic composition of Pb in ore deposits of the Betic Cordillera, Spain; origin and relationship to other European deposits

USGS Publications Warehouse

Arribas , Antonio; Tosdal, Richard M.

1994-01-01

The Betic Cordillera in southern Spain is a complex Alpine fold belt that resulted from the Cretaceous through Cenozoic collision of Africa with Europe. The region is illustrative of one of the characteristics of the Alpine-Mediterranean orogen: the occurrence over a limited area of mineral deposits with a wide variety of host rocks, mineralization ages, and styles. The metamorphic basement in the Betic zone is characterized by a nappe structure of superimposed tectonostratigraphic units and consists of lower Paleozoic to Lower Triassic clastic metasedimentary rocks. This is overlain by Middle to Upper Triassic platform carbonate rocks with abundant strata-bound F-Pb-Zn-(Ba) deposits (e.g., Sierra de Gador, Sierra Alhamilla). Cretaceous to Paleogene subduction-related compression in southeastern Spain was followed by Miocene postcollisional extension and resulted in the formation of the Almeria-Cartagena volcanic belt and widespread hydrothermal activity and associated polymetallic mineralization. Typical Miocene hydrothermal deposits include volcanic-hosted Au (e.g., Rodalquilar) and Ag-rich base metal (e.g., Cabo de Gata, Mazarron) deposits as well as complex polymetallic veins, mantos, and irregular replacement bodies which are hosted by Paleozoic and Mesozoic metamorphic rocks and Neogene sedimentary and volcanic rocks (e.g., Cartagena, Sierra Almagrera, Sierra del Aguilon, Loma de Bas).Lead isotope compositions were measured on sulfide samples from nine ore districts and from representative fresh samples of volcanic and basement rock types of the region. The results have been used to evaluate ore-forming processes in southeastern Spain with emphasis on the sources of metals. During a Late Triassic mineralizing event, Pb was leached from Paleozoic clastic metasedimentary rocks and incorporated in galena in strata-bound F-Pb-Zn-(Ba) deposits ( 206 Pb/ 204 Pb = 18.332 + or - 12, 207Pb/ 204 Pb = 15.672 + or - 12, 208 Pb/ 204 Pb = 38.523 + or - 46). The second

Fungal degradation of calcium-, lead- and silicon-bearing minerals.

PubMed

Adeyemi, Ademola O; Gadd, Geoffrey M

2005-06-01

The aim of this study was to examine nutritional influence on the ability of selected filamentous fungi to mediate biogenic weathering of the minerals, apatite, galena and obsidian in order to provide further understanding of the roles of fungi as biogeochemical agents, particularly in relation to the cycling of metals and associated elements found in minerals. The impact of three organic acid producing fungi (Aspergillus niger, Serpula himantioides and Trametes versicolor) on apatite, galena and obsidian was examined in the absence and presence of a carbon and energy source (glucose). Manifestation of fungal weathering included corrosion of mineral surfaces, modification of the mineral substrate through transformation into secondary minerals (i.e. crystal formation) and hyphal penetration of the mineral substrate. Physicochemical interactions of fungal metabolites, e.g. H+ and organic acids, with the minerals are thought to be the primary driving forces responsible. All experimental fungi were capable of mineral surface colonization in the absence and presence of glucose but corrosion of the mineral surface and secondary mineral formation were affected by glucose availability. Only S. himantioides and T. versicolor were able to corrode apatite in the absence of glucose but none of the fungi were capable of doing so with the other minerals. In addition, crystal formation with galena was entirely dependent on the availability of glucose. Penetration of the mineral substrates by fungal hyphae occurred but this did not follow any particular pattern. Although the presence of glucose in the media appeared to influence positively the mineral penetrating abilities of the fungi, the results obtained also showed that some geochemical change(s) might occur under nutrient-limited conditions. It was, however, unclear whether the hyphae actively penetrated the minerals or were growing into pre-existing pores or cracks.

Lead in ancient Rome's city waters.

PubMed

Delile, Hugo; Blichert-Toft, Janne; Goiran, Jean-Philippe; Keay, Simon; Albarède, Francis

2014-05-06

It is now universally accepted that utilization of lead for domestic purposes and water distribution presents a major health hazard. The ancient Roman world was unaware of these risks. How far the gigantic network of lead pipes used in ancient Rome compromised public health in the city is unknown. Lead isotopes in sediments from the harbor of Imperial Rome register the presence of a strong anthropogenic component during the beginning of the Common Era and the Early Middle Ages. They demonstrate that the lead pipes of the water distribution system increased Pb contents in drinking water of the capital city by up to two orders of magnitude over the natural background. The Pb isotope record shows that the discontinuities in the pollution of the Tiber by lead are intimately entwined with the major issues affecting Late Antique Rome and its water distribution system.

The lead (Pb) isotope signature, behaviour and fate of traffic-related lead pollution in roadside soils in The Netherlands.

PubMed

Walraven, N; van Os, B J H; Klaver, G Th; Middelburg, J J; Davies, G R

2014-02-15

In this study the origin, behaviour and fate of anthropogenic Pb in sandy roadside soils were assessed by measuring soil characteristics, Pb isotope composition and content. In 1991 and 2003 samples were taken at different depth intervals at approximately 8 and 75 m from two highways in The Netherlands. The Pb isotope composition of the litter layer ((206)Pb/(207)Pb=1.12-1.14) differs from the deeper soil samples ((206)Pb/(207)Pb=1.20-1.21). Based on a mixing model it is concluded that the samples contain two Pb sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. (206)Pb/(207)Pb ratios demonstrate that the roadside soils were polluted to a depth of ~15 cm. Within this depth interval, anthropogenic Pb content is associated with organic matter. Although Pb pollution only reached a depth of ~15 cm, this does not mean that the topsoils retain all anthropogenic Pb. Due to the low pH and negligible binding capacity of soils at depths >15 cm, anthropogenic Pb migrated towards groundwater after reaching depths of >15 cm. The Pb isotope composition of the groundwater ((206)Pb/(207)Pb=1.135-1.185) establishes that groundwater is polluted with anthropogenic Pb. The contribution of anthropogenic Pb to the groundwater varies between ~30 and 100%. Based on the difference in soil Pb content and Pb isotope compositions over a period of 12 years, downward Pb migration is calculated to vary from 72 ± 95 to 324 ± 279 mg m(-2)y(-1). Assuming that the downward Pb flux is constant over time, it is calculated that 35-90% of the atmospherically delivered Pb has migrated to the groundwater. Copyright © 2013 Elsevier B.V. All rights reserved.

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

NASA Astrophysics Data System (ADS)

Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-11-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

PubMed Central

Chen, Mengli; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-01-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element

Metal enrichment and lead isotope analysis for source apportionment in the urban dust and rural surface soil.

PubMed

Yu, Yang; Li, Yingxia; Li, Ben; Shen, Zhenyao; Stenstrom, Michael K

2016-09-01

To understand the metal accumulation in the environment and identify its sources, 29 different metal contents and lead (Pb) isotope ratios were determined for 40 urban dust samples, 36 surface soil samples, and one river sediment sample collected in the municipality of Beijing, China. Results showed that cadmium, copper (Cu), mercury, Pb, antimony (Sb), and zinc demonstrated to be the typical urban contaminants and mostly influenced by the adjacent human activities with higher content to background ratios and SD values. Among the 29 metal elements investigated, Cu and Sb were found to be the most distinct elements that were highly affected by the developing level and congestion status of the cities with much higher contents in dust in more developed and congested cities. There was a relatively wider range of Pb isotope ratios of country surface soil than those of urban dust. The results of source identification based on Pb isotope ratios showed that coal combustion was the first largest Pb source and vehicle exhaust was the second largest source. The sum of them accounted for 74.6% mass proportion of overall Pb pollution on average. The surface soil sample collected at an iron mine had the highest (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios indicating ore had much higher ratios than other sources. The fine particle subsamples had higher (204)Pb/(206)Pb, (207)Pb/(206)Pb, and (208)Pb/(206)Pb ratios than the coarse particle subsamples indicating more anthropogenic sources of coal combustion and vehicle exhaust for fine particles and more background influence for coarse particles. These results help with pinpointing the major Pb sources and applying suitable measures for the target sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lead isotopes and trace metal ratios of aerosols as tracers of Pb pollution sources in Kanpur, India

NASA Astrophysics Data System (ADS)

Sen, Indra; Bizimis, Michael; Tripathi, Sachchida; Paul, Debajyoti; Tyagi, Swati; Sengupta, Deep

2015-04-01

The anthropogenic flux of Pb in the Earth's surface is almost an order of magnitude higher than its corresponding natural flux [1]. Identifying the sources and pathways of anthropogenic Pb in environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb- isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, an industrial city in northern India. The Pb concentration in the airborne particulate matter varies between 14-216 ng/m3, while the other heavy metals vary by factor of 10 or less, e.g. Cd=0.3-3 ng/m3, As=0.4-3.5 ng/m3, Zn=36-161 ng/m3, and Cu=3-22 ng/m3. The 206Pb/207Pb, 208Pb/206Pb, and 208Pb/207Pb vary between 1.112 - 1.129, 2.123-2.141, and 2.409-2.424 respectively, and are highly correlated with each other (R2>0.9). Pb isotopes and trace metal data reveals that coal combustion is the major source of anthropogenic Pb in the atmosphere, with limited contribution from mining and smelting processes. We further conclude that combination of Pb isotope ratios and V/Pb ratios are powerful tracers for Pb source apportionment studies, which is otherwise difficult to differentiate based only on Pb systematics [1] Sen and Peucker-Ehrenbrink (2012), Environ. Sci. Technol.(46), 8601-8609

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

NASA Technical Reports Server (NTRS)

Simon, Justin

2017-01-01

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Hazardous-waste-characterization survey of unknown drums at the 21st Tactical Fighter Wing, Elmendorf and Shemya Air Force Bases, and Galena and King Salmon Airports, Alaska. Final report 2-13 Aug 91

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bishop, M.S.

1991-12-01

At the request of the USAF Regional Hospital Elmendorf/SGPB (PACAF), the Armstrong Laboratory, Occupational and Environmental Health Directorate, conducted a hazardous waste characterization survey of unknown drums at Elmendorf AFB from 2 Aug - 13 Aug 91. The scope of the survey was to sample and characterize drums of unknown material stored at Elmendorf AFB, Shemya AFB, and Galena and King Salmon Airports. Several waste streams were sampled at Elmendorf AFB to revalidate sample results from a previous survey.

Fishing for isotopes in the Brookhaven Lab Isotope Producer (BLIP) cooling water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fitzsimmons, Jonathan

Be-7 has been used in environmental studies; the isotope is produced during BLIP irradiations and accumulates in the 320 gallons of cooling water. Be-7 has a 53.24 day half-life, so the optimal production/purification time is at the end of the BLIP run season. To purify Be-7 fifteen to twenty gallons of BLIP cooling water are removed and pumped through ion exchange columns that retain Be-7. This labor intensive approach captures ~15 mCi of Be-7, but the solution requires further purification. The method can lead to increased radiation exposure to staff. The ideal way to capture isotopes from large volumes ismore » to reach in to the solution and selectively pull out the desired isotope. It is a lot like fishing.« less

Isotopic identification of natural vs. anthropogenic lead sources in marine sediments from the inner Ría de Vigo (NW Spain).

PubMed

Álvarez-Iglesias, P; Rubio, B; Millos, J

2012-10-15

San Simón Bay, the inner part of the Ría de Vigo (NW Spain), an area previously identified as highly polluted by Pb, was selected for the application of Pb stable isotope ratios as a fingerprinting tool in subtidal and intertidal sediment cores. Lead isotopic ratios were determined by inductively coupled plasma mass spectrometry on extracts from bulk samples after total acid digestion. Depth-wise profiles of (206)Pb/(207)Pb, (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb and (208)Pb/(207)Pb ratios showed, in general, an upward decrease for both intertidal and subtidal sediments as a consequence of the anthropogenic activities over the last century, or centuries. Waste channel samples from a nearby ceramic factory showed characteristic Pb stable isotope ratios different from those typical of coal and petrol. Natural isotope ratios from non-polluted samples were established for the study area, differentiating sediments from granitic or schist-gneiss sources. A binary mixing model employed on the polluted samples allowed estimating the anthropogenic inputs to the bay. These inputs represented between 25 and 98% of Pb inputs in intertidal samples, and 9-84% in subtidal samples, their contributions varying with time. Anthropogenic sources were apportioned according to a three-source model. Coal combustion-related emissions were the main anthropogenic source Pb to the bay (60-70%) before the establishment of the ceramic factory in the area (in the 1970s) which has since constituted the main source (95-100%), followed by petrol-related emissions. The Pb inputs history for the intertidal area was determined for the 20th century, and, for the subtidal area, the 19th and 20th centuries. Copyright © 2012 Elsevier B.V. All rights reserved.

Microscopic model for the isotope effect in the high-Tc oxides

NASA Astrophysics Data System (ADS)

Kresin, V. Z.; Wolf, S. A.

1994-02-01

An unconventional microscopic mechanism relating Tc and the isotope substitution for the doped superconductors such as the high-Tc oxides is proposed. Strong nonadiabaticity, when it is impossible, strictly speaking, to separate fully the nuclear and electronic degrees of freedom, leads to a peculiar dependence of the carrier concentration n on the ionic mass M. This case corresponds, for example, to the isotopic substitution of the axial oxygen in YBa2Cu3O7-x. Because of the dependence of Tc on n, this leads to the dependence of Tc on M, that is to the isotope effect. The minimum value of the isotope coefficient corresponds to Tc=Tmaxc.

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Hintelmann, Holger; Lu, ShengYong

2003-06-01

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

Bibliography of selected references on the hydrogeologic and chemical properties of the Galena-Platteville bedrock unit in Illinois and Wisconsin, 1877-1997

USGS Publications Warehouse

Brown, Timothy A.; Dunning, Charles P.; Batten, William G.

1997-01-01

This report presents selected references concerning the Galena-Platteville deposits in Illinois and Wisconsin published from 1877 to 1997. Sources of the bibliographic information are the Universities of Illinois and Wisconsin Library Computer Systems; Illinet Online; the Illinois and Wisconsin District Libraries of the U.S. Geological Survey; U.S. Geological Survey Selected Water Resources Abstracts; U.S. Environmental Protection Agency reports; and Federal, State, and local agencies, corporations, and consultants. The bibliography is arranged alphabetically, by county, in Illinois and Wisconsin. The references available for each county are arranged alphabetically by author. In addition, one or more selected hydrogeologic key words describing the content of the reference follow each listing. These key words are geophysical properties, hydraulic properties, inorganic geochemistry, lithology, organic geochemistry, physical properties, and water use. Included in the bibliography are 186 references obtained for 15 counties in Illinois and 21 counties in Wisconsin.

GEOLOGY, SULFUR ISOTOPES AND THE ORIGIN OF THE HEATH STEELE ORE DEPOSITS, NEWCASTLE, N.B., CANADA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dechow, E.

The Heath Steele mine is located 35 miles northwest of Newcastle, New Brunswick, Canada. Middle Ordovician Tetagouche Group rocks, consisting of siliceous and basic volcanic rocks, and fine-grained quartz sericite schists and porphyry, have been folded into a steeply plunging recumbent anticline. The ore deposits of zinc, lead, and copper are associated with minor folding and/or sheared dilatent zones at or near the contact between porphyry and fine-grained senicitic schist. Mineralogically the sulfide bodies consist of early, euhedral arsenopyrite, magnetite, and pyrite, followed by interstitial pyrrhotite, sphalerite, chalcopyrite and galena. Minor minerals are ternantite-tetrahedrite, bismuthinite, marcasite, hematite, and some graphite.more » Supergene minerals consist of chalcocite, covellite, and marcasite with a little native silver. Little hypogene replacement has taken place between the minerals, which show a "porphyritic" texture. Sulfur isotope ratios were determined for over 150 sulfide and sulfate specimens from five of the seven ore bodies, and from granite, acid and basic volcanics, porphyry, and sediments. The results indicate that there is no detectable fractionation either during hypogene mineralization or supergene enrichment. The spread (21.82 to 22.02) covered by the ratios is narrow, and suggestive of a well homogenized source of mineral solutions. The enrichment of S/sup 34/ in the ore sulfides and the presence of graphite, evident from mineralographic studies and mass spectrometric analysis, suggests reduction of original sulfates (known to be enriched in S/sup 34/) by organic carbon at temperatures in excess of 500 deg C. A calculation based on the isotopic exchange reaction between sulfide and sulfate under equilibrium conditions and the spread of the ratios indicates a temperature of 700 to 800 deg C for the source. Finally the ratios determined for sulfides in a gneissic granite close to Heath Steele have the same ratio as the ore

A European lead isotope signal recorded from 6000 to 300 years BP in coastal marshes (SW France)

NASA Astrophysics Data System (ADS)

Alfonso, S.; Grousset, F.; Massé, L.; Tastet, J.-P.

Cores covering the last 6000 years were recovered from two marshes from south-western France. They were studied in an attempt to build a reliable regional record of heavy metal pollution. The cores were dated using 14C and historical data. Both Pb concentrations and Pb isotopic composition ( 206Pb/ 207Pb and 208Pb/ 206Pb) were measured in bulk sediment samples using the inductively coupled plasma-mass spectrometer technique. The evolution of the 206Pb/ 207Pb ratio recorded in both marshes reveals a good correlation with the worldwide Pb production during the last 5000 years. The lead isotopic records reveal some general trends, along with a few typical events such as the imprints of the pre-anthropogenic background between 6000 and 2300 years BP, the mining activity during the Roman and Greek periods from 2300 to 1700 years BP, the fall of the Roman Empire and the mining activity in Central Europe since the 11th century AD. These results are also consistent with records obtained in other European environments. Consequently, the European atmospheric signal is recorded in these marshes, hiding expected local riverine contributions. Thus, such records may contribute to the construction of a chronological standard curve for continental environments. However, it will be necessary to study other records more accurately dated to obtain an adequate precision before such a reference curve can be set-up.

Lead mobilization during tectonic reactivation of the western Baltic Shield

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romer, R.L.; Wright, J.E.

Lead isotope data from sulfide deposits of the western part of the Baltic Shield define mixing lines in the [sup 206]Pb/[sup 204]Pb-[sup 207]Pb/[sup 204]Pb diagram. Lead from two types of sulfide deposits have been investigated: (1) Exhalative and volcanogenic deposits that are syngenetic with their host rocks; and (2) vein deposits. The syngenetic deposits locally show a very wide range of lead isotopic compositions that reflect a variable addition of highly radiogenic lead, while the vein deposits, although they have radiogenic lead isotopic compositions, exhibit only limited isotopic variations. In different provinces of the shield, both types of deposits fallmore » on the same lead mixing array. The slope of the lead mixing lines varies as a function of the age of basement rocks and the age of the tectonic event which produced the lead mobilization and therefore relates the source rock age with the age of lead mobilization. Calculated mixing ages fall into several short time periods that correspond either to orogenic events or to major phases of continental rifting. The orogenic events are the ca 360--430 Ma Caledonian, ca 900--1100 Ma Sveconorwegian, and the ca 1800--1900 Ma Svecofennian orogenic cycles. The rifting events correspond to the formation of the ca 280 Ma Oslo rift and the Ordovician (ca 450 Ma) graben system in the area of the present Gulf of Bothnia. Each mixing age indicates that lead was mobilized, probably as a consequence of mild thermal disturbances, and that the crust was permeable to lead migration. The data show that the geographic distribution of sulfide deposits with highly radiogenic lead isotopic compositions coincides with old graben systems, orogenic belts, and orogenic forelands on the Baltic Shield. The ages of vein deposits and their geographic distribution demonstrate multiple tectonic reactivation of the interior of the Baltic Shield in response to orogenic events at its margin. 68 refs., 6 refs., 4 tabs.« less

Isotopic equilibration between dissolved and suspended particulate lead in the Atlantic Ocean - Evidence from Pb-210 and stable Pb isotopes

NASA Technical Reports Server (NTRS)

Sherrell, Robert M.; Boyle, Edward A.; Hamelin, Bruno

1992-01-01

Vertical profiles of, on one hand, the stable Pb isotopic composition, and on the other, the ratio of total Pb to Pb-210 in suspended particles, are noted to closely track contemporaneous depth variations in these ratios for dissolved Pb throughout the upper 2 km of the Sargasso Sea near Bermuda. A simple flux model suggests that the effect of deep ocean scavenging processes on the flux and isotopic composition of Pb sinking on large particles was minor throughout the preanthropogenic, and most of the anthropogenic era: but it has become more important as surface inputs decrease to preleaded gasoline levels, perhaps exceeding the contribution of surface-derived Pb flux in the next decade.

Stable Isotopes in Evaluation of Greenhouse Gas Emissions

USDA-ARS?s Scientific Manuscript database

Isotopes offer a unique way to have natural tracers present in the ecosystem to track produced greenhouse gases (GHG) through multiple scales. Isotopes are simply atoms of the same element (same number of protons) with differing number of neutrons. This differing number of neutrons leads to differen...

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Kinetic analysis of lead metabolism in healthy humans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rabinowitz, M.B.; Wetherill, G.W.; Kopple, J.D.

The steady state kinetics of lead metabolism were studied in five healthy men with stable isotope tracers. Subjects lived in a metabolic unit and ate constant low lead diets. Their intake was supplemented each day with 79 to 204 ..mu..g of enriched lead-204 as nitrate which was ingested with meals for 1 to 124 days. The concentration and isotopic composition of lead was determined serially in blood, urine, feces, and diet and less commonly in hair, nails, sweat, bone, and alimentary tract secretions by isotopic dilution, mass spectrometric analysis. The data suggest a three-compartmental model for lead metabolism. The firstmore » compartment encompasses blood and is 1.5 to 2.2 times larger than the blood mass. It contains approximately 1.7 to 2.0 mg of lead and has a mean life of 35 days. This pool is in direct communication with ingested lead, urinary lead, and pools two and three. The second compartment is largely composed of soft tissue, contains about 0.3 to 0.9 mg of lead, and has a mean life of approximately 40 days. This pool gives rise to lead in hair, nails, sweat, and salivary, gastric, pancreatic, and biliary secretions. Pool three resides primarily in the skeleton, contains the vast quantity of body lead, and has a very slow mean life. Bones appear to differ in their rates of lead turnover. Within the relatively small changes in blood lead observed in the present study, the transfer coefficients between the pools remained constant.« less

Isotopic source signatures for atmospheric lead: the Southern Hemisphere

NASA Astrophysics Data System (ADS)

Bollhöfer, A.; Rosman, K. J. R.

2000-10-01

Aerosols collected between 1994 and 1999 at more than 70 different sites affecting the Southern Hemisphere have been measured for their 206Pb/ 207Pb, 208Pb/ 207Pb and 206Pb/ 204Pb ratios and Pb concentrations. Lower ratios are found at the southern tips of Africa, Australia and South America probably due to the supply of alkyllead from a common supplier such as Associated Octel. The ratios increase in a northerly direction probably due to a changing market share in alkyllead or an increasing industrial Pb contribution. The geographical variations in isotopic signatures made it possible to broadly characterize the different regions that influence the Southern Hemisphere. Brazil and Argentina exhibited 206Pb/ 207Pb, 208Pb/ 207Pb and 206Pb/ 204Pb ratios in aerosols of 1.141-1.184, 2.416-2.442 and 17.77-18.57, respectively. Mexican aerosols had values of 1.188-1.197, 2.452-2.463 and 18.46-18.73. Aerosols sampled in Chile had low ratios in the South of 1.063-1.094, 2.337-2.373 and 16.46-17.13 which increased in a northerly direction. Emissions from South Africa were characterized by ratios 1.067-1.090, 2.340-2.358 and 16.53-16.99. In 1994-1995 Australia and New Zealand had ratios of 1.060-1.193, 2.324-2.445 and 16.08-18.54. In 1997 however, the range was narrower: 1.072-1.112, 2.342-2.398 and 16.55-17.36, respectively. These isotopic signatures are potentially useful for tracing sources of pollution and the movement of air-masses on a global scale.

Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana, Cuba.

PubMed

Alvarez, Alfredo Montero; Estévez Alvarez, Juan R; do Nascimento, Clístenes Williams Araújo; González, Iván Pupo; Rizo, Oscar Díaz; Carzola, Lázaro Lima; Torres, Roberto Ayllón; Pascual, Jorge Gómez

2017-01-01

Epiphytic lichens, collected from 119 sampling sites grown over "Roistonea Royal Palm" trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The 206 Pb/ 207 Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L -1 ) confirms the official statement that leaded gasoline is no longer used in Cuba.

Isotopic signatures suggest important contributions from recycled gasoline, road dust and non-exhaust traffic sources for copper, zinc and lead in PM10 in London, United Kingdom

NASA Astrophysics Data System (ADS)

Dong, Shuofei; Ochoa Gonzalez, Raquel; Harrison, Roy M.; Green, David; North, Robin; Fowler, Geoff; Weiss, Dominik

2017-09-01

The aim of this study was to improve our understanding of what controls the isotope composition of Cu, Zn and Pb in particulate matter (PM) in the urban environment and to develop these isotope systems as possible source tracers. To this end, isotope ratios (Cu, Zn and Pb) and trace element concentrations (Fe, Al, Cu, Zn, Sb, Ba, Pb, Cr, Ni and V) were determined in PM10 collected at two road sites with contrasting traffic densities in central London, UK, during two weeks in summer 2010, and in potential sources, including non-combustion traffic emissions (tires and brakes), road furniture (road paint, manhole cover and road tarmac surface) and road dust. Iron, Ba and Sb were used as proxies for emissions derived from brake pads, and Ni, and V for emissions derived from fossil fuel oil. The isotopic composition of Pb (expressed using 206Pb/207Pb) ranged between 1.1137 and 1.1364. The isotope ratios of Cu and Zn expressed as δ65CuNIST976 and δ66ZnLyon ranged between -0.01‰ and +0.51‰ and between -0.21‰ and +0.33‰, respectively. We did not find significant differences in the isotope signatures in PM10 over the two weeks sampling period and between the two sites, suggesting similar sources for each metal at both sites despite their different traffic densities. The stable isotope composition of Pb suggests significant contribution from road dust resuspension and from recycled leaded gasoline. The Cu and Zn isotope signatures of tires, brakes and road dust overlap with those of PM10. The correlation between the enrichments of Sb, Cu, Ba and Fe in PM10 support the previously established hypothesis that Cu isotope ratios are controlled by non-exhaust traffic emission sources in urban environments (Ochoa Gonzalez et al., 2016). Analysis of the Zn isotope signatures in PM10 and possible sources at the two sites suggests significant contribution from tire wear. However, temporary additional sources, likely high temperature industrial emissions, need to be invoked

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

Distribution, origin, and transformation of metal and metalloid pollution in vegetable fields, irrigation water, and aerosols near a Pb-Zn mine.

PubMed

Luo, Liqiang; Chu, Binbin; Liu, Ying; Wang, Xiaofang; Xu, Tao; Bo, Ying

2014-01-01

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind.Highlights• Mining activities generated heavy metal pollution in fields around a Pb-Zn mine• The elements from water and soils are strongly correlated• Anglesite and cerussite are evidence of galena transformation into secondary minerals• Particulate matter is an important transport carrier of pollution.

Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

PubMed

Fortunato, G; Wunderli, S

2003-09-01

The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

König, Stephan; Wille, Martin; Voegelin, Andrea; Schoenberg, Ronny

2016-08-01

This study presents Mo isotope data for arc lavas from different subduction zones that range between δ 98 / 95 Mo = - 0.72 and + 0.07 ‰. Heaviest isotope values are observed for the most slab fluid dominated samples. Isotopically lighter signatures are related to increasing relevance of terrigenous sediment subduction and sediment melt components. Our observation complements previous conclusions that an isotopically heavy Mo fluid flux likely mirrors selective incorporation of isotopically light Mo in secondary minerals within the subducting slab. Analogue to this interpretation, low δ 98 / 95 Mo flux that coincides with terrigenous sediment subduction and sediment melting cannot be simply related to a recycled input signature. Instead, breakdown of the controlling secondary minerals during sediment melting may release the light component and lead to decreasing δ 98 / 95 Mo influx into subarc mantle sources. The natural range between slab dehydration and hydrous sediment melting may thus cause a large spread of δ 98 / 95 Mo in global subduction zone magmas.

Lead in ancient Rome’s city waters

PubMed Central

Delile, Hugo; Blichert-Toft, Janne; Goiran, Jean-Philippe; Keay, Simon; Albarède, Francis

2014-01-01

It is now universally accepted that utilization of lead for domestic purposes and water distribution presents a major health hazard. The ancient Roman world was unaware of these risks. How far the gigantic network of lead pipes used in ancient Rome compromised public health in the city is unknown. Lead isotopes in sediments from the harbor of Imperial Rome register the presence of a strong anthropogenic component during the beginning of the Common Era and the Early Middle Ages. They demonstrate that the lead pipes of the water distribution system increased Pb contents in drinking water of the capital city by up to two orders of magnitude over the natural background. The Pb isotope record shows that the discontinuities in the pollution of the Tiber by lead are intimately entwined with the major issues affecting Late Antique Rome and its water distribution system. PMID:24753588

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

USGS Publications Warehouse

Odigie, Kingsley; Cohen, A.D.; Swarzenski, Peter W.; Flegal, R

2014-01-01

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77–0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82–0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions

Electron–Rotor Interaction in Organic–Inorganic Lead Iodide Perovskites Discovered by Isotope Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Jue; Yang, Mengjin; Ma, Xiangchao

We report on the carrier-rotor coupling effect in perovskite organic-inorganic hybrid lead iodide (CH3NH3PbI3) compounds discovered by isotope effects. Deuterated organic-inorganic perovskite compounds including CH3ND3PbI3, CD3NH3PbI3, and CD3ND3PbI3 were synthesized. Devices made from regular CH3NH3PbI3 and deuterated CH3ND3PbI3 exhibit comparable performance in band gap, current-voltage, carrier mobility, and power conversion efficiency. However, a time-resolved photoluminescence (TRPL) study reveals that CH3NH3PbI3 exhibits notably longer carrier lifetime than that of CH3ND3PbI3, in both thin-film and single crystal formats. Furthermore, the comparison in carrier lifetime between CD3NH3PbI3 and CH3ND3PbI3 single crystals suggests that vibrational modes in methylammonium (MA(+)) have little impact on carriermore » lifetime. In contrast, the fully deuterated compound CD3ND3PbI3 reconfirmed the trend of decreasing carrier lifetime upon the increasing moment of inertia of cationic MA(+). Polaron model elucidates the electron-rotor interaction.« less

Electron–Rotor Interaction in Organic–Inorganic Lead Iodide Perovskites Discovered by Isotope Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Jue; Yang, Mengjin; Ma, Xiangchao

We report on the carrier-rotor coupling effect in perovskite organic-inorganic hybrid lead iodide (CH3NH3PbI3) compounds discovered by isotope effects. Deuterated organic-inorganic perovskite compounds including CH3ND3PbI3, CD3NH3PbI3, and CD3ND3PbI3 were synthesized. Devices made from regular CH3NH3PbI3 and deuterated CH3ND3PbI3 exhibit comparable performance in band gap, current-voltage, carrier mobility, and power conversion efficiency. However, a time-resolved photoluminescence (TRPL) study reveals that CH3NH3PbI3 exhibits notably longer carrier lifetime than that of CH3ND3PbI3, in both thin-film and single-crystal formats. Furthermore, the comparison in carrier lifetime between CD3NH3PbI3 and CH3ND3PbI3 single crystals suggests that vibrational modes in methylammonium (MA+) have little impact on carrier lifetime.more » In contrast, the fully deuterated compound CD3ND3PbI3 reconfirmed the trend of decreasing carrier lifetime upon the increasing moment of inertia of cationic MA+. Polaron model elucidates the electron-rotor interaction.« less

Electron-Rotor Interaction in Organic-Inorganic Lead Iodide Perovskites Discovered by Isotope Effects.

PubMed

Gong, Jue; Yang, Mengjin; Ma, Xiangchao; Schaller, Richard D; Liu, Gang; Kong, Lingping; Yang, Ye; Beard, Matthew C; Lesslie, Michael; Dai, Ying; Huang, Baibiao; Zhu, Kai; Xu, Tao

2016-08-04

We report on the carrier-rotor coupling effect in perovskite organic-inorganic hybrid lead iodide (CH3NH3PbI3) compounds discovered by isotope effects. Deuterated organic-inorganic perovskite compounds including CH3ND3PbI3, CD3NH3PbI3, and CD3ND3PbI3 were synthesized. Devices made from regular CH3NH3PbI3 and deuterated CH3ND3PbI3 exhibit comparable performance in band gap, current-voltage, carrier mobility, and power conversion efficiency. However, a time-resolved photoluminescence (TRPL) study reveals that CH3NH3PbI3 exhibits notably longer carrier lifetime than that of CH3ND3PbI3, in both thin-film and single-crystal formats. Furthermore, the comparison in carrier lifetime between CD3NH3PbI3 and CH3ND3PbI3 single crystals suggests that vibrational modes in methylammonium (MA(+)) have little impact on carrier lifetime. In contrast, the fully deuterated compound CD3ND3PbI3 reconfirmed the trend of decreasing carrier lifetime upon the increasing moment of inertia of cationic MA(+). Polaron model elucidates the electron-rotor interaction.

Feldspar palaeo-isochrons from early Archaean TTGs: Pb-isotope evidence for a high U/Pb terrestrial Hadean crust

NASA Astrophysics Data System (ADS)

Kamber, B. S.; Whitehouse, M. J.; Moorbath, S.; Collerson, K. D.

2001-12-01

Feldspar lead-isotope data for 22 early Archaean (3.80-3.82 Ga) tonalitic gneisses from an area south of the Isua greenstone belt (IGB),West Greenland, define a steep linear trend in common Pb-isotope space with an apparent age of 4480+/-77 Ma. Feldspars from interleaved amphibolites yield a similar array corresponding to a date of 4455+/-540 Ma. These regression lines are palaeo-isochrons that formed during feldspar-whole rock Pb-isotope homogenisation a long time (1.8 Ga) after rock formation but confirm the extreme antiquity (3.81 Ga) of the gneissic protoliths [1; this study]. Unlike their whole-rock counterparts, feldspar palaeo-isochrons are immune to rotational effects caused by the vagaries of U/Pb fractionation. Hence, comparison of their intercept with mantle Pb-isotope evolution models yields meaningful information regarding the source history of the magmatic precursors. The locus of intersection between the palaeo-isochrons and terrestrial mantle Pb-isotope evolution lines shows that the gneissic precursors of these 3.81 Ga gneisses were derived from a source with a substantially higher time-integrated U/Pb ratio than the mantle. Similar requirements for a high U/Pb source have been found for IGB BIF [2], IGB carbonate [3], and particularly IGB galenas [4]. Significantly, a single high U/Pb source that separated from the MORB-source mantle at ca. 4.3 Ga with a 238U/204Pb of ca. 10.5 provides a good fit to all these observations. In contrast to many previous models based on Nd and Hf-isotope evidence we propose that this reservoir was not a mantle source but the Hadean basaltic crust which, in the absence of an operating subduction process, encased the early Earth. Differentiation of the early high U/Pb basaltic crust could have occurred in response to gravitational sinking of cold mantle material or meteorite impact, and produced zircon-bearing magmatic rocks. The subchondritic Hf-isotope ratios of ca. 3.8 Ga zircons support this model [5] provided that

Lead and strontium isotopes as monitors of anthropogenic contaminants in the surficial environment: Chapter 12

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2018-01-01

Isotopic discrimination can be an effective tool in establishing a direct link between sources of Pb contamination and the presence of anomalously high concentrations of Pb in waters, soils, and organisms. Residential wells supplying water containing up to 1600 ppb Pb to houses built on the former Mohr orchards commercial site, near Allentown, Pennsylvania, United States, were evaluated to discern anthropogenic from geogenic sources. Pb and Sr isotopic data and REE data were determined for waters from residential wells, test wells (drilled for this study), and surface waters from pond and creeks. Local soils, sediments, bedrock, Zn-Pb mineralization and coal were also analyzed, together with locally used Pb-As pesticide. Pb isotope data for residential wells, test wells, and surface waters show substantial overlap with Pb data reflecting anthropogenic actions (e.g., burning fossil fuels, industrial and urban processing activities). Limited contributions of Pb from bedrock, soils, and pesticides are evident. High Pb concentrations in the residential waters are likely related to Pb in groundwater accumulating in sediment in the residential water tanks. The Pb isotope features of waters in underlying shallow aquifers that supply residential wells in the region are best interpreted as reflecting a legacy of anthropogenic Pb rather than geogenic Pb.

Lead isotopes in lichen transplants around a Cu smelter in Russia determined by MC-ICP-MS reveal transient records of multiple sources.

PubMed

Spiro, B; Weiss, D J; Purvis, O W; Mikhailova, I; Williamson, B J; Coles, B J; Udachin, V

2004-12-15

Transplants of the lichen Hypogymnia physodes, which is relatively tolerant to SO2 and heavy metals, were deployed for 3 months over a 60 km long SW-NE transect centered on a highly polluting Cu smelter and its adjoining town of Karabash, southern Urals, Russia. The abundance of 206Pb, 207Pb, 208Pb, and 204Pb were determined by MC-ICP-MS. The measurement of 204Pb revealed critical features, which would otherwise remain concealed: (i) The precise isotope ratios referenced to 204Pb allowed several different sources to be resolved even within the small area covered: (a) the obvious pollutant source of the Karabash Cu smelter; (b) two dispersed sources, likely to include soil with lower and different contributions of thorogenic and uranogenic lead; and (c) one anthropogenic source with higher contribution of 235U derived Pb. (ii) In part of the transect, the Pb isotope composition changed while the Pb concentrations remained the same. This indicates that the Pb content of the transplantation material from the background site was largely replaced and that the transplants provide a transient record reflecting a continuous accumulation and loss of environmental Pb, probably mainly in the form of extracellular particles. Overall, the method of lichen transplantation coupled with Pb isotope ratio determinations proved effective in assessing the usefulness of lichens in biomonitoring and in resolving different sources of atmospheric deposition.

Isotopically constrained lead sources in fugitive dust from unsurfaced roads in the southeast Missouri mining district.

PubMed

Witt, Emitt C; Pribil, Michael J; Hogan, John P; Wronkiewicz, David J

2016-09-01

The isotopic composition of lead (Pb) in fugitive dust suspended by a vehicle from 13 unsurfaced roads in Missouri was measured to identify the source of Pb within an established long-term mining area. A three end-member model using (207)Pb/(206)Pb and concentration as tracers resulted in fugitive dust samples plotting in the mixing field of well characterized heterogeneous end members. End members selected for this investigation include the (207)Pb/(206)Pb for 1) a Pb-mixture representing mine tailings, 2) aerosol Pb-impacted soils within close proximity to the Buick secondary recycling smelter, and 3) an average of soils, rock cores and drill cuttings representing the background conditions. Aqua regia total concentrations and (207)Pb/(206)Pb of mining area dust suggest that 35.4-84.3% of the source Pb in dust is associated with the mine tailings mixture, 9.1-52.7% is associated with the smelter mixture, and 0-21.6% is associated with background materials. Isotope ratios varied minimally within the operational phases of sequential extraction suggesting that mixing of all three Pb mixtures occurs throughout. Labile forms of Pb were attributed to all three end members. The extractable carbonate phase had as much as 96.6% of the total concentration associated with mine tailings, 51.8% associated with smelter deposition, and 34.2% with background. The next most labile geochemical phase (Fe + Mn Oxides) showed similar results with as much as 85.3% associated with mine tailings, 56.8% associated with smelter deposition, and 4.2% associated with the background soil. Published by Elsevier Ltd.

Isotopically constrained lead sources in fugitive dust from unsurfaced roads in the southeast Missouri mining district

USGS Publications Warehouse

Witt, Emitt C.; Pribil, Michael; Hogan, John P; Wronkiewicz, David

2016-01-01

The isotopic composition of lead (Pb) in fugitive dust suspended by a vehicle from 13 unsurfaced roads in Missouri was measured to identify the source of Pb within an established long-term mining area. A three end-member model using 207Pb/206Pb and concentration as tracers resulted in fugitive dust samples plotting in the mixing field of well characterized heterogeneous end members. End members selected for this investigation include the 207Pb/206Pb for 1) a Pb-mixture representing mine tailings, 2) aerosol Pb-impacted soils within close proximity to the Buick secondary recycling smelter, and 3) an average of soils, rock cores and drill cuttings representing the background conditions. Aqua regia total concentrations and 207Pb/206Pb of mining area dust suggest that 35.4–84.3% of the source Pb in dust is associated with the mine tailings mixture, 9.1–52.7% is associated with the smelter mixture, and 0–21.6% is associated with background materials. Isotope ratios varied minimally within the operational phases of sequential extraction suggesting that mixing of all three Pb mixtures occurs throughout. Labile forms of Pb were attributed to all three end members. The extractable carbonate phase had as much as 96.6% of the total concentration associated with mine tailings, 51.8% associated with smelter deposition, and 34.2% with background. The next most labile geochemical phase (Fe + Mn Oxides) showed similar results with as much as 85.3% associated with mine tailings, 56.8% associated with smelter deposition, and 4.2% associated with the background soil.

Nitrogen isotope effects induced by anammox bacteria

PubMed Central

Brunner, Benjamin; Contreras, Sergio; Lehmann, Moritz F.; Matantseva, Olga; Rollog, Mark; Kalvelage, Tim; Klockgether, Gabriele; Lavik, Gaute; Jetten, Mike S. M.; Kartal, Boran; Kuypers, Marcel M. M.

2013-01-01

Nitrogen (N) isotope ratios (15N/14N) provide integrative constraints on the N inventory of the modern ocean. Anaerobic ammonium oxidation (anammox), which converts ammonium and nitrite to dinitrogen gas (N2) and nitrate, is an important fixed N sink in marine ecosystems. We studied the so far unknown N isotope effects of anammox in batch culture experiments. Anammox preferentially removes 14N from the ammonium pool with an isotope effect of +23.5‰ to +29.1‰, depending on factors controlling reversibility. The N isotope effects during the conversion of nitrite to N2 and nitrate are (i) inverse kinetic N isotope fractionation associated with the oxidation of nitrite to nitrate (−31.1 ± 3.9‰), (ii) normal kinetic N isotope fractionation during the reduction of nitrite to N2 (+16.0 ± 4.5‰), and (iii) an equilibrium N isotope effect between nitrate and nitrite (−60.5 ± 1.0‰), induced when anammox is exposed to environmental stress, leading to the superposition of N isotope exchange effects upon kinetic N isotope fractionation. Our findings indicate that anammox may be responsible for the unresolved large N isotope offsets between nitrate and nitrite in oceanic oxygen minimum zones. Irrespective of the extent of N isotope exchange between nitrate and nitrite, N removed from the combined nitrite and nitrate (NOx) pool is depleted in 15N relative to NOx. This net N isotope effect by anammox is superimposed on the N isotope fractionation by the co-occurring reduction of nitrate to nitrite in suboxic waters, possibly enhancing the overall N isotope effect for N loss from oxygen minimum zones. PMID:24191043

Theoretical estimates of supernova-neutrino cross sections for the stable even-even lead isotopes: Charged-current reactions

NASA Astrophysics Data System (ADS)

Almosly, W.; Carlsson, B. G.; Suhonen, J.; Toivanen, J.; Ydrefors, E.

2016-10-01

A detailed study of the charged-current supernova electron neutrino and electron antineutrino scattering off the stable even-mass lead isotopes A =204 , 206, and 208 is reported in this work. The proton-neutron quasiparticle random-phase approximation (pnQRPA) is adopted to construct the nuclear final and initial states. Three different Skyrme interactions are tested for their isospin and spin-isospin properties and then applied to produce (anti)neutrino-nucleus scattering cross sections for (anti)neutrino energies below 80 MeV. Realistic estimates of the nuclear responses to supernova (anti)neutrinos are computed by folding the computed cross sections with a two-parameter Fermi-Dirac distribution of the electron (anti)neutrino energies. The computed cross sections are compared with earlier calculations and the analyses are extended to take into account the effects coming from the neutrino oscillations.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

Multivariate statistical and lead isotopic analyses approach to identify heavy metal sources in topsoil from the industrial zone of Beijing Capital Iron and Steel Factory.

PubMed

Zhu, Guangxu; Guo, Qingjun; Xiao, Huayun; Chen, Tongbin; Yang, Jun

2017-06-01

Heavy metals are considered toxic to humans and ecosystems. In the present study, heavy metal concentration in soil was investigated using the single pollution index (PIi), the integrated Nemerow pollution index (PIN), and the geoaccumulation index (Igeo) to determine metal accumulation and its pollution status at the abandoned site of the Capital Iron and Steel Factory in Beijing and its surrounding area. Multivariate statistical (principal component analysis and correlation analysis), geostatistical analysis (ArcGIS tool), combined with stable Pb isotopic ratios, were applied to explore the characteristics of heavy metal pollution and the possible sources of pollutants. The results indicated that heavy metal elements show different degrees of accumulation in the study area, the observed trend of the enrichment factors, and the geoaccumulation index was Hg > Cd > Zn > Cr > Pb > Cu ≈ As > Ni. Hg, Cd, Zn, and Cr were the dominant elements that influenced soil quality in the study area. The Nemerow index method indicated that all of the heavy metals caused serious pollution except Ni. Multivariate statistical analysis indicated that Cd, Zn, Cu, and Pb show obvious correlation and have higher loads on the same principal component, suggesting that they had the same sources, which are related to industrial activities and vehicle emissions. The spatial distribution maps based on ordinary kriging showed that high concentrations of heavy metals were located in the local factory area and in the southeast-northwest part of the study region, corresponding with the predominant wind directions. Analyses of lead isotopes confirmed that Pb in the study soils is predominantly derived from three Pb sources: dust generated during steel production, coal combustion, and the natural background. Moreover, the ternary mixture model based on lead isotope analysis indicates that lead in the study soils originates mainly from anthropogenic sources, which contribute much more

Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maggi, F.M.; Riley, W.J.

2009-06-01

The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O productionmore » and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.« less

Mesozoic Magmatism and Base-Metal Mineralization in the Fortymile Mining District, Eastern Alaska - Initial Results of Petrographic, Geochemical, and Isotopic Studies in the Mount Veta Area

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Slack, John F.; Aleinikoff, John N.; Mortensen, James K.

2009-01-01

We present here the initial results of a petrographic, geochemical, and isotopic study of Mesozoic intrusive rocks and spatially associated Zn-Pb-Ag-Cu-Au prospects in the Fortymile mining district in the southern Eagle quadrangle, Alaska. Analyzed samples include mineralized and unmineralized drill core from 2006 and 2007 exploration by Full Metal Minerals, USA, Inc., at the Little Whiteman (LWM) and Fish prospects, and other mineralized and plutonic samples collected within the mining district is part of the USGS study. Three new ion microprobe U-Pb zircon ages are: 210 +- 3 Ma for quartz diorite from LWM, 187 +- 3 Ma for quartz monzonite from Fish, and 70.5 +- 1.1 Ma for altered rhyolite porphyry from Fish. We also present 11 published and unpublished Mesozoic thermal ionization mass spectrometric U-Pb zircon and titanite ages and whole-rock geochemical data for the Mesozoic plutonic rocks. Late Triassic and Early Jurassic plutons generally have intermediate compositions and are slightly foliated, consistent with synkinematic intrusion. Several Early Jurassic plutons contain magmatic epidote, indicating emplacement of the host plutons at mesozonal crustal depths of greater than 15 km. Trace-element geochemical data indicate an arc origin for the granitoids, with an increase in the crustal component with time. Preliminary study of drill core from the LWM Zn-Pb-Cu-Ag prospect supports a carbonate-replacement model of mineralization. LWM massive sulfides consist of sphalerite, galena, and minor pyrite and chalcopyrite, in a gangue of calcite and lesser quartz; silver resides in Sb-As-Ag sulfosalts and pyrargyrite, and probably in submicroscopic inclusions within galena. Whole-rock analyses of LWM drill cores also show elevated In, an important metal in high-technology products. Hypogene mineralized rocks at Fish, below the secondary Zn-rich zone, are associated with a carbonate host and also may be of replacement origin, or alternatively, may be a magnetite

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

NASA Technical Reports Server (NTRS)

Nyquist, L. E.; Bogard, D. D.

1996-01-01

The original Mg-Fe zoning of eucritic pyroxenes has in nearly all cases been partly homogenized, an observation that has been combined with other petrographic and compositional criteria to establish a scale of thermal "metamorphism" for eucrites. To evaluate hypotheses explaining development of conditions on the HED parent body (Vesta?) leading to pyroxene homogenization against their chronological implications, it is necessary to know whether pyroxene metamorphism was recorded in the isotopic systems. However, identifying the effects of the thermal metamorphism with specific effects in the isotopic systems has been difficult, due in part to a lack of correlated isotopic and mineralogical studies of the same eucrites. Furthermore, isotopic studies often place high demands on analytical capabilities, resulting in slow growth of the isotopic database. Additionally, some isotopic systems would not respond in a direct and sensitive way to pyroxene homogenization. Nevertheless, sufficient data exist to generalize some observations, and to identify directions of potentially fruitful investigations.

Rare Isotopes Physics in the Multimessenger Era

NASA Astrophysics Data System (ADS)

Schatz, Hendrik

2018-06-01

While these isotopes only exist for fractions of seconds, their properties shape the resulting cosmic distribution of elements and the astronomical observables including spectra, neutrinos, and gravitational waves. The long standing challenge in nuclear astrophysics of the production of the relevant isotopes in the laboratory is now overcome with a new generation of rare isotope accelerator facilities now coming online. One example is the FRIB facility under construction at Michigan State University for the US Department of Energy, Office of Science, Office of Nuclear Physics. These new capabilities in nuclear physics coincide with advances in astronomy directly related to the cosmic sites where these isotopes are created, in particular in time domain and gravitational wave astronomy. I will discuss the importance of rare isotope physics in interpreting multi-messenger observations and how advances in nuclear physics and astronomy when combined promise to lead us towards a comprehensive theory of the origin of the elements.

Lead isotopes in trade wind aerosols at Barbados - The influence of European emissions over the North Atlantic

NASA Technical Reports Server (NTRS)

Hamelin, B.; Grousset, F. E.; Biscaye, P. E.; Zindler, A.; Prospero, J. M.

1989-01-01

Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contributions from different sources. Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt are presented. Aerosols sampled at Barbados during the 1969-1985 period have a Pb isotopic composition different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb that is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes.

The use of Pb isotopes to differentiate between contemporary and ancient sources of pollution in Greece

NASA Astrophysics Data System (ADS)

Åberg, G.; Charalampides, G.; Fosse, G.; Hjelmseth, H.

Stable lead isotopes are used to illustrate the relation source-receptor and to differentiate between sources of pollution in Greece. Air filters collected in the Kozani-Ptolemais lignite mining area, West Macedonia, point to an impact from gasoline lead as well as lead from the combustion of lignite. This is supported by lead isotope data of wheat grown on reclaimed land. Lead isotope analyses of contemporary teeth from the Lavrio sulphide mining area, southeast of Greece, show the imprint of previous mining activities as well as traffic emissions. Moreover, the Lavrio teeth can be distinguished from one tooth from Athens; the Athens tooth show a stronger impact of gasoline lead. Lead data also imply that the Greek top soil is contaminated by air pollution from earlier sulphide mining and smelting since Hellenic and Roman times.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

High-Precision (MC-ICPMS) Isotope Ratio Analysis Reveals Contrasting Sources of Elevated Blood Lead Levels of an Adult with Retained Bullet Fragments, and of His Child, in Milwaukee, Wisconsin.

PubMed

Smith, Kate E; Shafer, Martin M; Weiss, Debora; Anderson, Henry A; Gorski, Patrick R

2017-05-01

Exposure to the neurotoxic element lead (Pb) continues to be a major human health concern, particularly for children in US urban settings, and the need for robust tools for assessment of exposure sources has never been greater. The latest generation of multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) instrumentation offers the capability of using Pb isotopic signatures as a tool for environmental source tracking in public health. We present a case where MC-ICPMS was applied to isotopically resolve Pb sources in human clinical samples. An adult male and his child residing in Milwaukee, Wisconsin, presented to care in August 2015 with elevated blood lead levels (BLLs) (>200 μg/dL for the adult and 10 μg/dL for the child). The adult subject is a gunshot victim who had multiple bullet fragments embedded in soft tissue of his thigh for approximately 10 years. This study compared the high-precision isotopic fingerprints (<1 ‰ 2σ external precision) of Pb in the adult's and child's whole blood (WB) to the following possible Pb sources: a surgically extracted bullet fragment, household paint samples and tap water, and a Pb water-distribution pipe removed from servicing a house in the same neighborhood. Pb in the bullet and adult WB were nearly isotopically indistinguishable (matching within 0.05-0.56 ‰), indicating that bullet fragments embedded in soft tissue could be the cause of both acute and chronic elevated blood Pb levels. Among other sources investigated, no single source dominated the child's exposure profile as reflected in the elevated BLL.

Elemental and isotopic abundances in the solar wind

NASA Technical Reports Server (NTRS)

Geiss, J.

1972-01-01

The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

Isotopic Randomness and Maxwell's Demon

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2005-03-01

Isotopic disorder in crystals can lead to suppression of thermal conductivity, mobility variations and (weak) Anderson localization on isotopic fluctuations. The latter (AAB, J.ChemPhys.1984) is akin to polaron effect (self-localization due polarization). Possibility of isotopic patterning (IP) increases near melting point (thermally activated isotopic hopping swaps). Crystal near melting threshold become “informationally sensitive” as if its IP is operated by some external Maxwell’s Demon, MD (AAB, URAM J, 2002). At this state short range (e.g. electrostatic inverse square) forces evolve into long-range interactions (due to divergence of order parameter) and information sensitivity can be further amplified by (say) a single fast electron (e.g. beta-particle from decay of 14-C or other radioactive isotope) which may result in cascade of impact ionization events and (short time-scale) enhancement of screening by impact-generated non-equilibrium (non-thermal) electrons. In this state informationally driven (MD-controlled) IP (Eccles effect) can result in decrease of positional entropy signifying emergence of physical complexity out of pure information, similar to peculiar “jinni effect” on closed time loops in relativistic cosmology (R.J.Gott, 2001) or Wheeler’s “it from bit” metaphor. By selecting special IP, MD modifies ergodicity principle in favor of info rich states.

Effects of must concentration techniques on wine isotopic parameters.

PubMed

Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

2006-12-27

Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

Distribution of oceanic and continental leads in the Arabian-Nubian Shield

USGS Publications Warehouse

Stacey, J.S.; Stoeser, D.B.

1983-01-01

New common lead data for feldspar, whole-rock, and galena samples from the Arabian-Nubian Shield, together with data from previous work, can be divided into two main groups. Group I leads have oceanic (mantle) characteristics, whereas group II leads have incorporated a continental-crustal component of at least early Proterozoic age. The group I leads are found in rocks from the Red Sea Hills of Egypt and the western and southern parts of the Arabian Shield. Group II leads are found in rocks from the northeastern and eastern parts of the Arabian Shield, as well as from the southeastern Shield near Najran. They are also found in rocks to the south in Yemen, to the east in Oman, and to the west at Aswan, Egypt. This distribution of data suggests that the Arabian-Nubian Shield has an oceanic core flanked by rocks that have developed, at least in part, from older continental material. Two mechanisms are suggested by which this older lead component could have been incorporated into the late Proterozoic rocks, and each may have operated in different parts of the Shield. The older lead component either was derived directly from an underlying early Proterozoic basement or was incorporated from subducted pelagic sediments or sediments derived from an adjacent continent. New U-Pb zircon data indicate the presence of an early Proterozoic basement southeast of Jabal Dahul in the eastern Arabian Shield. These data, together with 2,000-Ma-old zircons from the Al Amar fault zone, verify the implication of the common lead data that at least a part of the eastern Arabian Shield has an older continental basement. Because continental margins are particularly favorable locations for development of ore deposits, these findings may have important economic implications, particularly for tin, tungsten, and molybdenum exploration. ?? 1983 Springer-Verlag.

Lead isotopes in trade wind aerosols at Barbados: the influence of European emissions over the North Atlantic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamelin, B.; Grousset, F.E.; Biscaye, P.E.

1989-11-15

Previous studies have shown that Pb can be used as a transient tracer in the atmosphere and the ocean because of strong time-variability of industrial inputs and because Pb isotopic composition can be used to identify contribution from different sources. We present Pb isotopic measurements on aerosols collected from the North Atlantic Ocean in the trade wind belt. Aerosols sampled at Barbados during the 1969--1985 period have a Pb isotopic compositions different from that observed by previous investigators in Bermuda corals and Sargasso Sea waters. Barbados aerosols appear to contain significant amounts of relatively unradiogenic industrial and automotive Pb thatmore » is derived from Europe and carried to Barbados by the trade winds. In contrast, Bermuda corals and Sargasso sea waters are influenced mainly by U.S.-derived emissions, which contain more radiogenic Pb originating from Missouri-type ores. This difference generates a strong latitudinal Europe-U.S.A. isotopic gradient, thus allowing study of trans-Atlantic atmospheric transport and ocean mixing processes. {copyright} American Geophysical Union 1989« less

Nature and origin of the nonsulfide zinc deposits in the Sierra Mojada District, Coahuila, Mexico: constraints from regional geology, petrography, and isotope analyses

NASA Astrophysics Data System (ADS)

Kyle, J. Richard; Ahn, Hyein; Gilg, H. Albert

2018-02-01

The Sierra Mojada District comprises multiple types of near-surface mineral concentrations ranging from polymetallic sulfide zones, "nonsulfide Zn" (NSZ) deposits, and a silver-rich Pb carbonate deposit hosted by lower Cretaceous carbonate strata. Hypogene concentrations of Fe-Zn-Pb-Cu-Ag sulfides and sulfosalts are locally preserved and are associated with hydrothermal dolomite and silica. Alteration mineralogy and sulfur isotope data suggest primary Zn-Pb-Ag mineralization from circa 200 °C hydrothermal fluids. The NSZ deposits dominantly consist of smithsonite and hemimorphite associated with local Mn-Fe oxides. The Red Zinc Zone consists of strata-bound zones dominantly of hemimorphite that fills pores in residual and resedimented Fe oxides. The White Zinc Zone shows local dissolution features, including internal sediments interbanded with and cemented by smithsonite. Similar Pb isotopic compositions of smithsonite, hemimorphite, and cerussite to Sierra Mojada galena document that the NSZ deposits originated from polymetallic carbonate-replacement sulfide deposits, with flow of metal-bearing groundwater being controlled by local topography and structural features in this extensional terrane. Oxygen isotope values for Sierra Mojada smithsonite are relatively constant (δ18OVSMOW = 20.9 to 23.3‰) but are unusually low compared to other supergene smithsonites. Using δ18OVSMOW (- 8‰) of modern groundwater at nearby Cuatrociénegas, smithsonite formational temperatures are calculated to have been between 26 to 35 °C. Smithsonite precipitation was favored by near-neutral conditions typical of carbonate terranes, whereas hemimorphite precipitated by reaction with wallrock silica and locally, or episodically, more acidic conditions resulting from sulfide oxidation. Transition to, and stabilization of, the modern desert climate over the past 9000 years from the Late Pleistocene wetter, cooler climate of northern Mexico resulted in episodic drawdown of the water

Tracking the weathering of basalts on Mars using lithium isotope fractionation models

PubMed Central

Losa‐Adams, Elisabeth; Gil‐Lozano, Carolina; Gago‐Duport, Luis; Uceda, Esther R.; Squyres, Steven W.; Rodríguez, J. Alexis P.; Davila, Alfonso F.; McKay, Christopher P.

2015-01-01

Abstract Lithium (Li), the lightest of the alkali elements, has geochemical properties that include high aqueous solubility (Li is the most fluid mobile element) and high relative abundance in basalt‐forming minerals (values ranking between 0.2 and 12 ppm). Li isotopes are particularly subject to fractionation because the two stable isotopes of lithium—7Li and 6Li—have a large relative mass difference (∼15%) that results in significant fractionation between water and solid phases. The extent of Li isotope fractionation during aqueous alteration of basalt depends on the dissolution rate of primary minerals—the source of Li—and on the precipitation kinetics, leading to formation of secondary phases. Consequently, a detailed analysis of Li isotopic ratios in both solution and secondary mineral lattices could provide clues about past Martian weathering conditions, including weathering extent, temperature, pH, supersaturation, and evaporation rate of the initial solutions in contact with basalt rocks. In this paper, we discuss ways in which Martian aqueous processes could have lead to Li isotope fractionation. We show that Li isotopic data obtained by future exploration of Mars could be relevant to highlighting different processes of Li isotopic fractionation in the past, and therefore to understanding basalt weathering and environmental conditions early in the planet's history. PMID:27642264

Automated method for simultaneous lead and strontium isotopic analysis applied to rainwater samples and airborne particulate filters (PM10).

PubMed

Beltrán, Blanca; Avivar, Jessica; Mola, Montserrat; Ferrer, Laura; Cerdà, Víctor; Leal, Luz O

2013-09-03

A new automated, sensitive, and fast system for the simultaneous online isolation and preconcentration of lead and strontium by sorption on a microcolumn packed with Sr-resin using an inductively coupled plasma mass spectrometry (ICP-MS) detector was developed, hyphenating lab-on-valve (LOV) and multisyringe flow injection analysis (MSFIA). Pb and Sr are directly retained on the sorbent column and eluted with a solution of 0.05 mol L(-1) ammonium oxalate. The detection limits achieved were 0.04 ng for lead and 0.03 ng for strontium. Mass calibration curves were used since the proposed system allows the use of different sample volumes for preconcentration. Mass linear working ranges were between 0.13 and 50 ng and 0.1 and 50 ng for lead and strontium, respectively. The repeatability of the method, expressed as RSD, was 2.1% and 2.7% for Pb and Sr, respectively. Environmental samples such as rainwater and airborne particulate (PM10) filters as well as a certified reference material SLRS-4 (river water) were satisfactorily analyzed obtaining recoveries between 90 and 110% for both elements. The main features of the LOV-MSFIA-ICP-MS system proposed are the capability to renew solid phase extraction at will in a fully automated way, the remarkable stability of the column which can be reused up to 160 times, and the potential to perform isotopic analysis.

Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

PubMed

Nonose, Naoko; Suzuki, Toshihiro; Shin, Ki-Cheol; Miura, Tsutomu; Hioki, Akiharu

2017-06-29

A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208 Pb and a solution of enriched 204 Pb ( 208 Pb- 204 Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208 Pb: 204 Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208 Pb: 204 Pb in the 208 Pb- 204 Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206 Pb: 204 Pb, 15.6278 ± 0.0036 for 207 Pb: 204 Pb, 38.0626 ± 0.0089 for 208 Pb: 204 Pb, 2.104406 ± 0.00013 for 208 Pb: 206 Pb, and 0.863888 ± 0.000036 for 207 Pb: 206 Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, or one eighth, for 208 Pb: 206 Pb and 207 Pb: 206 Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, the latter contribution is two or three times larger than the former. When the coupling of

Thiopental and Phenytoin as Novel Ionophores for Potentiometric Determination of Lead (II) Ions

PubMed Central

Rizk, Nashwa M.H.; Abbas, Samah S.; Hamza, Salem M.; Abd EL-Karem, Yasser M.

2009-01-01

Two novel polymeric membrane sensors for the analysis of Pb(II) have been developed based on two therapeutic drugs, thiopental (TP) and phenytoin (PT) as two new ionophores and potassium tetrakis(p-chlorophenyl) borate (KTpClPB) as a lipophilic additive, in plasticized PVC membranes. The sensors show a Nernstian response for Pb(II) ions over the wide concentration ranges of 1×10−2 – 7×10−6 M and 1×10−2 – 8×10−6 M for the sensors based on thiopental and phenytoin, respectively. The proposed sensors have a fast response time and can be used for more than nine weeks without any considerable divergence in potentials. The sensors exhibit comparatively good selectivity with respect to alkaline, alkaline earth and some transition and heavy metal ions. They were employed for direct determination of lead in solder alloys and in galena rocks with a good agreement with the obtained results by atomic absorption spectroscopy. PMID:22573991

Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

PubMed

Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

2015-05-27

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

Isotopic Clues to Mars Crust-Atmosphere Interactions

NASA Image and Video Library

2016-09-29

Chemistry that takes place in the surface material on Mars can explain why particular xenon (Xe) and krypton (Kr) isotopes are more abundant in the Martian atmosphere than expected. The isotopes -- variants that have different numbers of neutrons -- are formed in the loose rocks and material that make up the regolith -- the surface layer down to solid rock. The chemistry begins when cosmic rays penetrate into the surface material. If the cosmic rays strike an atom of barium (Ba), the barium can lose one or more of its neutrons (n0). Atoms of xenon can pick up some of those neutrons – a process called neutron capture – to form the isotopes xenon-124 and xenon-126. In the same way, atoms of bromine (Br) can lose some of their neutrons to krypton, leading to the formation of krypton-80 and krypton-82 isotopes. These isotopes can enter the atmosphere when the regolith is disturbed by impacts and abrasion, allowing gas to escape. http://photojournal.jpl.nasa.gov/catalog/PIA20847

Applying geochemical signatures of atmospheric dust to distinguish current mine emissions from legacy sources

NASA Astrophysics Data System (ADS)

Dong, Chenyin; Taylor, Mark Patrick

2017-07-01

Resolving the source of environmental contamination is the critical first step in remediation and exposure prevention. Australia's oldest silver-zinc-lead mine at Broken Hill (>130 years old) has generated a legacy of contamination and is associated with persistent elevated childhood blood lead (Pb) levels. However, the source of environmental Pb remains in dispute: current mine emissions; remobilized mine-legacy lead in soils and dusts; and natural lead from geological weathering of the gossan ore body. Multiple lines of evidence used to resolve this conundrum at Broken Hill include spatial and temporal variations in dust Pb concentrations and bioaccessibility, Pb isotopic compositions, particle morphology and mineralogy. Total dust Pb loading (mean 255 μg/m2/day) and its bioaccessibility (mean 75% of total Pb) is greatest adjacent to the active mining operations. Unweathered galena (PbS) found in contemporary dust deposits contrast markedly to Pb-bearing particles from mine-tailings and weathered gossan samples. Contemporary dust particles were more angular, had higher sulfur content and had little or no iron and manganese. Dust adjacent to the mine has Pb isotopic compositions (208Pb/207Pb: 2.3197; 206Pb/207Pb: 1.0406) that are a close match (99%) to the ore body with values slightly lower (94%) at the edge of the city. The weight of evidence supports the conclusion that contemporary dust Pb contamination in Broken Hill is sourced primarily from current mining activities and not from weathering or legacy sources.

Past leaded gasoline emissions as a nonpoint source tracer in riparian systems: A study of river inputs to San Francisco Bay

USGS Publications Warehouse

Dunlap, C.E.; Bouse, R.; Flegal, A.R.

2000-01-01

Variations in the isotopic composition of lead in 1995-1998 river waters flowing into San Francisco Bay trace the washout of lead deposited in the drainage basin from leaded gasoline combustion. At the confluence of the Sacramento and San Joaquin rivers where they enter the Bay, the isotopic compositions of lead in the waters define a linear trend away from the measured historical compositions of leaded gas in California. The river waters are shifted away from leaded gasoline values and toward an isotopic composition similar to Sierra Nevadan inputs which became the predominant source of sedimentation in San Francisco Bay following the onset of hydraulic gold mining in 1853. Using lead isotopic compositions of hydraulic mine sediments and average leaded gasoline as mixing end members, we calculate that more than 50% of the lead in the present river water originated from leaded gasoline combustion. The strong adsorption of lead (log K(d) > 7.4) to particulates appears to limit the flushing of gasoline lead from the drainage basin, and the removal of that lead from the system may have reached an asymptotic limit. Consequently, gasoline lead isotopes should prove to be a useful nonpoint source tracer of the environmental distribution of particle- reactive anthropogenic metals in freshwater systems.

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: A window into and through regional metamorphism

USGS Publications Warehouse

Seal, Robert R.; Ayuso, Robert A.; Foley, Nora K.; Clark, Sandra H.B.

2001-01-01

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ34S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ34S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ34S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for 206Pb/204Pb from 18.005–18.294, for 207Pb/204Pb from 15.567–15.645, and for 208Pb/204Pb from 37.555–38.015. The data

Particular geoscientific perspectives on stable isotope analysis in the arboreal system

NASA Astrophysics Data System (ADS)

Helle, Gerhard; Balting, Daniel; Pauly, Maren; Slotta, Franziska

2017-04-01

In geosciences stable isotopes of carbon, oxygen and hydrogen from the tree ring archive have been used for several decades to trace the course of past environmental and climatological fluctuations. In contrast to ice cores, the tree ring archive is of biological nature (like many other terrestrial archives), but provides the opportunity to establish site networks with very high resolution in space and time. Many of the basic physical mechanisms of isotope shifts are known, but biologically mediated processes may lead to isotope effects that are poorly understood. This implies that the many processes within the arboreal system leading to archived isotope ratios in wood material are governed by a multitude of environmental variables that are not only tied to the isotopic composition of atmospheric source values (precipitation, CO2), but also to seasonally changing metabolic flux rates and pool sizes of photosynthates within the trees. Consequently, the extraction of climate and environmental information is particularly challenging and reconstructions are still of rather qualitative nature. Over the last 10 years or so, monitoring studies have been implemented to investigate stable isotope, climate and environmental signal transfer within the arboreal system to develop transfer or response functions that can translate the relevant isotope values extracted from tree rings into climate or other environmental variables. To what extent have these efforts lead to a better understanding that helps improving the meaningfulness of tree ring isotope signals? For example, do monitoring studies help deciphering the causes for age-related trends in tree ring stable isotope sequences that are published in a growing number of papers. Are existing monitoring studies going into detail enough or is it already too much effort for the outcome? Based on what we know already particularly in mesic habitats, tree ring stable isotopes are much better climate proxies than other tree ring

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

Baumgartner, L. P.; Mueller, T.; Skora, S.; Begue, F.

2007-12-01

Stable isotopes are powerful tools for deciphering the fluid flow histories of metamorphic terrains. The nature of fluid flow, fluid sources, and fluid fluxes can be delineated in well constrained studies. Continuum mechanics models for stable isotope fluid-rock exchange were developed and used over the last three decades in an attempt to accurately interpret the signatures left behind by fluid flow in the earths crust. The efforts have been hampered by the realization that the exchange of many stable isotopes, e.g. oxygen and carbon, by intracrystalline diffusion, hence without re-organization of the crystal lattice, appears to be too slow to achieve significant exchange. This should lead to relatively flat isotopic exchange profiles on hand-, outcrop, or aureole scale. Nevertheless, isotopic fronts are typically sharp (sub mm to cm scale), when measured in the field. This has lead to the suggestion that these sharp fronts correspond to the sides of infiltration fronts, implying the data to have been collected at a high angle to the infiltration direction. Nevertheless, the fact that the oxygen and carbon fronts are located at the same place is not explained by this. A review of published carbon and oxygen data reveals that many contact aureoles show linear trends in oxygen-carbon isotope ratio diagrams for carbonate sample suits. This implies that the fluid composition infiltrating the aureoles had essentially an X(CO2) of 0.5. This is in contrast to skarn mineralogy developed, which requires a water-rich fluid, in agreement with the general notion that igneous fluids are water-rich. These and other observations indicate that the mass transport equation used for stable isotope exchange needs to be improved to model appropriately the actual isotope kinetics during fluid-rock exchange. Detailed isotope studies on systems where net transport reactions are driven by mass transport have led us to identify different exchange mechanisms, including: a) the stable isotope

Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

USGS Publications Warehouse

Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.

2004-01-01

The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (<27 ppm) and Tl (<37 ppm). Late tan sphalerite has distinctly lower Fe (< 0.9 wt %) and higher Tl (up to 355 ppm), Mn (up to 177 ppm), and Ge (426 ppm), relative to earlier sphalerite. Wide ranges in concentrations of Ag, Cu, Pb, and Sb characterize all sphalerite types, particularly yellow-brown sphalerite and red-brown sphalerite, and most likely reflect submicroscopic inclusions of galena, chalcopyrite and/or tetrahedrite in the sphalerite. In situ ion microprobe sulfur isotope analyses show a progression from extremely low ??34S values for stage 1 (as low as -37.20???) to much higher values for yellow-brown sphalerite (mean of 3.3???; n = 30) and red-brown sphalerite (mean of 3.4; n = 20). Late tan sphalerite is isotopically light (-16.4 to -27.2???). The textural, chem ical, and isotopic data indicate the following paragenesis: (1) deposition of early brown sphalerite with abundant barite, minor pyrite, and trace galena immediately beneath the sea floor in unconsolidated mud; (2) deposition

Geochemistry, Nd-Pb Isotopes, and Pb-Pb Ages of the Mesoproterozoic Pea Ridge Iron Oxide-Apatite–Rare Earth Element Deposit, Southeast Missouri

USGS Publications Warehouse

Ayuso, Robert A.; Slack, John F.; Day, Warren C.; McCafferty, Anne E.

2016-01-01

magnetite ore shared a common origin from a similar source.Lead isotope ratios are diverse: (1) host rhyolite has 206Pb/204Pb from 24.261 to 50.091; (2) Pea Ridge and regional galenas have 206Pb/204Pb from 16.030 to 33.548; (3) REE-rich breccia, magnetite ore, and specular hematite rock are more radiogenic than galena; (4) REE-rich breccias have high 206Pb/204Pb (38.122–1277.61) compared to host rhyolites; and (5) REE-rich breccias are more radiogenic than magnetite ore and specular-hematite rock, having 206Pb/204Pb up to 230.65. Radiogenic 207Pb/206Pb age estimates suggest the following: (1) rhyolitic host rocks have ages of ~1.50 Ga, (2) magnetite ore is ~1.44 Ga, and (3) REE-rich breccias are ~1.48 Ga. These estimates are broadly consistent and genetically link the host rhyolite, REE-rich breccia, and magnetite ore as being contemporaneous.Alteration style and mineralogical or textural distinctions among the magnetite-rich rocks and REE-rich breccias do not correlate with different isotopic sources. In our model, magmatic fluids leached metals from the coeval felsic rocks (rhyolites), which provided the metal source reflected in the compositions of the REE-rich breccias and mineralized rocks. This model allows for the likelihood of contributions from other genetically related felsic and intermediate to more mafic rocks stored deeper in the crust. The deposit thus records an origin as a magmatic-hydrothermal system that was not affected by Nd and Pb remobilization processes, particularly if these processes also triggered mixing with externally sourced metal-bearing fluids. The Pea Ridge deposit was part of a single, widespread, homogeneous mixing system that produced a uniform isotopic composition, thus representing an excellent example of an igneous-dominated system that generated coeval magmatism and REE mineralization. Geochemical features suggest that components in the Pea Ridge deposit originated from sources in an orogenic margin. Basaltic magmatism produced

Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

PubMed

Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

2016-05-01

Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

Assay Methods for 238U, 232Th, and 210Pb in Lead and Calibration of 210Bi Bremsstrahlung Emission from Lead

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orrell, John L.; Aalseth, Craig E.; Arnquist, Isaac J.

2016-02-13

Assay methods for measuring 238U, 232Th, and 210Pb concentrations in refined lead are presented. The 238U and 232Th concentrations are assayed via inductively coupled plasma mass spectrometry (ICP-MS) after anion exchange column separation on dissolved lead samples. The 210Pb concentration is inferred through α-spectroscopy of a daughter isotope, 210Po, after chemical precipitation separation on dissolved lead samples. Subsequent to the 210Po α-spectroscopy assay, a method for evaluating 210Pb concentrations in solid lead samples was developed via measurement of bremsstrahlung radiation from β-decay of a daughter isotope, 210Bi, by employing a 14-crystal array of high purity germanium (HPGe) detectors. Ten sourcesmore » of refined lead were assayed. The 238U concentrations were <34 microBq/kg and the 232Th concentrations ranged <0.6 – 15 microBq/kg, as determined by the ICP-MS assay method. The 210Pb concentrations ranged from ~0.1 – 75 Bq/kg, as inferred by the 210Po α-spectroscopy assay method.« less

Isotopic fractionation of volatile species during bubble growth in magmas

NASA Astrophysics Data System (ADS)

Watson, E. B.

2016-12-01

Bubbles grow in decompressing magmas by simple expansion and also by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate isotopes, raising the possibility that the isotopic character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the complete absence of equilibrium vapor/melt isotopic fractionation. None of the foregoing is conceptually new, but recent experimental studies have established the existence of isotope mass effects on diffusion in silicate melts for several elements (Li, Mg, Ca, Fe), and this finding has now been extended to the volatile (anionic) element chlorine (Fortin et al. 2016; this meeting). Knowledge of isotope mass effects on diffusion of volatile species opens the way for quantitative models of diffusive fractionation during bubble growth. Significantly different effects are anticipated for "passive" volatiles (e.g., noble gases and Cl) that are partitioned into existing bubbles but play little role in nucleation and growth, as opposed to "active" volatiles whose limited solubilities lead to bubble nucleation during magma decompression. Numerical solution of the appropriate diffusion/mass-conservation equations reveals that the isotope effect on passive volatiles partitioned into bubbles growing at a constant rate in a static system depends (predictably) upon R/D, Kd and D1/D2 (R = growth rate; D = diffusivity; Kd = bubble/melt partition coefficient; D1/D2 = diffusivity ratio of the isotopes of interest). Constant R is unrealistic, but other scenarios can be explored by including the solubility and EOS of an "active" volatile (e.g., CO2) in numerical simulations of bubble growth. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble.

Lead isotope evolution across the Neoproterozoic boundary between craton and juvenile crust, Bayuda Desert, Sudan

NASA Astrophysics Data System (ADS)

Evuk, David; Lucassen, Friedrich; Franz, Gerhard

2017-11-01

Metaigneous mafic and ultramafic rocks from the juvenile Neoproterozoic Arabian Nubian Shield (ANS) and the Proterozoic, reworked Saharan Metacraton (SMC) have been analysed for major- and trace elements and Sr, Nd, and Pb isotopes. Most of the rocks are amphibolites metamorphosed at amphibolite facies conditions, some with relicts of a granulite facies stage. The other rocks are metapyroxenites, metagabbros, and some ultramafic rocks. Trace element compositions of the metabasaltic (dominantly tholeiitic) rocks resemble the patterns of island arcs and primitive lavas from continental arcs. Variable Sr and Nd isotope ratios indicate depleted mantle dominance for most of the samples. 207Pb/204Pb signatures distinguish between the influence of high 207Pb/204Pb old SMC crust and depleted mantle signatures of the juvenile ANS crust. The Pb isotope signatures for most metabasaltic rocks, metapyroxenites and metagabbros from SMC indicate an autochthonous formation. The interpretation of the new data together with published evidence from mafic xenoliths on SMC and ophiolite from ANS allows an extrapolation of mantle evolution in time. There are two lines of evolution in the regional mantle, one, which incorporates potential upper crust material during Neoproterozoic, and a second one with a depleted mantle signature since pre-Neoproterozoic that still is present in the Red Sea and Gulf of Aden spreading centres.

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

PubMed

Gourgiotis, Alkiviadis; Manhès, Gérard; Louvat, Pascale; Moureau, Julien; Gaillardet, Jérôme

2015-09-30

During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated. Copyright © 2015 John Wiley & Sons, Ltd.

Pb isotope systematics in volcanic river system: Constraints about weathering processes

NASA Astrophysics Data System (ADS)

Negrel, P. J.; Millot, R.; Petelet-Giraud, E.; Guerrot, C.

2012-12-01

We present a series of lead isotopes in soils and sediments developed on volcanic rocks forming a small watershed flowing through the Massif Central (France). The Massif Central volcanic province is a widespread area of Tertiary to Recent continental alkaline volcanism comprising alkali basalts and basanites. The Allanche watershed has an area of 160 km2, a maximum altitude in the watershed of 1400 m (a.s.l.) and the relief between the extreme sampling points of 340 m The river is 29 km long from headwaters to the outlet and from its origin in the Cézallier area to its mouth in the Allagnon river (a tributary of the Allier river), the Allanche river flows through the volcanic terrains of the lava plateau (11 to 2.5 Ma). Main bedrocks are basanites (nepheline or leucitic basalts), with SiO2 around 41-45%, low Na2O + K2O (<5%), and with modal or normative nepheline or leucite and a ground mass of clinopyroxene and plagioclase. Surrounding rocks are feldspatic basalts with SiO2 close to 46-49%, low Na2O + K2O (<5%). The main phase in these basalts is plagioclase with normative nepheline, hyperstene and olivine. Crustal contamination (e.g. by granite, gneiss or metasedimentary granulite, as stated by Downes, 1987, doi: 10.1144/GSL.SP.1987.030.01.25) has occurred in the differentiated magmas of both series, as witnessed by lead isotopic variations in conjunction with Rb/La ratios and lead contents. Using Pb isotope ratios, major and trace elements (from Négrel and Deschamps, 1996, Aquatic Geochemistry, 2, 1-27) we therefore compare sediments and soils evolution over the Allanche river watershed. K and Ca are considered as mobile reference elements and illustrate the weathering state of soils and sediments relative to parent rocks through a large decrease in K and Ca content when compared to Si; the sediments being less depleted than soils. Lead, with regards to Si shows three behaviour with depleted Si content- same lead content that bedrock, depleted Si content- less

Barite-polymetallic mineralization of Zmeinogorsk ore district and some genetic aspects of its formation

NASA Astrophysics Data System (ADS)

Bestemianova, K. V.; Grinev, O. M.

2017-12-01

Zmeinogorsky ore district is located in the northwest part of Ore Altai megatrough, which has long-lasting history of its development and complicated geological structure. Within the ore district, which is the northwest part of the devonian Zmeinogorsk-Bystrushinsky trough, ore mineralization is associated with the system of northwest border faults and cross branch faults. There were four main stages and five phases of minerogenesis. The first stage is the stage of oregenesis beginning and quartz-chlorite-sericite wall-rock alteration rocks formation. Ore deposition and intense tectonics took place during the second stage. The third stage is the most longstanding and productive ore formation stage. There are five distinct minerogenesis phases within this stage. The fourth stage expressed in erosion development and supergene alteration of already formed ore bodies with oxidation zone formation. Main ore minerals are pyrite, chalcopyrite, sphalerite and galena. Minor minerals are tetrahedrite, bornite, tennantite and chalcocite. Precious metals minerals are acanthite, gold, electrum, gold and silver amalgams. Barren minerals are barite, quartz, calcite, gypsum. According to obtained data average isotopic composition of third stage sulphides is: pyrite -0,2‰, chalcopyrite 0‰, galena +0,5‰, sphalerite -1,2‰ for the first complex; chalcopyrite -1,9‰, galena -3,4‰, sphalerite -2,3‰, tetrahedrite -3,7‰ for the second complex; tennantite -12,8‰, bornite -8,9‰ for the third complex. Sulfur isotopic compoisiton variations indicate source inhomogeneity. Thus, there was dominant source change from mantle one in the beginning to crustal one in the end. Main oregenesis stages took place in the range of temperatures between 170 and 210°С and in the mineral-forming solutions salinity range between 3 and 10 wt % NaCl equiv.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

Isotopic evolution of Mauna Loa volcano

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kammer, David P.

1991-04-01

In an effort to understand the temporal helium isotopic variations in Mauna Loa volcano, we have measured helium, strontium and lead isotopes in a suite of Mauna Loa lavas that span most of the subaerial eruptive history of the volcano. The lavas range in age from historical flows to Ninole basalt which are thought to be several hundred thousand years old. Most of the samples younger than 30 ka in age (Kau Basalt) are radiocarbon-dated flows, while the samples older than 30 ka are stratigraphically controlled (Kahuku and Ninole Basalt). The data reveal a striking change in the geochemistry of the lavas approximately 10 ka before present. The lavas older than 10 ka are characterized by high 3He/ 4He ( ˜ 16-20 times atmospheric), higher 206Pb/ 204Pb ( ˜ 18.2), and lower 87Sr/ 86Sr ( ˜ 0.70365) ratios than the younger Kau samples (having He, Pb and Sr ratios of approximately 8.5 × atmospheric, 18.1 and 0.70390, respectively). The historical lavas are distinct in having intermediate Sr and Pb isotopic compositions with 3He/ 4He ratios similar to the other young Kau basalt ( ˜ 8.5 × atmospheric). The isotopic variations are on a shorter time scale (100 to 10,000 years) than has previously been observed for Hawaiian volcanoes, and demonstrate the importance of geochronology and stratigraphy to geochemical studies. The data show consistency between all three isotope systems, which suggests that the variations are not related to magma chamber degassing processes, and that helium is not decoupled from the other isotopes. However, the complex temporal evolution suggests that three distinct mantle sources are required to explain the isotopic data. Most of the Mauna Loa isotopic variations could be explained by mixing between a plume type source, similar to Loihi, and an asthenospheric source with helium isotopic composition close to MORB and elevated Sr isotopic values. An asthenospheric source, or variation within the plume source, is considered more likely than

INFLUENCE OF AGING ON PYROMORPHITE FORMATION AND DISSOLUTION

EPA Science Inventory

Published literature has clearly demonstrated that the reaction of a lead (Pb) source as either Pb-minerals (angelesite, cerrusite, or galena), goethite adsorbed lead, Pb-contaminated soils, or an in-vitro bioavailable assay with a phosphate reserve (apatite or hydroxyapatite) re...

Paleoproxies: Heavy Stable Isotope Perspectives

NASA Astrophysics Data System (ADS)

Nagler, T. F.; Hippler, D.; Siebert, C.; Kramers, J. D.

2002-12-01

Recent advances in isotope ratio mass spectrometry, namely multiple collector ICP-MS and refined TIMS techniques, will significantly enhance the ability to measure heavy stable isotope fractionation, which will lead to the development of a wide array of process-identifying (bio)-geochemical tools. Thus far research in this area is not easily assessable to scientists outside the isotope field. This is due to the fact that analyzing heavy stable isotopes does not provide routine numbers which are per se true (the preciser the truer) but is still a highly experimental field. On the other hand resolving earth science problems requires specialists familiar with the environment being studied. So what is in there for paleoceanographers? In a first order approach, relating isotope variations to physical processes is straightforward. A prominent example are oxygen isotope variations with temperature. The total geological signal is of course far more complicated. At low temperatures, heavy stable isotopes variations have been reported for e.g. Ca, Cr, Fe, Cu, Zn, Mo and Tl. Fractionation mechanisms and physical parameters responsible for the observed variations are not yet resolved for most elements. Significant equilibrium isotope fractionation is expected from redox reactions of transition metals. However a difference in coordination number between two coexisting speciations of an element in the same oxidation state can also cause fractionation. Protonation of dissolved Mo is one case currently discussed. For paleoceanography studies, a principal distinction between transition metals essential for life (V to Zn plus Mo) or not will be helpful. In case of the former group, distinction between biogenic and abiogenic isotope fractionation will remain an important issue. For example, abiotic Fe redox reactions result in isotope fractionations indistinguishable in direction and magnitude from microbial effects. Only a combination of different stable isotope systems bears the

High Resolution Gamma Ray Analysis of Medical Isotopes

NASA Astrophysics Data System (ADS)

Chillery, Thomas

2015-10-01

Compton-suppressed high-purity Germanium detectors at the University of Massachusetts Lowell have been used to study medical radioisotopes produced at Brookhaven Linac Isotope Producer (BLIP), in particular isotopes such as Pt-191 used for cancer therapy in patients. The ability to precisely analyze the concentrations of such radio-isotopes is essential for both production facilities such as Brookhaven and consumer hospitals across the U.S. Without accurate knowledge of the quantities and strengths of these isotopes, it is possible for doctors to administer incorrect dosages to patients, thus leading to undesired results. Samples have been produced at Brookhaven and shipped to UML, and the advanced electronics and data acquisition capabilities at UML have been used to extract peak areas in the gamma decay spectra. Levels of Pt isotopes in diluted samples have been quantified, and reaction cross-sections deduced from the irradiation parameters. These provide both cross checks with published work, as well as a rigorous quantitative framework with high quality state-of-the-art detection apparatus in use in the experimental nuclear physics community.

Lead Isotope Geochemistry of Mississippi Valley-Type Pb-Zn Deposits of the Ozark Region, U.S. Midcontinent: Constraints on the Origin of Ore Metals

NASA Astrophysics Data System (ADS)

Potra, A.

2015-12-01

The Ozark region of the U.S. midcontinent is one of the world's most important provinces of MVT mineralization, hosting world-class ore deposits. The ores in the Tri-State (TS) and Northern Arkansas (NA) districts, dominated by sphalerite, are mainly hosted by platform carbonate rocks and vary in age from Ordovician and Mississippian for NA and Mississippian for TS. The deposits are considered to have formed from a regional hydrothermal flow system consisting of sedimentary brines discharged from the Arkoma basin and adjacent platform during the Late Pennsylvanian to Early Permian Ouachita orogeny. New MC-ICP-MS Pb isotope analyses of sphalerites are presented in order to compare and contrast the isotopic signature of ores from the NA and TS districts with those from other MVT districts from central and eastern US and trace metal sources. The Pb isotope ratios of ores from the TS District (208Pb/204Pb between 40.7443 and 41.2626; 207Pb/204Pb between 15.8633 and 15.9571; 206Pb/204Pb between 21.8373 and 22.1956) plot in an area that is superimposed on the Pb isotope field defined by samples from the Central Missouri District, suggesting similar metal sources. The sphalerites are less radiogenic than samples from the Upper Mississippi Valley District, but more radiogenic than samples from any other MVT district. Sphalerites from the NA District have lower Pb isotope values (208Pb/204Pb between 39.4633 and 40.8863; 207Pb/204Pb between 15.8216 and 15.9176; 206Pb/204Pb between 20.2396 and 21.6438) than the TS District ores; they plot below the field defined by samples from the Illinois-Kentucky district and overlap the field defined by ores from the Southeast Missouri (Viburnum and Old Lead Belt) district, implying similar metal sources. Current data suggest that basement of Grenvillian age (1 - 1.2 by), thought to be present in Arkansas, to the south of the Viburnum Trend, may be a likely source of the radiogenic Pb component. Pb data from ores in the NA and the

Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

USGS Publications Warehouse

Pietruszka, Aaron J.; Neymark, Leonid

2017-01-01

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to (207Pb/206Pb and 208Pb/206Pb, or 20XPb/206Pb) or better than (206Pb/204Pb,207Pb/204Pb, and 208Pb/204Pb, or 20XPb/204Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the 20XPb/206Pb and 20

Reconnaissance geochemical exploration of the plutons of quartz monzonite and granite in the Jabal Lababa and Ar Rayth areas, southern Asir, Kingdom of Saudi Arabia

USGS Publications Warehouse

Overstreet, W.C.; Assegaff, A.B.; Jambi, Mohammed; Hussain, M.A.; Selner, G.I.; Matzko, J.J.

1985-01-01

Three nonmagnetic high-density concentrates containing 1,000 to 15,000 ppm lead were found on the granitic pluton near Ar Rayth. The source of the lead is not galena, and high values for lead appear to be characteristic of the pluton but do not indicate an ore deposit.

Ammunition is the principal source of lead accumulated by California condors re-introduced to the wild.

PubMed

Church, Molly E; Gwiazda, Roberto; Risebrough, Robert W; Sorenson, Kelly; Chamberlain, C Page; Farry, Sean; Heinrich, William; Rideout, Bruce A; Smith, Donald R

2006-10-01

The endangered California Condor (Gymnogyps californianus) was reduced to a total population of 22 birds by the end of 1982. Their captive-bred descendants are now being released back into the wild in California, Arizona, and Baja California, where monitoring indicates they may accumulate lead to toxic levels. Fragments of ammunition in the carcasses of game animals such as deer, elk, and feral pigs not retrieved by hunters or in gut piles left in the field have been considered a plausible source of the lead, though little direct evidence is available to support this hypothesis. Here, we measured lead concentrations and isotope ratios in blood from 18 condors living in the wild in central California, in 8 pre-release birds, and in diet and ammunition samples to determine the importance of ammunition as a source of exposure. Blood lead levels in pre-release condors were low (average 27.7 ng/mL, SD 4.9 ng/ mL) and isotopically similar to dietary and background environmental lead in California. In contrast, blood lead levels in free-flying condors were substantially higher (average 246 ng/mL, SD 229 ng/mL) with lead isotopic compositions that approached or matched those of the lead ammunition. A two-endmember mixing model defined by the background 207Pb/206Pb ratio of representative condor diet samples (0.8346) and the upper 207Pb/206Pb ratio of the ammunition samples (0.8184) was able to account for the blood lead isotopic compositions in 20 out of the 26 live condors sampled in this study (i.e., 77%). Finally, lead in tissues and in a serially sampled growing feather recovered postmortem from a lead-poisoned condor in Arizona evidence acute exposure from an isotopically distinct lead source. Together, these data indicate that incidental ingestion of ammunition in carcasses of animals killed by hunters is the principal source of elevated lead exposure that threatens the recovery in the wild of this endangered species.

Dual-isotope PET using positron-gamma emitters.

PubMed

Andreyev, A; Celler, A

2011-07-21

Positron emission tomography (PET) is widely recognized as a highly effective functional imaging modality. Unfortunately, standard PET cannot be used for dual-isotope imaging (which would allow for simultaneous investigation of two different biological processes), because positron-electron annihilation products from different tracers are indistinguishable in terms of energy. Methods that have been proposed for dual-isotope PET rely on differences in half-lives of the participating isotopes; these approaches, however, require making assumptions concerning kinetic behavior of the tracers and may not lead to optimal results. In this paper we propose a novel approach for dual-isotope PET and investigate its performance using GATE simulations. Our method requires one of the two radioactive isotopes to be a pure positron emitter and the second isotope to emit an additional high-energy gamma in a cascade simultaneously with positron emission. Detection of this auxiliary prompt gamma in coincidence with the annihilation event allows us to identify the corresponding 511 keV photon pair as originating from the same isotope. Two list-mode datasets are created: a primary dataset that contains all detected 511 keV photon pairs from both isotopes, and a second, tagged (much smaller) dataset that contains only those PET events for which a coincident prompt gamma has also been detected. An image reconstructed from the tagged dataset reflects the distribution of the second positron-gamma radiotracer and serves as a prior for the reconstruction of the primary dataset. Our preliminary simulation study with partially overlapping (18)F/(22)Na and (18)F/(60)Cu radiotracer distributions showed that in these two cases the dual-isotope PET method allowed for separation of the two activity distributions and recovered total activities with relative errors of about 5%.

Mercury isotope constraints on the source for sediment-hosted lead-zinc deposits in the Changdu area, southwestern China

NASA Astrophysics Data System (ADS)

Xu, Chunxia; Yin, Runsheng; Peng, Jiantang; Hurley, James P.; Lepak, Ryan F.; Gao, Jianfeng; Feng, Xinbin; Hu, Ruizhong; Bi, Xianwu

2018-03-01

The Lanuoma and Cuona sediment-hosted Pb-Zn deposits hosted by Upper Triassic limestone and sandstone, respectively, are located in the Changdu area, SW China. Mercury concentrations and Hg isotopic compositions from sulfide minerals and potential source rocks (e.g., the host sedimentary rocks and the metamorphic basement) were investigated to constrain metal sources and mineralization processes. In both deposits, sulfide minerals have higher mercury (Hg) concentrations (0.35 to 1185 ppm) than the metamorphic basement rocks (0.05 to 0.15 ppm) and sedimentary rocks (0.02 to 0.08 ppm). Large variations of mass-dependent fractionation (3.3‰ in δ202Hg) and mass-independent fractionation (0.3‰ in Δ199Hg) of Hg isotopes were observed. Sulfide minerals have Hg isotope signatures that are similar to the hydrothermal altered rocks around the deposit, and similar to the metamorphic basement, but different from barren sedimentary rocks. The variation of Δ199Hg suggests that Hg in sulfides was mainly derived from the underlying metamorphic basement. Mercury isotopes could be a geochemical tracer in understanding metal sources in hydrothermal ore deposits.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

USGS Publications Warehouse

Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

2015-01-01

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN

ISOTOPIC EVIDENCE ON THE ORIGIN AND AGE OF THE BLIND RIVER URANIUM DEPOSITS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mair, J.A.; Maynes, A.D.; Patchett, J.E.

Isotopic analyses of lead extracted from a variety of minerals from Blind River. Ontario, are repeated. The detrital minerals monazite and zircon both give leadratio ages of 2500 million years. The uraainite ore gives a lead- ratio age of 1700 m a. Other isotopic evidence is quoted to suggest that the age of the sediment in which the uranium is found may also be approximately 1700 m y, or older. The lead found in pyrite, pyrrhotite, sericite, and feldspar has anomalous isotopic ratios which can be explained by the hypothesis that they received additions of radiogenic lead from the uraninitesmore » (presumed to be 1700 m y old) 1200 to 1300 m y ago. In any case the age of these minerals, in the sense of time of last chemical alteration, is not greater than 1450 plus or minus 150 m y. All our measurements can be interpreted without asauming a major period of mineralization more recent than 1000 m y ago, although we are unable to rule out such a possibility from our evidence. (auth)« less

Combining lead isotopes and cluster analysis to distinguish the Guarani and Serra Geral Aquifer Systems and contaminated waters in a highly industrialized area in Southern Brazil.

PubMed

Kuhn, Isadora Aumond; Roisenberg, Ari

2017-10-01

The Rio dos Sinos Watershed area is located at the Middle-West region of the Rio Grande do Sul State, Southern Brazil, along thirty two municipalities and affecting 1.5 million inhabitants and many important industrial centers. Three main aquifers are recognized in the study area: the unconfined-fractured Serra Geral Aquifer System, the porous Guarani Aquifer System, and the Permian Aquitard. This study aims to understand groundwater, surface water and human activity interactions in the Rio dos Sinos Watershed, evaluating the application of stable lead isotopic ratios analyzed for this propose. Thirty six groundwater samples, 8 surface water samples and 5 liquid effluents of tanneries and landfills samples were measured using a Thermal Ionization Mass Spectrometer Thermo-Finnigan and a Neptune Multi-Collector Inductively Coupled Plasma Mass Spectrometer. Groundwater isotopic ratios have a wider range compared to the surface water, with less radiogenic averages 208 Pb/ 204 Pb = 38.1837 vs 38.4050 (standard deviation = 0.2921 vs 0.1343) and 206 Pb/ 204 Pb = 18.2947 vs 18.4766 (standard deviation = 0.2215 vs 0.1059), respectively. Industrial liquid effluents (tanneries and industrial landfill) have averages 208 Pb/ 204 Pb = 38.1956 and 206 Pb/ 204 Pb = 18.3169, distinct from effluent samples of domestic sanitary landfill (averages 208 Pb/ 204 Pb = 38.2353 and 206 Pb/ 204 Pb = 18.6607). Hierarchical cluster analysis led to distinguish six groups of groundwater, representing the three aquifers that occur in the area, two clusters suggesting groundwater mixtures and one demonstrating a highly contaminated groundwater. By analyzing the cluster results and wells' stratigraphic profiles it was possible to distinguish the different aquifers in the area. The Serra Geral Aquifer System has 206 Pb/ 204 Pb ratios between 18.4718 and 18.7089; 207 Pb/ 204 Pb between 15.6692 and 15.6777; 208 Pb/ 204 Pb between 38.6826 and 38.7616; 207 Pb/ 206 Pb between 0.8372 and 0

Post-17th-century changes of European lead emissions recorded in high-altitude alpine snow and ice.

PubMed

Schwikowski, Margit; Barbante, Carlo; Doering, Thomas; Gaeggeler, Heinz W; Boutron, Claude; Schotterer, Ulrich; Tobler, Leo; van de Velde, Katja; Ferrari, Christophe; Cozzi, Giulio; Rosman, Kevin; Cescon, Paolo

2004-02-15

Lead concentrations and lead isotope ratios were analyzed in two firn/ice cores covering the period from 1650 to 1994, which were obtained from the 4450 m high glacier saddle Colle Gnifetti located in the Monte Rosa massif at the Swiss-Italian border. This study presents the first glaciochemical time series with annual resolution, spanning several centuries of lead concentrations and lead isotopic compositions in precipitation in Europe. Lead concentrations in firn dated from the 1970s are approximately 25 times higher than in ice dated from the 17th century, confirming the massive rise in lead pollution in Europe during the last few centuries. A decline of the lead concentration is then observed during the last two decades, i.e., from 1975 to 1994. The lead isotope ratio 206Pb/207Pb decreased from about 1.18 in the 17th and 18th centuries to about 1.12 in the 1970s. These variations are in good agreement with available information on variations in anthropogenic lead emissions from West European countries, especially from the use of lead additives in gasoline.

Isotopic insights into biological regulation of zinc in contaminated systems

USGS Publications Warehouse

Wanty, Richard B.; Balistrieri, Laurie S.; Wesner, Jeff S.; Walters, David; Schmidt, Travis S.; Podda, Francesca; De Giudici, G.; Stricker, Craig A.; Kraus, Johanna M.; Lattanzi, Pierfranco; Wolf, Ruth E.; Cidu, R.

2015-01-01

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Radiogenic Isotopes in Weathering and Hydrology

NASA Astrophysics Data System (ADS)

Blum, J. D.; Erel, Y.

2003-12-01

as on the observation that radiogenic isotopes are sometimes preferentially released compared to nonradiogenic isotopes of the same element during acid leaching of rocks ( Hart and Tilton, 1966; Silver et al., 1984; Erel et al., 1991). A major finding of these investigations was that weathering often results in anomalously young Rb-Sr isochron ages, and discordant Pb-Pb ages. Rubidium is generally retained relative to strontium in whole-rock samples, and in some cases radiogenic strontium and lead are lost preferentially to common strontium and lead from weathered minerals.The most widely utilized of these isotopic systems is Rb-Sr, followed by U-Pb. The K-Ar system is not directly applicable to most studies of rock-water interaction, because argon is a noble gas, and upon release during mineral weathering mixes with atmospheric argon, limiting its usefulness as a tracer in most weathering applications. Argon and other noble gas isotopes have, however, found important applications in hydrology (see Chapter 5.15). Three other isotopic systems commonly used in geochronology and petrology include Sm-Nd, Lu-Hf, and Re-Os. These parent and daughter elements are in very low abundance and concentrated in trace mineral phases. Sm-Nd, Lu-Hf, and Re-Os have been used in a few weathering studies but have not been utilized extensively in investigations of weathering and hydrology.The decay of 87Rb to 87Sr has a half-life of 48.8 Gyr, and this radioactive decay results in natural variability in the 87Sr/86Sr ratio in rubidium-bearing minerals (e.g., Blum, 1995). The trace elements rubidium and strontium are geochemically similar to the major elements potassium and calcium, respectively. Therefore, minerals with high K/Ca ratios develop high 87Sr/86Sr ratios over geologic timescales. Once released into the hydrosphere, strontium retains its isotopic composition without significant fractionation by geochemical or biological processes, and is therefore a good tracer for sources and

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also

Origine du soufre associé aux minéralisations Pb-Zn de type Mississippi Valley de la chaîne des Beni Snassen orientaux (Maroc nord-oriental)

NASA Astrophysics Data System (ADS)

Bouabdellah, Mohammed; Boudchiche, Lahbib; Ouahhabi, Benali; Naciri, Tayeb

2008-12-01

Sulfur isotope data measured on samples of galena from the main Mississippi Valley-type prospects of the eastern Beni Snassen belt preclude an igneous source for sulfur, pointing instead to a sedimentary source. Negative δ 34S values are interpreted to being derived from bacteriogenic reduction of Jurassic seawater sulphate. Positive δ 34S values are considered to be hydrothermal sulfide transported with metal-bearing fluid. Mixing of these two fluids resulted in the deposition of the Pb ore.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

The calibration of the intramolecular nitrogen isotope distribution in nitrous oxide measured by isotope ratio mass spectrometry.

PubMed

Westley, Marian B; Popp, Brian N; Rust, Terri M

2007-01-01

Two alternative approaches for the calibration of the intramolecular nitrogen isotope distribution in nitrous oxide using isotope ratio mass spectrometry have yielded a difference in the 15N site preference (defined as the difference between the delta15N of the central and end position nitrogen in NNO) of tropospheric N2O of almost 30 per thousand. One approach is based on adding small amounts of labeled 15N2O to the N2O reference gas and tracking the subsequent changes in m/z 30, 31, 44, 45 and 46, and this yields a 15N site preference of 46.3 +/- 1.4 per thousand for tropospheric N2O. The other involves the synthesis of N2O by thermal decomposition of isotopically characterized ammonium nitrate and yields a 15N site preference of 18.7 +/- 2.2 per thousand for tropospheric N2O. Both approaches neglect to fully account for isotope effects associated with the formation of NO+ fragment ions from the different isotopic species of N2O in the ion source of a mass spectrometer. These effects vary with conditions in the ion source and make it impossible to reproduce a calibration based on the addition of isotopically enriched N2O on mass spectrometers with different ion source configurations. These effects have a much smaller impact on the comparison of a laboratory reference gas with N2O synthesized from isotopically characterized ammonium nitrate. This second approach was successfully replicated and leads us to advocate the acceptance of the site preference value 18.7 +/- 2.2 per thousand for tropospheric N2O as the provisional community standard until further independent calibrations are developed and validated. We present a technique for evaluating the isotope effects associated with fragment ion formation and revised equations for converting ion signal ratios into isotopomer ratios. Copyright 2007 John Wiley & Sons, Ltd.

A Hydrogen and He Isotope Nanoprobe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doyle, Barney L.; Van Deusen, Stuart B.

Materials that incorporate hydrogen and helium isotopes are of great interest at Sandia and throughout the NNSA and DOE. The Ion Beam Lab at SNL-NM has invented techniques using micron to mm-size MeV ion beams to recoil these light isotopes (Elastic Recoil Detection or ERD) that can very accurately make such measurements. However, there are many measurements that would benefit NW and DOE that require much better resolution, such as the distribution of H isotopes (and 3He) in individual grains of materials relevant to TPBARs, H and He-embrittlement of weapon components important to Tritium Sustainment Programs, issues with GTSs, batteries…more » Higher resolution would also benefit the field of materials science in general. To address these and many other issues, nm-scale lateral resolution is required. This LDRD demonstrated that neutral H atoms could be recoiled through a thin film by 70 keV electrons and detected with a Channeltron electron multiplier (CEM). The electrons were steered away from the CEM by strong permanent magnets. This proved the feasibility that the high energy electrons from a transmissionelectron- microscope-TEM can potentially be used to recoil and subsequently detect (e-ERD), quantify and map the concentration of H and He isotopes with nm resolution. This discovery could lead to a TEM-based H/He-isotope nanoprobe with 1000x higher resolution than currently available.« less

Carbon isotopes in mollusk shell carbonates

NASA Astrophysics Data System (ADS)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

Lead-203 as a label for radioimaging

DOEpatents

Srivastava, Suresh C.; Meinken, George E.

1990-01-01

A radiopharmaceutical composition comprising a radioactive isotope of lead (Pb-203) in combination with a pharmaceutical or an antibody or antibody fragment and a bifunctional chelating agent. These compositions are especially useful in the imaging and diagnosis of tumors and tumor metastases.

Lead-203 as a label for radioimaging

DOEpatents

Srivastava, Suresh C.; Meinken, George E.

1990-02-06

A radiopharmaceutical composition comprising a radioactive isotope of lead (Pb-203) in combination with a pharmaceutical or an antibody or antibody fragment and a bifunctional chelating agent. These compositions are especially useful in the imaging and diagnosis of tumors and tumor metastases.

Isotopic Biogeochemistry

NASA Technical Reports Server (NTRS)

Hayes, J. M.

1985-01-01

An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

Uranium Isotope Ratios in Modern and Precambrian Soils

NASA Astrophysics Data System (ADS)

DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

2015-12-01

Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Tracing cadmium, zinc and lead sources in bivalves from the coasts of western Canada and the USA using isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Orians, Kristin J.

2012-01-01

Environmental monitoring and remediation require techniques to identify the source and fate of metals emissions. The measurement of heavy metal isotopic signatures, made possible by the advent of the MC-ICP-MS, is a powerful new geochemical tool, which may be used to trace the source of these metals in the environment. In a multi-tracer study, Cd, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western Canada (British Columbia), Hawaii, and the USA East Coast. Variability in the δ 114/110Cd values of bivalves (-1.20‰ to -0.09‰) is attributed to differences in the relative contributions of Cd from natural and anthropogenic sources between sites. Cadmium isotopic compositions (δ 114/110Cd = -0.69‰ to -0.09‰) identify high Cd levels in B.C. oysters as primarily natural (i.e., upwelling of Cd rich intermediate waters in the North Pacific), with some variability attributed to anthropogenic sources (e.g., mining and smelting). Variability in the δ 66/64Zn values exhibited by the B.C. bivalves is relatively small (0.28-0.36‰). Despite the low Pb levels found in B.C. oysters, Pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources. Although the Cd concentrations of the USA East Coast bivalves are primarily lower than those of B.C. oysters, their relatively light Cd isotopic compositions (δ 114/110Cd = -1.20‰ to -0.54‰) indicate the significance of anthropogenic Cd sources and are attributed to the high prevalence of industry on this coast. The δ 114/110Cd values of USA East Coast bivalves include the lightest ever reported, with the exception of values reported for extraterrestrial materials. In addition, the Pb isotopic compositions of bivalves from the USA East Coast indicate Pb emissions from the combustion of

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

Noble Gas Isotope Evidence for Mantle Volatiles in the Cu-Mo Porphyry and Main Stage Polymetallic Veins at Butte, Montana

NASA Astrophysics Data System (ADS)

Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.

2017-12-01

Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

Contamination risk of stable isotope samples during milling.

PubMed

Isaac-Renton, M; Schneider, L; Treydte, K

2016-07-15

Isotope analysis of wood is an important tool in dendrochronology and ecophysiology. Prior to mass spectrometry analysis, wood must be homogenized, and a convenient method involves a ball mill capable of milling samples directly in sample tubes. However, sample-tube plastic can contaminate wood during milling, which could lead to biological misinterpretations. We tested possible contamination of whole wood and cellulose samples during ball-mill homogenization for carbon and oxygen isotope measurements. We used a multi-factorial design with two/three steel milling balls, two sample amounts (10 mg, 40 mg), and two milling times (5 min, 10 min). We further analyzed abrasion by milling empty tubes, and measured the isotope ratios of pure contaminants. A strong risk exists for carbon isotope bias through plastic contamination: the δ(13) C value of polypropylene deviated from the control by -6.77‰. Small fibers from PTFE filter bags used during cellulose extraction also present a risk as the δ(13) C value of this plastic deviated by -5.02‰. Low sample amounts (10 mg) showed highest contamination due to increased abrasion during milling (-1.34‰), which is further concentrated by cellulose extraction (-3.38‰). Oxygen isotope measurements were unaffected. A ball mill can be used to homogenize samples within test tubes prior to oxygen isotope analysis, but not prior to carbon or radiocarbon isotope analysis. There is still a need for a fast, simple and contamination-free sample preparation procedure. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Pb isotope geochemistry of Piton de la Fournaise historical lavas

NASA Astrophysics Data System (ADS)

Vlastélic, Ivan; Deniel, Catherine; Bosq, Chantal; Télouk, Philippe; Boivin, Pierre; Bachèlery, Patrick; Famin, Vincent; Staudacher, Thomas

2009-07-01

Variations of Pb isotopes in historical lavas (1927-2007) from Piton de la Fournaise are investigated based on new (116 samples) and published (127 samples) data. Lead isotopic signal exhibits smooth fluctuations (18.87 < 206Pb/ 204Pb < 18.94) on which superimpose unradiogenic spikes ( 206Pb/ 204Pb down to 18.70). Lead isotopes are decoupled from 87Sr/ 86Sr and 143Nd/ 144Nd, which display small and barely significant variations, respectively. No significant change of Pb isotope composition occurred during the longest (> 3 years) periods of inactivity of the volcano (1939-1942, 1966-1972, 1992-1998), supporting previous inferences that Pb isotopic variations occur mostly during and not between eruptions. Intermediate compositions (18.904 < 206Pb/ 204Pb < 18.917) bracket the longest periods of quiescence. In this respect, the highly frequent occurrence of an intermediate composition (18.90 < 206Pb/ 204Pb < 18.91), which clearly defines an isotopic baseline during the most recent densely sampled period (1975-2007), either suggests direct sampling of plume melts or sampling of a voluminous magma reservoir that buffers Pb isotopic composition. Deviations from this prevalent composition occurred during well-defined time periods, namely 1977-1986 (radiogenic signature), 1986-1990 and 1998-2005 (unradiogenic signatures). The three periods display a progressive isotopic drift ending by a rapid return (mostly during a single eruption) to the isotopic baseline. The isotopic gradients could reflect progressive emptying of small magma reservoirs or magma conduits, which are expected to be more sensitive to wall-rock interactions than the main magma chamber. These gradients provide a lower bound ranging from 0.1 to 0.17 km 3 for the size of the shallow magma storage system. The isotopic shifts (March 1986, January 1990 and February 2005) are interpreted as refilling the plumbing system with deep melts that have not interacted with crustal components. The volume of magma erupted

Distribution and Source Identification of Pb Contamination in industrial soil

NASA Astrophysics Data System (ADS)

Ko, M. S.

2017-12-01

INTRODUCTION Lead (Pb) is toxic element that induce neurotoxic effect to human, because competition of Pb and Ca in nerve system. Lead is classified as a chalophile element and galena (PbS) is the major mineral. Although the Pb is not an abundant element in nature, various anthropogenic source has been enhanced Pb enrichment in the environment after the Industrial Revolution. The representative anthropogenic sources are batteries, paint, mining, smelting, and combustion of fossil fuel. Isotope analysis widely used to identify the Pb contamination source. The Pb has four stable isotopes that are 208Pb, 207Pb, 206Pb, and 204Pb in natural. The Pb is stable isotope and the ratios maintain during physical and chemical fractionation. Therefore, variations of Pb isotope abundance and relative ratios could imply the certain Pb contamination source. In this study, distributions and isotope ratios of Pb in industrial soil were used to identify the Pb contamination source and dispersion pathways. MATERIALS AND METHODS Soil samples were collected at depth 0­-6 m from an industrial area in Korea. The collected soil samples were dried and sieved under 2 mm. Soil pH, aqua-regia digestion and TCLP carried out using sieved soil sample. The isotope analysis was carried out to determine the abundance of Pb isotope. RESULTS AND DISCUSSION The study area was developed land for promotion of industrial facilities. The study area was forest in 1980, and the satellite image show the alterations of land use with time. The variations of land use imply the possibilities of bringing in external contaminated soil. The Pb concentrations in core samples revealed higher in lower soil compare with top soil. Especially, 4 m soil sample show highest Pb concentrations that are approximately 1500 mg/kg. This result indicated that certain Pb source existed at 4 m depth. CONCLUSIONS This study investigated the distribution and source identification of Pb in industrial soil. The land use and Pb

2. Historic American Buildings Survey Joseph Hill, Photographer October 28, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. Historic American Buildings Survey Joseph Hill, Photographer October 28, 1936 #1 DOORWAY MAXIENER HOUSE 104 South Bench Street, Galena, Ill. (Said to be oldest frame house in Galena) - Galena Doorways, Elizabeth Maxiener Cottage, 104 South Bench Street, Galena, Jo Daviess County, IL

Post-eruptive alteration of silicic ignimbrites and lavas, Gran Canaria, Canary Islands - Strontium, neodymium, lead, and oxygen isotopic evidence

NASA Technical Reports Server (NTRS)

Cousens, Brian L.; Spera, Frank J.; Dobson, Patrick F.

1993-01-01

The isotopic composition of lavas from oceanic islands provides important information about the composition and evolution of the earth's mantle. Isotopic analyses of Miocene comenditic, pantelleritic, and trachyphonolitic ignimbrites and lavas from the Canary islands were performed. Results provide evidence for posteruptive mobility of Rb and Sr during low temperature postemplacement interaction with circulating ground water. Calculated Sr isotope ratios define a magmatic trend in the stratigraph section. 87Sr/86Sr ratios in hydrated vitrophyte and devitrified matrix separates indicate significant posteruptive interaction with meteoric water starting soon after deposition. This process extends patchily through the entire pyroclastic flow and may be ongoing. 87Sr/86Sr ratios determined by whole rock analysis of silicic rocks from oceanic islands are suspect and should not be incorporated into mantle tracer studies. Anorthoclase phenocrysts are resistant to these processes and may produce useful data.

Lead spatio-temporal pattern identification in urban microenvironments using moss bags and the Kohonen self-organizing maps

NASA Astrophysics Data System (ADS)

Deljanin, Isidora; Antanasijević, Davor; Vuković, Gordana; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana

2015-09-01

The first investigation of the use of the Kohonen self-organizing map (SOM) which includes lead concentration and its isotopic composition in moss bags to assess the spatial and temporal patterns of lead in the urban microenvironments is presented in this paper. The moss bags experiment was carried out during 2011 in the city tunnel in Belgrade, as well as in street canyons at different heights (4, 8 and 16 m) and in public garages. The moss bags were exposed for 5 and 10 weeks. The results revealed that the 10 weeks period represents suitable exposure time in screening Pb isotopic composition in active biomonitoring analysis. The obtained results showed that the SOM analysis, by recognizing slight differences among moss samples regarding exposure time, horizontal and vertical spatial distribution, with both, contribution of stable lead isotopes and Pb concentration, could be recommended in biomonitoring analysis of lead distribution in urban microenvironments.

Environmental lead pollution threatens the children living in the Pearl River Delta region, China.

PubMed

Chen, Jianmin; Tong, Yongpeng; Xu, Jiazhang; Liu, Xiaoli; Li, Yulan; Tan, Mingguang; Li, Yan

2012-09-01

The objective of this study is to determine children's blood lead levels and identify sources of lead exposure. Childhood lead exposure constitutes a major pediatric health problem today in China. A blood lead screening survey program for children in the age group of 2-12 years residing in Pearl River Delta region, south of China, was carried out from Dec 2007 to Jan 2008. Blood lead levels and lead isotope ratios of a total of 761 participants were assessed by inductively coupled plasma mass spectroscopy. Measurements of urban environmental samples for source identification of children lead exposure were also performed. The geometric mean value of the children's blood lead levels was 57.05 μg/L, and 9.6% of them were higher than 100 μg/L. The blood lead levels were still much higher than those in developed countries. Based on the data of environmental lead source inventories, lead isotopic tracing revealed that there is about 6.7% past used gasoline Pb embedded in Shenzhen residential dust and about 15.6% in Guangzhou dust, respectively.

Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

USGS Publications Warehouse

Klemm, V.; Frank, M.; Levasseur, S.; Halliday, A.N.; Hein, J.R.

2008-01-01

Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

Pb-Sr isotopic and geochemical constraints on sources and processes of lead contamination in well waters and soil from former fruit orchards, Pennsylvania, USA: A legacy of anthropogenic activities

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2016-01-01

Isotopic discrimination can be an effective tool in establishing a direct link between sources of Pb contamination and the presence of anomalously high concentrations of Pb in waters, soils, and organisms. Residential wells supplying water containing up to 1600 ppb Pb to houses built on the former Mohr orchards commercial site, near Allentown, PA, were evaluated to discern anthropogenic from geogenic sources. Pb (n = 144) and Sr (n = 40) isotopic data and REE (n = 29) data were determined for waters from residential wells, test wells (drilled for this study), and surface waters from pond and creeks. Local soils, sediments, bedrock, Zn-Pb mineralization and coal were also analyzed (n = 94), together with locally used Pb-As pesticide (n = 5). Waters from residential and test wells show overlapping values of 206Pb/207Pb, 208Pb/207Pb and 87Sr/86Sr. Larger negative Ce anomalies (Ce/Ce*) distinguish residential wells from test wells. Results show that residential and test well waters, sediments from residential water filters in water tanks, and surface waters display broad linear trends in Pb isotope plots. Pb isotope data for soils, bedrock, and pesticides have contrasting ranges and overlapping trends. Contributions of Pb from soils to residential well waters are limited and implicated primarily in wells having shallow water-bearing zones and carrying high sediment contents. Pb isotope data for residential wells, test wells, and surface waters show substantial overlap with Pb data reflecting anthropogenic actions (e.g., burning fossil fuels, industrial and urban processing activities). Limited contributions of Pb from bedrock, soils, and pesticides are evident. High Pb concentrations in the residential waters are likely related to sediment build up in residential water tanks. Redox reactions, triggered by influx of groundwater via wells into the residential water systems and leading to subtle changes in pH, are implicated in precipitation of Fe oxyhydroxides

First-principles theory of anharmonicity and the inverse isotope effect in superconducting palladium-hydride compounds.

PubMed

Errea, Ion; Calandra, Matteo; Mauri, Francesco

2013-10-25

Palladium hydrides display the largest isotope effect anomaly known in the literature. Replacement of hydrogen with the heavier isotopes leads to higher superconducting temperatures, a behavior inconsistent with harmonic theory. Solving the self-consistent harmonic approximation by a stochastic approach, we obtain the anharmonic free energy, the thermal expansion, and the superconducting properties fully ab initio. We find that the phonon spectra are strongly renormalized by anharmonicity far beyond the perturbative regime. Superconductivity is phonon mediated, but the harmonic approximation largely overestimates the superconducting critical temperatures. We explain the inverse isotope effect, obtaining a -0.38 value for the isotope coefficient in good agreement with experiments, hydrogen anharmonicity being mainly responsible for the isotope anomaly.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

2013-12-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2016-01-01

The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

PubMed

Coplen, Tyler B; Qi, Haiping

2016-09-01

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

Time differences in the formation of meteorites as determined from the ratio of lead-207 to lead-206

USGS Publications Warehouse

Tatsumoto, M.; Knight, R.J.; Allegre, C.J.

1973-01-01

Measurements of the lead isotopic composition and the uranium, thorium, and lead concentrations in meteorites were made in order to obtain more precise radiometric ages of these members of the solar system. The newly determined value of the lead isotopic composition of Canyon Diablo troilite is as follows: 206Pb/204Pb = 9.307, 207Pb/204Pb = 10.294, and 208Pb/204Pb = 29.476. The leads of Angra dos Reis, Sioux County, and Nuevo Laredo achondrites are very radiogenic, the 206Pb/204Pb values are about 200, and the uranium-thorium-lead systems are nearly concordant. The ages of the meteorites as calculated from a single-stage 207Pb/206Pb isochron based on the newly determined primordial lead value and the newly reported 235U and 238U decay constants, are 4.528 ?? 10 9 years for Sioux County and Nuevo Laredo and 4.555 ?? 10 9 years for Angra dos Reis. When calculated with the uranium decay constants used by Patterson, these ages are 4.593 ?? 109 years and 4.620 ?? 109 years, respectively, and are therefore 40 to 70 ?? 106 years older than the 4.55 ?? 109 years age Patterson reported. The age difference of 27 ?? 106 years between Angra dos Reis and the other two meteorites is compatible with the difference between the initial 87Sr/86Sr ratio of Angra dos Reis and that of seven basaltic achondrites observed by Papanastassiou and Wasserburg. The time difference is also comparable to that determined by 129I-129Xe chronology. The ages of ordinary chondrites (H5 and L6) range from 4.52 to 4.57 ?? 109 years, and, here too, time differences in the formation of the parent bodies or later metamorphic events are indicated. Carbonaceous chondrites (C2 and C3) appear to contain younger lead components.

Effects of acidification on the isotopic ratios of Neotropical otter tooth dentin.

PubMed

Carrasco, Thayara S; Botta, Silvina; Machado, Rodrigo; Colares, Elton P; Secchi, Eduardo R

2018-05-30

Stable carbon and nitrogen isotope ratios are widely used in ecological studies providing important information on the trophic ecology and habitat use of consumers. However, some factors may lead to isotopic variability, which makes difficult the interpretation of data, such as the presence of inorganic carbon in mineralized tissues. In order to remove the inorganic carbon, acidification is a commonly used treatment. The effects of two methods of acidification were tested: (i) dentin acidification with 10% HCl using the 'drop-by-drop' technique, and (ii) dentin acidification in an 'HCl atmosphere', by exposing the dentin to vaporous 30% hydrochloric acid. Results were compared with untreated subsamples. The stable carbon and nitrogen ratios of untreated and acidified subsamples were measured using an elemental analyzer coupled to an isotope ratio mass spectrometer. The nitrogen isotopic ratios were statistically different between the two acidification treatments, but no significant changes in carbon isotopic ratios were found in acidified and untreated samples. The results indicated that acidification had no effect on carbon isotopic ratios of Neotropical otter tooth dentin, while introducing a source of error in nitrogen isotopic ratios. Therefore, we conclude that acidification is an unnecessary step for C and N stable isotope analysis. Copyright © 2018 John Wiley & Sons, Ltd.

Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

NASA Astrophysics Data System (ADS)

Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

2016-01-01

Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application.

Stable Isotope Ratios as Biomarkers of Diet for Health Research

PubMed Central

O’Brien, Diane M.

2016-01-01

Diet is a leading modifiable risk factor for chronic disease, but it remains difficult to measure accurately due to the error and bias inherent in self-reported methods of diet assessment. Consequently there is a pressing need for more objective biomarkers of diet for use in health research. The stable isotope ratios of light elements are a promising set of candidate biomarkers because they vary naturally and reproducibly among foods, and those variations are captured in molecules and tissues with high fidelity. Recent studies have identified valid isotopic measures of short and long-term sugar intake, meat intake, and fish intake in specific populations. These studies provide a strong foundation for validating stable isotopic biomarkers in the general United States population. Approaches to improve specificity for specific foods are needed, for example, by modeling intake using multiple stable isotope ratios, or by isolating and measuring specific molecules linked to foods of interest. PMID:26048703

Nitrogen isotopic components in the early solar system

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1994-01-01

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

Chromium isotope fractionation in ferruginous sediments

NASA Astrophysics Data System (ADS)

Bauer, Kohen W.; Gueguen, Bleuenn; Cole, Devon B.; Francois, Roger; Kallmeyer, Jens; Planavsky, Noah; Crowe, Sean A.

2018-02-01

Ferrous Fe is a potent reductant of Cr(VI), and while a number of laboratory studies have characterized Cr isotope fractionation associated with Cr(VI) reduction by ferrous iron, the expression of this fractionation in real-world ferrous Fe-rich environments remains unconstrained. Here we determine the isotope fractionation associated with Cr(VI) reduction in modern ferrous Fe-rich sediments obtained from the previously well studied Lake Matano, Indonesia. Whole core incubations demonstrate that reduction of Cr(VI) within ferruginous sediments provides a sink for Cr(VI) leading to Cr(VI) concentration gradients and diffusive Cr(VI) fluxes across the sediment water interface. As reduction proceeded, Cr(VI) remaining in the overlying lake water became progressively enriched in the heavy isotope (53Cr), increasing δ53Cr by 2.0 ± 0.1‰ at the end of the incubation. Rayleigh distillation modelling of the evolution of Cr isotope ratios and Cr(VI) concentrations in the overlying water yields an effective isotope fractionation of εeff = 1.1 ± 0.2‰ (53Cr/52Cr), whereas more detailed diagenetic modelling implies an intrinsic isotope fractionation of εint = 1.80 ± 0.04‰. Parallel slurry experiments performed using anoxic ferruginous sediment yield an intrinsic isotope fractionation of εint = 2.2 ± 0.1‰. These modelled isotope fractionations are corroborated by direct measurement of the δ53Cr composition on the upper 0.5 cm of Lake Matano sediment, revealing an isotopic offset from the lake water of Δ53Cr = 0.21-1.81‰. The data and models reveal that effective isotope fractionations depend on the depth at which Cr(VI) reduction takes place below the sediment water interface-the deeper the oxic non-reactive zone, the smaller the effective fractionation relative to the intrinsic fractionation. Based on the geochemistry of the sediment we suggest the electron donors responsible for reduction are a combination of dissolved Fe(II) and 0.5 M HCl extractable (solid

Intraspecific carbon and nitrogen isotopic variability in foxtail millet (Setaria italica).

PubMed

Lightfoot, Emma; Przelomska, Natalia; Craven, Martha; O Connell, Tamsin C; He, Lu; Hunt, Harriet V; Jones, Martin K

2016-07-15

Isotopic palaeodietary studies generally focus on bone collagen from human and/or animal remains. While plant remains are rarely analysed, it is known that plant isotope values can vary as a result of numerous factors, including soil conditions, the environment and type of plant. The millets were important food crops in prehistoric Eurasia, yet little is known about the isotopic differences within millet species. Here we compare the stable isotope ratios within and between Setaria italica plants grown in a controlled environment chamber. Using homogenised samples, we compare carbon isotope ratios of leaves and grains, and nitrogen isotope ratios of grains, from 29 accessions of Setaria italica. We find significant isotopic variability within single leaves and panicles, and between leaves and panicles within the same plant, which must be considered when undertaking plant isotope studies. We find that the leaves and grains from the different accessions have a ca 2‰ range in δ(13) C values, while the nitrogen isotope values in the grains have a ca 6‰ range. We also find an average offset of 0.9‰ between leaves and grains in their δ(13) C values. The variation found is large enough to have archaeological implications and within- and between-plant isotope variability should be considered in isotope studies. The range in δ(15) N values is particularly significant as it is larger than the typical values quoted for a trophic level enrichment, and as such may lead to erroneous interpretations of the amount of animal protein in human or animal diets. It is therefore necessary to account for the variability in plant stable isotope values during palaeodietary reconstructions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.

2010-11-25

H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes onmore » both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.« less

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

Lead Isotope Compositions of Acid Residues from Olivine-Phyric Shergottite Tissint: Implications for Heterogeneous Shergottite Source Reservoirs

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

2015-01-01

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions and trace element abundances. These correlations have been interpreted as indicating the presence of a reduced, incompatible element- depleted reservoir and an oxidized, incompatible- element-enriched reservoir. The former is clearly a depleted mantle source, but there is ongoing debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former requires the ancient Martian crust to be the enriched source (crustal assimilation), whereas the latter requires isolation of a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and trace element concentration analyses of sequential acid-leaching fractions (leachates and the final residues) from the geochemically depleted olivine-phyric shergottite Tissint. The results suggest that the Tissint magma is not isotopically uniform and sampled at least two geochemical source reservoirs, implying that either crustal assimilation or magma mixing would have played a role in the Tissint petrogenesis.

Reduction of arsenic content in a complex galena concentrate by Acidithiobacillus ferrooxidans

PubMed Central

Makita, Mario; Esperón, Margarita; Pereyra, Benito; López, Alejandro; Orrantia, Erasmo

2004-01-01

Background Bioleaching is a process that has been used in the past in mineral pretreatment of refractory sulfides, mainly in the gold, copper and uranium benefit. This technology has been proved to be cheaper, more efficient and environmentally friendly than roasting and high pressure moisture heating processes. So far the most studied microorganism in bioleaching is Acidithiobacillus ferrooxidans. There are a few studies about the benefit of metals of low value through bioleaching. From all of these, there are almost no studies dealing with complex minerals containing arsenopyrite (FeAsS). Reduction and/or elimination of arsenic in these ores increase their value and allows the exploitation of a vast variety of minerals that today are being underexploited. Results Arsenopyrite was totally oxidized. The sum of arsenic remaining in solution and removed by sampling represents from 22 to 33% in weight (yield) of the original content in the mineral. The rest of the biooxidized arsenic form amorphous compounds that precipitate. Galena (PbS) was totally oxidized too, anglesite (PbSO4) formed is virtually insoluble and remains in the solids. The influence of seven factors in a batch process was studied. The maximum rate of arsenic dissolution in the concentrate was found using the following levels of factors: small surface area of particle exposure, low pulp density, injecting air and adding 9 K medium to the system. It was also found that ferric chloride and carbon dioxide decreased the arsenic dissolution rate. Bioleaching kinetic data of arsenic solubilization were used to estimate the dilution rate for a continuous culture. Calculated dilution rates were relatively small (0.088–0.103 day-1). Conclusion Proper conditions of solubilization of arsenic during bioleaching are key features to improve the percentage (22 to 33% in weight) of arsenic removal. Further studies are needed to determine other factors that influence specifically the solubilization of arsenic in

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pizzarello, Sandra, E-mail: pizzar@asu.edu

2014-12-01

HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organicmore » compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.« less

Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

NASA Astrophysics Data System (ADS)

Coleman, M.; Rhorssen, M.; Mielke, R. E.

2008-12-01

Isotopic variations measured within a single crystal of hydrated magnesium sulfate are greater than 30 permil for delta 2-H, almost 10 permil for δ18O in water of hydration; and greater than 3 permil in sulfate oxygen. These results are interpreted to indicate the relative humidity of the system during evaporation (15 to 20 percent in this test case) and constrain the volume of water involved. The theoretical basis of this system is the isotopic fractionation between the species in solution and those precipitated as evaporite salts. Precipitation preferentially accumulates more of the heavy isotopes of sulfur and oxygen in mineral sulfate, relative to sulfate in solution. During the course of mineral growth this leads to successive depletion of the respective heavier isotopes in the residual brine reflected in a parallel trend in successive precipitates or even in successive zones within a single crystal. The change in isotopic composition at any one time during the process, relative to the initial value, can be described by an isotopic version of the Rayleigh Fractionation equation, depending only on the extent of the completion of the process and the relevant fractionation factor. Evaporation preferentially removes isotopically lighter hydrogen and oxygen leading to successive extents of enrichment in the respective heavier isotopes in the residual water. However, the relative effects on hydrogen and oxygen isotopes differs as function of relative humidity [1]. ALL OF THESE CHANGES ARE PRESERVED IN THE MINERAL ISOTOPE COMPOSITIONS. We precipitated barium sulfate from epsomite or gypsum samples, which was reduced at 1450°C in the presence of graphite and glassy carbon in a Finnigan TC/EA to produce CO for O isotopic analysis in a Finnigan 253 mass spectrometer, while a separate subsample was oxidized to SO2 in a Costech Elemental Analyzer. However, to make progress with this approach we needed to make a large number of measurements of hydration water and so we

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

Corcoran, Loretta; Seward, Terry; Handler, Monica R.

2015-04-01

Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

Shergottite Lead Isotope Signature in Chassigny and the Nakhlites

NASA Technical Reports Server (NTRS)

Jones, J. H.; Simon, J. I.

2017-01-01

The nakhlites/chassignites and the shergottites represent two differing suites of basaltic martian meteorites. The shergottites have ages less than or equal to 0.6 Ga and a large range of initial Sr-/Sr-86 and epsilon (Nd-143) ratios. Conversely, the nakhlites and chassignites cluster at 1.3-1.4 Ga and have a limited range of initial Sr-87/Sr-86 and epsilon (Nd-143). More importantly, the shergottites have epsilon (W-182) less than 1, whereas the nakhlites and chassignites have epsilon (W-182) approximately 3. This latter observation precludes the extraction of both meteorite groups from a single source region. However, recent Pb isotopic analyses indicate that there may have been interaction between shergottite and nakhlite/chassignite Pb reservoirs.Pb Analyses of Chassigny: Two different studies haveinvestigated 207Pb/204Pb vs. 206Pb/204Pb in Chassigny: (i)TIMS bulk-rock analyses of successive leaches and theirresidue [3]; and (ii) SIMS analysis of individual minerals[4]. The bulk-rock analyses fall along a regression of SIMSplagioclase analyses that define an errorchron that is olderthan the Solar System (4.61±0.1 Ga); i.e., these define amixing line between Chassigny’s principal Pb isotopic components(Fig. 1). Augites and olivines in Chassingy (notshown) also fall along or near the plagioclase regression [4].This agreement indicates that the whole-rock leachateslikely measure indigenous, martian Pb, not terrestrial contamination[5]. SIMS analyses of K-spars and sulfides definea separate, sub-parallel trend having higher 207Pb/206Pbvalues ([4]; Fig. 1). The good agreement between the bulkrockanalyses and the SIMS analyses of plagioclases alsoindicates that the Pb in the K-spars and sulfides cannot be amajor component of Chassigny.The depleted reservoir sampled by Chassigny plagioclaseis not the same as the solar system initial (PAT) andrequires a multi-stage origin. Here we show a two-stagemodel (Fig. 1) with a 238U/204Pb (µ) of 0.5 for 4.5-2.4 Gaand a µ of

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, C.A.; Worden, E.F.

1995-08-22

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

Formation of recent Pb-Ag-Au mineralization by potential sub-surface microbial activity

NASA Astrophysics Data System (ADS)

Tornos, Fernando; Velasco, Francisco; Menor-Salván, César; Delgado, Antonio; Slack, John F.; Escobar, Juan Manuel

2014-08-01

Las Cruces is a base-metal deposit in the Iberian Pyrite Belt, one of the world’s best-known ore provinces. Here we report the occurrence of major Pb-Ag-Au mineralization resulting from recent sub-surface replacement of supergene oxyhydroxides by carbonate and sulphide minerals. This is probably the largest documented occurrence of recent microbial activity producing an ore assemblage previously unknown in supergene mineralizing environments. The presence of microbial features in the sulphides suggests that these may be the first-described natural bacteriomorphs of galena. The low δ13C values of the carbonate minerals indicate formation by deep anaerobic microbial processes. Sulphur isotope values of sulphides are interpreted here as reflecting microbial reduction in a system impoverished in sulphate. We suggest that biogenic activity has produced around 3.1 × 109 moles of reduced sulphur and 1010 moles of CO2, promoting the formation of ca. 1.19 Mt of carbonates, 114,000 t of galena, 638 t of silver sulphides and 6.5 t of gold.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd

Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

DOEpatents

Harney, Robert C.; Bloom, Stewart D.

1978-01-01

Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances.

Using biochemical and isotope geochemistry to understand the environmental and public health implications of lead pollution in the lower Guadiana River, Iberia: a freshwater bivalve study.

PubMed

Company, R; Serafim, A; Lopes, B; Cravo, A; Shepherd, T J; Pearson, G; Bebianno, M J

2008-11-01

Lead is a natural component of aquatic ecosystems with no known biological role and is highly toxic. Its toxicity stems from its ability to mimic biologically important metals and to produce membrane damage through lipid peroxidation (LPO). Most lead poisoning symptoms are thought to occur by interfering with an essential enzyme, delta-aminolevulinic acid dehydratase (ALAD), the activity of which is markedly inhibited by lead. The purpose of this work was to study the levels and effects of lead pollution (responses of ALAD and oxidative stress biomarker LPO) in the freshwater bivalve Corbicula fluminea along the lower Guadiana River (Portugal and Spain); a major river system impacted by historic mining pollution and more recent anthropogenic inputs. The results show that the enzymatic activity of ALAD is negatively correlated with the total Pb concentration of the whole tissue suggesting that ALAD has considerable potential as a biomarker of lead exposure in C. fluminea. To identify the sources of lead to which bivalves have been exposed, high precision (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)/Pb ratios for C. fluminea confirm that historical mining activities in the Iberian Pyrite Belt are the dominant source of lead pollution in the lower Guadiana River. The isotope patterns however exhibit marked seasonal and geographic variation in response to rainfall and river water management. Locally, other anthropogenic sources of lead have been detected in C. fluminea close to population centres, thus adding to its versatility as a freshwater bio-indicator. Overall, the study highlights the value of natural ecosystems as monitors of water quality and their importance for public health assessment and surveillance.

High risk of lead contamination for scavengers in an area with high moose hunting success.

PubMed

Legagneux, Pierre; Suffice, Pauline; Messier, Jean-Sébastien; Lelievre, Frédérick; Tremblay, Junior A; Maisonneuve, Charles; Saint-Louis, Richard; Bêty, Joël

2014-01-01

Top predators and scavengers are vulnerable to pollutants, particularly those accumulated along the food chain. Lead accumulation can induce severe disorders and alter survival both in mammals (including humans) and in birds. A potential source of lead poisoning in wild animals, and especially in scavengers, results from the consumption of ammunition residues in the tissues of big game killed by hunters. For two consecutive years we quantified the level lead exposure in individuals of a sentinel scavenger species, the common raven (Corvus corax), captured during the moose (Alces alces) hunting season in eastern Quebec, Canada. The source of the lead contamination was also determined using stable isotope analyses. Finally, we identified the different scavenger species that could potentially be exposed to lead by installing automatic cameras targeting moose gut piles. Blood lead concentration in ravens increased over time, indicating lead accumulation over the moose-hunting season. Using a contamination threshold of 100 µg x L(-1), more than 50% of individuals were lead-contaminated during the moose hunting period. Lead concentration was twice as high in one year compared to the other, matching the number of rifle-shot moose in the area. Non-contaminated birds exhibited no ammunition isotope signatures. The isotope signature of the lead detected in contaminated ravens tended towards the signature from lead ammunition. We also found that black bears (Ursus americanus), golden eagles and bald eagles (Aquila chrysaetos and Haliaeetus leucocephalus, two species of conservation concern) scavenged heavily on moose viscera left by hunters. Our unequivocal results agree with other studies and further motivate the use of non-toxic ammunition for big game hunting.

High Risk of Lead Contamination for Scavengers in an Area with High Moose Hunting Success

PubMed Central

Legagneux, Pierre; Suffice, Pauline; Messier, Jean-Sébastien; Lelievre, Frédérick; Tremblay, Junior A.; Maisonneuve, Charles; Saint-Louis, Richard; Bêty, Joël

2014-01-01

Top predators and scavengers are vulnerable to pollutants, particularly those accumulated along the food chain. Lead accumulation can induce severe disorders and alter survival both in mammals (including humans) and in birds. A potential source of lead poisoning in wild animals, and especially in scavengers, results from the consumption of ammunition residues in the tissues of big game killed by hunters. For two consecutive years we quantified the level lead exposure in individuals of a sentinel scavenger species, the common raven (Corvus corax), captured during the moose (Alces alces) hunting season in eastern Quebec, Canada. The source of the lead contamination was also determined using stable isotope analyses. Finally, we identified the different scavenger species that could potentially be exposed to lead by installing automatic cameras targeting moose gut piles. Blood lead concentration in ravens increased over time, indicating lead accumulation over the moose-hunting season. Using a contamination threshold of 100 µg.L−1, more than 50% of individuals were lead-contaminated during the moose hunting period. Lead concentration was twice as high in one year compared to the other, matching the number of rifle-shot moose in the area. Non-contaminated birds exhibited no ammunition isotope signatures. The isotope signature of the lead detected in contaminated ravens tended towards the signature from lead ammunition. We also found that black bears (Ursus americanus), golden eagles and bald eagles (Aquila chrysaetos and Haliaeetus leucocephalus, two species of conservation concern) scavenged heavily on moose viscera left by hunters. Our unequivocal results agree with other studies and further motivate the use of non-toxic ammunition for big game hunting. PMID:25389754

Childhood lead poisoning from the smelter in Torreon, Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soto-Jimenez, Martin F., E-mail: martin@ola.icmyl.unam.mx; Flegal, Arthur R.

2011-05-15

Lead concentrations and isotopic compositions in blood samples of 34 children (ages 2-17 years) living within a 113 km{sup 2} area of a silver-zinc-lead smelter plant in Torreon, Mexico were compared to those of associated environmental samples (soil, aerosols, and outdoor and indoor dust) to identify the principal source(s) of environmental and human lead contamination in the area. Lead concentrations of soil and outdoor dust ranged 130-12,050 and 150-14,365 {mu}g g{sup -1}, respectively. Concentrations were greatest near the smelter, with the highest levels corresponding with the prevailing wind direction, and orders of magnitude above background concentrations of 7.3-33.3 {mu}g g{supmore » -1}. Atmospheric lead depositions in the city varied between 130 and 1350 {mu}g m{sup -2} d{sup -1}, again with highest rates <1 km from the smelter. Blood lead (PbB) concentrations (11.0{+-}5.3 {mu}g dl{sup -1}) levels in the children ranged 5.0-25.8 {mu}g dl{sup -1}, which is 3-14 times higher than the current average (1.9 {mu}g dl{sup -1}) of children (ages 1-5 years) in the US. Lead isotopic ratios ({sup 206}Pb/{sup 207}Pb, {sup 208}Pb/{sup 207}Pb) of the urban dust and soil (1.200{+-}0.009, 2.467{+-}0.003), aerosols (1.200{+-}0.002, 2.466{+-}0.002), and PbB (1.199{+-}0.001, 2.468{+-}0.002) were indistinguishable from each other, as well as those of the lead ores processed at the smelter (1.199{+-}0.007, 2.473{+-}0.007). Consequently, an elevated PbB concentrations of the children in Torreon, as well as in their environment, are still dominated by industrial emissions from the smelter located within the city, in spite of new controls on atmospheric releases from the facility. - Highlights: {yields} Pb contents in environmental samples evidenced chronic Pb pollution in Torreon. {yields} Pb stable isotopes evidenced contemporary emissions from the Ag-Cod-Pb-Zn smelter. {yields} Pb urban dust and soil account for most of the childhood lead poisoning in Torreon

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

NASA Astrophysics Data System (ADS)

von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

2014-01-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

Stable Isotope Identification of Nitrogen Sources for United ...

EPA Pesticide Factsheets

We used natural abundance stable isotope data to evaluate nitrogen sources to U.S. west coast estuaries. We collected δ15N of macroalgae data and supplemented this with available data from the literature for estuaries from Mexico to Alaska. Stable isotope ratios of green macroalgae were compared to δ15N of dissolved inorganic nitrogen of oceanic and watershed end members. There was a latitudinal gradient in δ15N of macroalgae with southern estuaries being 7 per mil heavier than northern estuaries. Gradients in isotope data were compared to nitrogen sources estimated by the USGS using the SPARROW model. In California estuaries, the elevation of isotope data appeared to be related to anthropogenic nitrogen sources. In Oregon systems, the nitrogen levels of streams flowing into the estuaries are related to forest cover, rather than to developed land classes. In addition, the δ15N of macroalgae suggested that the ocean and nitrogen-fixing trees in the watersheds were the dominant nitrogen sources. There was also a strong gradient in δ15N of macroalgae with heavier sites located near the estuary mouth. In some Oregon estuaries, there was an elevation an elevation of δ15N above marine end members in the vicinity of wastewater treatment facility discharge locations, suggesting isotopes may be useful for distinguishing inputs along an estuarine gradient. Nutrients are the leading cause of water quality impairments in the United States, and as a result too

Graphic and algebraic solutions of the discordant lead-uranium age problem

USGS Publications Warehouse

Stieff, L.R.; Stern, T.W.

1961-01-01

Uranium-bearing minerals that give lead-uranium and lead-lead ages that are essentially in agreement, i.e. concordant, generally are considered to have had a relatively simple geologic history and to have been unaltered since their deposition. The concordant ages obtained on such materials are, therefore, assumed to approach closely the actual age of the minerals. Many uranium-bearing samples, particularly uranium ores, give the following discordant age sequences; Pb206 U238 < Pb207 U235 ??? Pb207 Pb206 or, less frequently, Pb207 Pb206 ??? Pb207 U235 < Pb206 U238. These discordant age sequences have been attributed most often to uncertainties in the common lead correction, selective loss of radio-active daughter products, loss or gain of lead or uranium, or contamination by an older generation of radiogenic lead. The evaluation of discordant lead isotope age data may be separated into two operations. The first operation, with which this paper is concerned, is mechanical in nature and involves the calculation of the different possible concordant ages corresponding to the various processes assumed to have produced the discordant ages. The second operation is more difficult to define and requires, in part, some personal judgement. It includes a synthesis of the possible concordant age solutions with other independent geologic and isotopic evidence. The concordant age ultimately chosen as most acceptable should be consistent not only with the known events in the geologic history of the area, the age relations of the enclosing rocks, and the mineralogic and paragenetic evidence, but also with other independent age measurements and the isotopic data obtained on the lead in related or associated non-radioactive minerals. The calculation of the possible concordant ages from discordant age data has been greatly simplified by Wetherill's graphical method of plotting the mole ratios of radiogenic Pb206 U238 ( N206 N238) vs. radiogenic Pb207 U235 ( N207 N235) after correcting

Getting the Lead Out of Bermuda; The Legacy of a Forty Year Record in the North Atlantic Using a Transient Experiment in the Atmosphere and Water

NASA Astrophysics Data System (ADS)

Church, T. M.; Alleman, L. Y.; Veron, A. J. J.; Boyle, E. A.; Zurbrick, C.; Patterson, C. C.; Flegal, A. R., Jr.

2015-12-01

Some forty years ago, Schaule and Patterson established the first accurate profile of lead in waters off Bermuda. In evidence was a massive environmental insult from lead emissions being carried seaward by the atmosphere over the Sargasso Sea. Further documentation was possible using contiguous time series in the atmosphere on Bermuda, surface sea water nearby and recorded in local corals. Lead had then an overwhelming source from the combustion of gasoline, primarily in the USA and secondarily in Europe. These were carried to Bermuda on seasonally alternating temperate and trade winds from the west and east, respectively. The anthropogenic sources were well distinguished based on the unique radiogenic nature of stable lead isotopes in the gasoline being used by these countries. Subsequently, decreasing use in the west (USA) followed by that in the east (Europe) was isotopically evident. As such, the two signatures were subjected to transient mixing in the atmosphere and subsequently with depth in ocean. A transient experiment uses data during 1996-1998, a period of transition in leaded gasoline use in the USA and Europe. Here are complimentary records of lead concentration and stable isotopes in atmospheric deposition and surface waters. The results allow an isotopic mass balance, indicating much of the lead in Bermuda surface water at that time may not have been deposited locally. As such, it may be presumed to reflect easterly advection of some lead at the surface under limited scavenging via the prevailing subtropical gyre circulation. These annual circulation periods are consistent with both physical data and another lead isotopic mass balance in the east. Going forward, Bermuda time series of trace elements and isotopes such as lead could continue to record climatological (e.g. NAO) transients in atmospheric scavenging, potential impact on surface ecosystems, and changes in mixing into deeper waters of the Sargasso Sea and points further afield.

ISOTOPE CONVERSION DEVICE

DOEpatents

Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

1957-12-01

This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

Illuminating hydrological processes at the soil-vegetation-atmosphere interface with water stable isotopes

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Leistert, Hannes; Gimbel, Katharina; Weiler, Markus

2016-09-01

Water stable isotopes (18O and 2H) are widely used as ideal tracers to track water through the soil and to separate evaporation from transpiration. Due to the technical developments in the last two decades, soil water stable isotope data have become easier to collect. Thus, the application of isotope methods in soils is growing rapidly. Studies that make use of soil water stable isotopes often have a multidisciplinary character since an interplay of processes that take place in the vadose zone has to be considered. In this review, we provide an overview of the hydrological processes that alter the soil water stable isotopic composition and present studies utilizing pore water stable isotopes. The processes that are discussed include the water input as precipitation or throughfall, the output as evaporation, transpiration, or recharge, and specific flow and transport processes. Based on the review and supported by additional data and modeling results, we pose a different view on the recently proposed two water world hypothesis. As an alternative to two distinct pools of soil water, where one pool is enriched in heavy isotopes and used by the vegetation and the other pool does not undergo isotopic fractionation and becomes recharge, the water gets successively mixed with newly introduced rainwater during the percolation process. This way, water initially isotopically enriched in the topsoil loses the fractionation signal with increasing infiltration depth, leading to unfractionated isotopic signals in the groundwater.

Stable carbon and nitrogen isotope enrichment in primate tissues

PubMed Central

Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

2010-01-01

Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

Isotope scattering and phonon thermal conductivity in light atom compounds: LiH and LiF

DOE PAGES

Lindsay, Lucas R.

2016-11-08

Engineered isotope variation is a pathway toward modulating lattice thermal conductivity (κ) of a material through changes in phonon-isotope scattering. The effects of isotope variation on intrinsic thermal resistance is little explored, as varying isotopes have relatively small differences in mass and thus do not affect bulk phonon dispersions. However, for light elements isotope mass variation can be relatively large (e.g., hydrogen and deuterium). Using a first principles Peierls-Boltzmann transport equation approach the effects of isotope variance on lattice thermal transport in ultra-low-mass compound materials LiH and LiF are characterized. The isotope mass variance modifies the intrinsic thermal resistance viamore » modulation of acoustic and optic phonon frequencies, while phonon-isotope scattering from mass disorder plays only a minor role. This leads to some unusual cases where values of isotopically pure systems ( 6LiH, 7Li 2H and 6LiF) are lower than the values from their counterparts with naturally occurring isotopes and phonon-isotope scattering. However, these differences are relatively small. The effects of temperature-driven lattice expansion on phonon dispersions and calculated κ are also discussed. This work provides insight into lattice thermal conductivity modulation with mass variation and the interplay of intrinsic phonon-phonon and phonon-isotope scattering in interesting light atom systems.« less

A METHOD TO IMPROVE DOSE ASSESSMENT BY RECONSTRUCTION OF THE COMPLETE ISOTOPES INVENTORY.

PubMed

Bonin, Alice; Tsilanizara, Aimé

2017-06-01

Radiation shielding assessments may underestimate the expected dose if some isotopes at trace level are not considered in the isotopes inventory of the shielded radioactive materials. Indeed, information about traces is not often available. Nevertheless, the activation of some minor isotopic traces may significantly contribute to the dose build-up. This paper presents a new method (Isotopes Inventory Reconstruction-IIR) estimating the concentration of the minor isotopes in the irradiated material at the beginning of the cooling period. The method requires the solution of the inverse problem describing the irradiated material's decay. In a mixture of an irradiated uranium-plutonium oxide shielded by a set-up made of stainless-steel, porous polyethylene plaster and lead methyl methacrylate, the comparison between different methods proves that the IIR-method allows better assessment of the dose than other approximate methods. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

The isotopic record of atmospheric lead fall-out on an Icelandic salt marsh since AD 50.

PubMed

Marshall, William A; Clough, Robert; Gehrels, W Roland

2009-04-01

We report a record of atmospheric Pb deposition at a coastal site in western Iceland that spans the last two millennia. The elemental concentrations of Pb, Al, Li and Ti are determined using ICP-MS from a sediment monolith collected from a salt marsh. Multicollector (MC) ICP-MS analysis is used to obtain isotopic ratios of stable Pb. The Pb/Ti and Pb/Li ratios are used to separate natural Pb background concentrations from Pb derived from remote anthropogenic sources. The pollution record in western Iceland is subdued in comparison with Pb records from the European mainland, but the isotopic character, profile and timing of Pb deposition show good agreement with the atmospheric Pb fall-out reported from sites in Scandinavia and northwestern Europe. At the bottom of the sequence we isolate a low-level (0.1-0.4 mg kg(-1)) Pb enrichment signal dated to AD 50-150. The isotopic signature and timing of this signal suggest Roman metal working industries as the source. In the subsequent millennium there was no significant or very low (i.e. elemental concentrations<0.01 mg kg(-1)) anthropogenic Pb deposition at the site up to, and including, the early Medieval period. Above a pumice layer, dated to AD 1226-1227, a small increase in Pb deposition is found. This trend is maintained until a more substantive and progressive increase is signalled during the late 1700s and early 1800s. This is followed by a substantial enrichment signal in the sediments (>3.0 mg kg(-1)) that is interpreted as derived from industrial coal burning and metal working during the 19th and 20th centuries in northern Europe. During the late 20th century, significant fall-out from European fuel additives reached Iceland.

Electron linac for medical isotope production with improved energy efficiency and isotope recovery

DOEpatents

Noonan, John; Walters, Dean; Virgo, Matt; Lewellen, John

2015-09-08

A method and isotope linac system are provided for producing radio-isotopes and for recovering isotopes. The isotope linac is an energy recovery linac (ERL) with an electron beam being transmitted through an isotope-producing target. The electron beam energy is recollected and re-injected into an accelerating structure. The ERL provides improved efficiency with reduced power requirements and provides improved thermal management of an isotope target and an electron-to-x-ray converter.

Association of gold with uraninite and pyrobitumen in the metavolcanic rock hosted hydrothermal Au-U mineralisation at Rompas, Peräpohja Schist Belt, northern Finland

NASA Astrophysics Data System (ADS)

Molnár, Ferenc; Oduro, Harry; Cook, Nick D. J.; Pohjolainen, Esa; Takács, Ágnes; O'Brien, Hugh; Pakkanen, Lassi; Johanson, Bo; Wirth, Richard

2016-06-01

-ordered graphite in calcsilicate veins. Mean random reflectance data for pyrobitumen indicate 270-340 °C maximum temperature of thermal maturation—this temperature range is also considered as the temperature of gold deposition. Results of multiple sulphur isotope analyses of organic material-, pyrite- and acid-volatile-bound sulphur show distinct ranges of δ34S values for SORG and SCRS in uraninite-pyrobitumen (from -6.99 to -3.55‰ and from -10.02 to -4.41‰, respectively) and uraninite-pyrobitumen-native gold mineral associations (from +1.36 to +6.87‰ and from +0.42 to +9.7‰, respectively). Δ33S data indicate local occurrence of nonmass-dependent sulphur isotope fractionation owing to interaction of fluids with organic material. Concentration of lead in uraninite is depleted along the gold mineral filled fractures whereas the uranogenic lead isotope contents of galena, altaite and hunchuite deposited in the same fractures are extremely high, suggesting that the dominant source of lead for the crystallisation of these minerals was the radiogenic lead content of uraninite. Taking into account this source of radiogenic lead, the calculated Pb-Pb model ages for the lead minerals are between 1.75 and 1.70 Ga. Sulphur and tellurium removal from the fluid by reaction with radiogenic lead released by uraninite appears to be an important mechanism in the strongly localised deposition of gold minerals. Scavenging of sulphur by pyrobitumen nodules from gold transporting fluids was an additional process triggering precipitation of gold. Carbon particles and organic functional groups in pyrobitumen probably acted as nucleation and adsorption centres for gold minerals.

APPARATUS AND TECHNIC FOR THE ADMINISTRATION OF INTRACAVITARY RADIOACTIVE ISOTOPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michaud, N.J.; Liegner, L.M.

1961-08-01

The method of administration of radioactive isotopes in the treatment of pleural effusions and ascites associated with cancer will vary according to the therapeutic technic. A procedure with a suitable apparatus that utilizes an economical and sterile disposable package is described. The radioactive isotope, whether colloidal chromic phosphate (P/sup 32/) or colloidal gold (Au/sup 198/), can be obtained in th e exact amount prescribed. The entire apparatus is assembled within a few minutes under sterile conditions. Before the hypodermic needles are inserted into the radioactive isotope vial, the air is removed from the tubing by the flow of saline inmore » each segment. Each section is then clamped. The shielded radioactive isotope is then placed on a table or stand and the rubber seal of the vial is swabbed with alcohol or iodine. The inflow needle is inserted just through the rubber stopper and the outflow needle is inserted to the bottom of the vial. This procedure is carried out without removing the vial from the lead container. (auth)« less

Calcium and Titanium Isotope Fractionation in CAIS: Tracers of Condensation and Inheritance in the Early Solar Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Simon, J. I.; Jordan, M. K.; Tappa, M. J.; Kohl, I. E.; Young, E. D.

2016-01-01

The chemical and isotopic compositions of calcium-aluminum-rich inclusions (CAIs) can be used to understand the conditions present in the protoplantary disk where they formed. The isotopic compositions of these early-formed nebular materials are largely controlled by chemical volatility. The isotopic effects of evaporation/sublimation, which are well explained by both theory and experimental work, lead to enrichments of the heavy isotopes that are often exhibited by the moderately refractory elements Mg and Si. Less well understood are the isotopic effects of condensation, which limits our ability to determine whether a CAI is a primary condensate and/or retains any evidence of its primordial formation history.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

Vertical distribution of hydraulic characteristics and water quality in three boreholes in the Galena-Platteville Aquifer at the Parson's Casket Hardware Superfund site, Belvidere, Illinois, 1990

USGS Publications Warehouse

Mills, P.C.

1993-01-01

The U.S. Geological Survey investigated contaminant migration in the Galena-Platteville aquifer at the Parson's Casket Hardware site in Belvidere, Ill. This report presents the results of the first phase of the investigation, from August through December 1990. A packer assembly was used to isolate various depth intervals in three 150-foot-deep boreholes in the dolomite aquifer. Aquifer-test data include vertical distributions of vertical hydraulic gradient, horizontal hydraulic conductivity (K), and response of water levels in observation wells to borehole pumping. Water-quality data include vertical distributions of field-measured properties and laboratory determinations of concentrations of volatile organic compounds (VOC's). vertical hydraulic gradients in the aquifer were downward. The downward gradients ranged from less than 0.01 to 0.37 foot/foot. The largest gradient was associated with an elevated-K interval at 115 to 125 feet below land surface. The hydraulic characteristics of strata within the aquifer seem to be generally consistent across the site. The strata can be subdivided into five hydraulic units with the following approximate depth ranges-and K's : (1) a 1- to 5-foot-thick weathered surface at about 35 feet below land surface, 1-200 ft/d (feet per day); (2) 35-80 feet, 0.05-0.5 ft/d; (3) 80-115 feet, 0.5 ft/d; (4) 115-125 feet, 0.5-10 ft/d; and (5) 125-150 feet, 0.5 ft/d. Water-level drawdowns were detected in one shallow bedrock observation well during pumping of some of the packed intervals in a nearby borehole, indicating that the degree of vertical connection between some intervals in the aquifer may be greater than that between others. During development pumping of one borehole, drawdowns were detected in a nearby well screened in the lower part of the overlying glacial-drift deposits, indicating hydraulic connection between the glacial drift aquifer and the bedrock aquifer. VOC's were detected throughout the upper half (about 150 feet ) of

Lead isotope ratios in six lake sediment cores from Japan Archipelago: Historical record of trans-boundary pollution sources.

PubMed

Hosono, Takahiro; Alvarez, Kelly; Kuwae, Michinobu

2016-07-15

Sediment cores from six lakes situated from north to south on the Japanese Archipelago were collected during 2009-2010 to investigate the hypothesis that deposition of lead (Pb) was coming from East Asia (including China, South Korea and eastern part of Russia). Accumulation rates and ages of the lake sediment were estimated by the (210)Pb constant rate of supply model and (137)Cs inputs to reconstruct the historical trends of Pb accumulation. Cores from four lakes located in the north and central Japan, showed clear evidence of Pb pollution with a change in the (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios in the recent sediment as compared to the deeper sediment. Among the six studied lakes, significant inputs of anthropogenic lead emissions were observed at Lake Mikazuki (north Hokkaido in north Japan), Lake Chokai (north of Honshu), and Lake Mikuriga (central part of Honshu). Pb isotopic comparison of collected core sediment and previously reported data for wet precipitation and aerosols from different Asian regions indicate that, before 1900, Pb accumulated in these three lakes was not affected by trans-boundary sources. Lake Mikazuki started to receive Pb emissions from Russia in early 1900s, and during the last two decades, this lake has been affected by trans-boundary Pb pollution from northern China. Lake Chokai has received Pb pollutant from northern China since early 1900s until 2009, whereas for the Lake Mikuriga the major Pb contaminant was transported from southern China during the past 100years. The results of our study demonstrate that Japan Archipelago has received trans-boundary Pb emissions from different parts of East Asian region depending on location, and the major source region has changed historically. Copyright © 2016 Elsevier B.V. All rights reserved.

Are leaf physiological traits related to leaf water isotopic enrichment in restinga woody species?

PubMed

Rosado, Bruno H P; De Mattos, Eduardo A; Sternberg, Leonel Da S L

2013-09-01

During plant-transpiration, water molecules having the lighter stable isotopes of oxygen and hydrogen evaporate and diffuse at a faster rate through the stomata than molecules having the heavier isotopes, which cause isotopic enrichment of leaf water. Although previous models have assumed that leaf water is well-mixed and isotopically uniform, non-uniform stomatal closure, promoting different enrichments between cells, and different pools of water within leaves, due to morpho-physiological traits, might lead to inaccuracies in isotopic models predicting leaf water enrichment. We evaluate the role of leaf morpho-physiological traits on leaf water isotopic enrichment in woody species occurring in a coastal vegetation of Brazil known as restinga. Hydrogen and oxygen stable isotope values of soil, plant stem and leaf water and leaf traits were measured in six species from restinga vegetation during a drought and a wet period. Leaf water isotopic enrichment relative to stem water was more homogeneous among species during the drought in contrast to the wet period suggesting convergent responses to deal to temporal heterogeneity in water availability. Average leaf water isotopic enrichment relative to stem water during the drought period was highly correlated with relative apoplastic water content. We discuss this observation in the context of current models of leaf water isotopic enrichment as a function of the Péclet effect. We suggest that future studies should include relative apoplastic water content in isotopic models.

1. Historic American Buildings Survey Joseph Hill, Photographer October 1936 ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. Historic American Buildings Survey Joseph Hill, Photographer October 1936 #12 EARLY RED BRICK HOUSE, Elk and Prospect Sts., Galena, Illinois - Galena Doorways, Red Brick House, Elk & Prospect Streets, Galena, Jo Daviess County, IL

The geology, mineralogy and paragenesis of the Castrovirreyna lead-zinc-silver deposits, Peru

USGS Publications Warehouse

Lewis, Richard Wheatley

1964-01-01

The Castrovirreyna mining district lies in the Andean Cordillera of South Central Peru, and has been worked sporadically since its discovery in 1591. Supergene silver ores were first mined. Currently the district produces about 20,000 tons of lead-zinc ore and 5000 tons of silver ore annually. The district is underlain by Tertiary andesitic rocks interbedded with basalts and intruded by small bodies of quartz latite porphyry. The terrane reflects recent glaciation and is largely covered by glacial debris. The ore deposits are steeply dipping veins that strike N. 60? E. to S. 50? E., and average 60 centimeters wide and 300 meters long. The principal veins are grouped around three centers, lying 5 kilometers apart along a line striking N. 55? E. They are, from east to west: San Genaro, Caudalosa, and La Virreyna. A less important set of veins, similarly aligned, lies 2 kilometers to the north. Most of the veins were worked to depths of about 30 meters, the limit of supergene enrichment; but in the larger veins hypogene ores have been worked to depths of over 150 meters. Galena, sphalerite, chalcopyrite, and tetrahedrite are common to all veins, but are most abundant in the westernmost veins at La Virreyna. In the center of the district, around Caudalosa, land sulfantimonides are the commonest ore minerals, and at the eastern end, around San Genaro and Astohuaraca, silver sulfosalts predominate. Supergene enrichment of silver is found at shallow depths in all deposits. Silver at San Genaro, however, was concentrated towards the surface by migration along hypogene physico-chemical gradients in time and space, as vein material was reworked by mineralizing fluids. The pattern of wallrock alteration throughout the district grades from silicification and scricitization adjacent to the veins, through argillization and propylitization, to widespread chloritization farther away. Mineralization can be divided into three stages: 1) Preparatory stage, characterized by

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Observation of the isotope effect in sub-kelvin reactions

NASA Astrophysics Data System (ADS)

Lavert-Ofir, Etay; Shagam, Yuval; Henson, Alon B.; Gersten, Sasha; Kłos, Jacek; Żuchowski, Piotr S.; Narevicius, Julia; Narevicius, Edvardas

2014-04-01

Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.

Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

NASA Astrophysics Data System (ADS)

Hogberg, K.; Stachel, T.; Stern, R. A.

2016-11-01

stages of influx, availability of the mantle-type fluid at the site of diamond growth became limited, leading to Rayleigh fractionation. These fractionation trends are clearly depicted by δ15N-[N] but are not detected when examining co-variation diagrams involving δ13C. Also on the level of individual diamonds, large (≥ 5‰) variations in δ15N are associated with δ13C values that typically are constant within analytical uncertainty. The much smaller isotope fractionation factor for carbon (considering carbonate- or methane-rich fluids as possible carbon sources) compared to nitrogen leads to an approximately one order of magnitude lower sensitivity of δ13C values to Rayleigh fractionation processes (i.e. during fractionation, a 1‰ change in δ13C is associated with a 10‰ change in δ15N). As a consequence, even minor heterogeneity in the primary isotopic composition of diamond forming carbon (e.g., due to addition of minor subducted carbon) will completely blur any possible co-variations with δ15N or [N]. We suggest this strong difference in isotope effects for C and N to be the likely cause of observations of an apparently decoupled behaviour of carbon and nitrogen isotopes in diamond.

Isotope separation by photochromatography

DOEpatents

Suslick, Kenneth S.

1977-01-01

An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

Stable isotopes in mid-ocean ridge hydrothermal systems: Interactions between fluids, minerals, and organisms

USGS Publications Warehouse

Shanks, Wayne C.; Böhlke, John Karl; Seal, Robert R.; Humphries, S.D.; Zierenberg, Robert A.; Mullineaux, Lauren S.; Thomson, Richard E.

1995-01-01

Studies of abundance variations of light stable isotopes in nature have had a tremendous impact on all aspects of geochemistry since the development, in 1947, of a gas source isotope ratio mass spectrometer capable of measuring small variations in stable isotope ratios (Nice, 1947]. Stable isotope geochemistry is now a mature field, as witnessed by the proliferation of commercially available mass spectrometers installed at virtually every major academic, government, and private-sector research geochemistry laboratory. A recent search of a literature database revealed over 3,000 articles that utilized stable isotope geochemistry over the last 20 years. Nonetheless, many exciting new technical developments are leading to exciting new discoveries and applications. In particular, micro-analytical techniques involving new generations of laser- and ion-microprobes are revolutionizing the types of analyses that can be done on spot sizes as small as a few tens of micrometers [Shanks and Criss, 1989]. New generations of conventional gas source and thermal ionization mass spectrometers, with high levels of automation and increased sensitivity and precision, are allowing analyses of large numbers of samples, like those needed for stable isotope stratigraphy in marine sediments, and are enabling the development and application of new isotopic systems.

Stable isotopes in mid-ocean ridge hydrothermal systems: Interactions between fluids, minerals, and organisms

NASA Astrophysics Data System (ADS)

Shanks, W. C., III; Böhlke, J. K.; Seal, R. R., II

Studies of abundance variations of light stable isotopes in nature have had a tremendous impact on all aspects of geochemistry since the development, in 1947, of a gas source isotope ratio mass spectrometer capable of measuring small variations in stable isotope ratios [Nier, 1947] Stable isotope geochemistry is now a mature field, as witnessed by the proliferation of commercially available mass spectrometers installed at virtually every major academic, government, and private-sector research geochemistry laboratory. A recent search of a literature database revealed over 3,000 articles that utilized stable isotope geochemistry over the last 20 years. Nonetheless, many exciting new technical developments are leading to exciting new discoveries and applications. In particular, micro analytical techniques involving new generations of laser- and ion-microprobes are revolutionizing the types of analyses that can be done on spot sizes as small as a few tens of micrometers [Shanks and Criss, 1989]. New generations of conventional gas source and thermal ionization mass spectrometers, with high levels of automation and increased sensitivity and precision, are allowing analyses of large numbers of samples, like those needed for stable isotope stratigraphy in marine sediments, and are enabling the development and application of new isotopic systems.

Historical perspective on lead biokinetic models.

PubMed Central

Rabinowitz, M

1998-01-01

A historical review of the development of biokinetic model of lead is presented. Biokinetics is interpreted narrowly to mean only physiologic processes happening within the body. Proceeding chronologically, for each epoch, the measurements of lead in the body are presented along with mathematical models in an attempt to trace the convergence of observations from two disparate fields--occupational medicine and radiologic health--into some unified models. Kehoe's early balance studies and the use of radioactive lead tracers are presented. The 1960s saw the joint application of radioactive lead techniques and simple compartmental kinetic models used to establish the exchange rates and residence times of lead in body pools. The applications of stable isotopes to questions of the magnitudes of respired and ingested inputs required the development of a simple three-pool model. During the 1980s more elaborate models were developed. One of their key goals was the establishment of the dose-response relationship between exposure to lead and biologic precursors of adverse health effects. PMID:9860905

Fractionation of lithium isotopes in magmatic systems as a natural consequence of cooling

NASA Astrophysics Data System (ADS)

Gallagher, Kerry; Elliott, Tim

2009-02-01

High-temperature, diffusive fractionation has been invoked to account for striking Li isotopic variability recently observed within individual phenocrysts and xenolith minerals. It has been argued that chemical potential gradients required to drive such diffusion arise from changes in Li partitioning between coexisting phases during cooling. If so, Li isotopic zoning should be a common occurrence but the role of temperature-dependent partition coefficients in generating Li isotopic variability remains to be tested in a quantitative manner. Here we consider a basic scenario of a phenocryst in a cooling lava, using simple parameterisations of the temperature dependence of Li partitioning and diffusivity in clinopyroxene. Our model initially produces an asymmetric isotope profile across the crystal with a δ7Li minimum that remains close to the edge of a crystal. Such a distinctive shape mimics Li isotopic profiles documented in some olivine and clinopyroxene phenocrysts, which have isotopically normal cores but anomalously light rims. The temperature dependence of both the diffusivity and the partition coefficient of Li are key factors in generating this form of diffusion profile. Continued diffusion leads to an inversion in the sense of isotopic change between core and rim and results in the whole phenocryst attaining markedly light isotopic values. Our calculations show that significant Li isotopic zoning can occur as a natural consequence of cooling magmatic systems. Crystals that have experienced more complex thermal histories (e.g. re-entrained cumulates versus true phenocrysts) will therefore exhibit contrasting isotopic profiles and, as such, these data may be useful for tracing sub-volcanic processes.